Curved photosensitive glass, preparation method therefor and use thereof

Abstract

Embodiments of the present application provide a curved photosensitive glass, a preparation method therefor, and a use thereof. By means of causing the curved photosensitive glass to satisfy a specific composition, particularly by controlling the contents of CeO2, Sb2O3 and Ag2O within specific ranges, an exposed region of the curved photosensitive glass has good shielding performance and exhibits a uniform black color after hot bending treatment; in addition, an unexposed region thereof has good light transmittance. The glass can meet requirements in fields such as mobile phone cover plates and smart watches.

Description

Curved photosensitive glass and preparation method and use thereof

[0001] Cross-reference to Related Applications

[0002] The present application claims priority to the Chinese patent application No. 202411042026.2, filed on July 31, 2024, entitled "Curved photosensitive glass and preparation method and use thereof", the entire content of which is incorporated herein by reference. TECHNICAL FIELD

[0003] The present application relates to the technical field of glass, in particular to a curved photosensitive glass and a preparation method and use thereof. BACKGROUND

[0004] After the photosensitive glass is subjected to ultraviolet exposure and heat treatment, an opaque area that blocks light can be formed in the exposed area. The light transmittance of the area is low, and the area has the performance of blocking light compared to the glass part that is not exposed. Therefore, the photosensitive glass can be applied to the field of mobile phone cover plate, smart watch back cover, etc., to avoid signal crosstalk between different wavelengths of test light. However, the current curved photosensitive glass, especially after heat bending treatment, still has the problem of insufficient shielding performance for visible light and near-infrared light in the exposed area. Therefore, the application of the curved photosensitive glass in the field of mobile phone cover plate, smart watch, etc. cannot fully meet the requirements.

[0005] SUMMARY

[0006] The purpose of the present application is to provide a curved photosensitive glass with an exposed area having good shielding performance, which can meet the requirements of the field of mobile phone cover plate, smart watch, etc.

[0007] To achieve the above purpose, the present application provides the following technical solutions:

[0008] In a first aspect, a curved photosensitive glass is provided, which includes an exposed area and a non-exposed area. The curved photosensitive glass contains the following components in terms of mass percentage of oxides: SiO2: 65.00% to 75.00%, Al2O3: 5.00% to 10.00%, Li2O: 7.00% to 15.00%, Na2O: 1.00% to 4.00%, K2O: 1.00% to 4.00%, ZrO2: 5.00% to 8.00%, Ag2O: 0.15% to 0.80%, CeO2: 0.05% to 0.15%, and Sb2O3: 0.1% to 0.50%.

[0009] Optionally, the curved photosensitive glass contains the following components in terms of mass percentage of oxides:

[0010] SiO2 is 66.00% to 74.60%, preferably, SiO2 is 66.50% to 74.00%; and / or,

[0011] Al2O3 is 5.10% to 9.70%, preferably, Al2O3 is 5.20% to 9.40%; and / or,

[0012] Li2O is 7.10% to 14.50%, preferably, Li2O is 8.00% to 14.50%; and / or,

[0013] Na2O is 1.00% to 3.80%, preferably, Na2O is 1.00% to 3.75%; and / or,

[0014] K2O is 1.40% to 3.90%, preferably, K2O is 1.40% to 3.85%; and / or,

[0015] ZrO2 is 5.00% to 7.50%, preferably, ZrO2 is 5.10% to 7.50%; and / or,

[0016] Ag2O is 0.15% to 0.60%, preferably, Ag2O is 0.15% to 0.50%; and / or,

[0017] CeO2 is 0.05% to 0.14%, preferably, CeO2 is 0.07% to 0.14%; and / or,

[0018] Sb2O3 is 0.20% to 0.50%, preferably, Sb2O3 is 0.20% to 0.48%.

[0019] Optionally, the curved photosensitive glass comprises one or more of 3D photosensitive glass, 4D photosensitive glass, 5D photosensitive glass, special-shaped photosensitive glass, and four-curved photosensitive glass.

[0020] Optionally, the curved photosensitive glass is obtained by processing a base glass, wherein the processing comprises radiation treatment and subsequent heat treatment, and heat bending treatment.

[0021] Optionally, the base glass has the same or substantially the same composition as the curved photosensitive glass.

[0022] Optionally, the curved photosensitive glass has a thickness of 0.3 to 2.0 mm, preferably 0.3 to 1.0 mm.

[0023] Optionally, when the thickness of the curved photosensitive glass is 0.30-1.00 mm, the transmittance T1 of the exposed area of the curved photosensitive glass at a wavelength of 550 nm is 0.00%-5.00%, preferably the transmittance T1 is 0.00%-3%; and / or,

[0024] 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 90% or more; and / or,

[0025] When the thickness of the curved photosensitive glass is 0.30-1.00 mm, the transmittance T3 of the exposed area of the curved photosensitive glass at a wavelength of 850 nm is 0.00%-8.00%, preferably the transmittance T3 is 0.00%-5%; and / or,

[0026] 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 90% or more; and / or,

[0027] When the thickness of the curved photosensitive glass is 0.30-1.00 mm, the transmittance T5 of the exposed area of the curved photosensitive glass at a wavelength of 900 nm is 0.00%-10.00%, preferably the transmittance T5 is 0.00%-8%; and / or,

[0028] 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 90% or more.

[0029] Optionally, the crystal phase of the exposed area of the curved photosensitive glass comprises one or more of lithium metasilicate, lithium disilicate, petalite, quartz, spodumene, eucryptite, zinc oxide, Ag nanocrystal, Cu nanocrystal, Au nanocrystal, Bi nanocrystal.

[0030] Optionally, the non-exposed area of the curved photosensitive glass is substantially free of crystal phase or comprises one or more of lithium metasilicate, lithium disilicate, petalite, quartz, spodumene, eucryptite, zinc oxide, Ag nanocrystal, Cu nanocrystal, Au nanocrystal, Bi nanocrystal.

[0031] Optionally, the crystal phase of the exposed area and the non-exposed area of the curved photosensitive glass is the same.

[0032] In a second aspect, a preparation method of the curved photosensitive glass is provided, and the method comprises:

[0033] obtaining a substrate glass;

[0034] 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.

[0035] 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.

[0036] Optionally, the composition of the substrate glass is the same as or substantially the same as that of the curved photosensitive glass.

[0037] Optionally, the thickness of the substrate glass is 0.3 to 2.0 mm; preferably 0.3 to 1.0 mm.

[0038] Optionally, the radiation treatment method includes ultraviolet irradiation treatment.

[0039] Optionally, the wavelength of the ultraviolet irradiation treatment is 300nm-320nm, and the intensity of the ultraviolet irradiation treatment is 20mw / cm. 2 -360mw / cm 2 The ultraviolet irradiation treatment time is 5 min-60 min.

[0040] Optionally, the masking process includes masking using masking inks and / or photomasks.

[0041] Optionally, the heat treatment includes nucleation and crystallization.

[0042] Optionally, the heating rate of the nucleation treatment is 1℃ / min-10℃ / min; and / or,

[0043] The nucleation treatment temperature is 430℃-500℃; and / or,

[0044] The nucleation treatment time is 30 min-360 min; and / or,

[0045] The heating rate for crystallization treatment is 1℃ / min-10℃ / min; and / or,

[0046] The crystallization treatment temperature is higher than the nucleation treatment temperature, and the crystallization treatment temperature is 500℃-800℃; and / or,

[0047] The crystallization treatment time is 30 min to 480 min.

[0048] In a third aspect, a strengthened curved photosensitive glass having a thickness of t is provided, comprising a strengthened layer extending from a surface of the curved photosensitive glass body inwardly, the strengthened layer having a thickness of 0-0.22t, the strengthened layer comprising, in terms of mass percent of oxides: 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 being lower than the Li2O content at the center;

[0049] The strengthened curved photosensitive glass comprises, in terms of mass percent of oxides at the center: 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%;

[0050] The strengthened curved photosensitive glass comprises a non-exposed region and an exposed region.

[0051] Optionally, the chemical strengthening comprises single-step chemical strengthening or multi-step chemical strengthening.

[0052] Optionally, the single-step chemical strengthening employs a salt bath containing NaNO3; preferably, the content of NaNO3 is 30-100wt%; preferably, the single-step chemical strengthening employs a mixed salt bath containing NaNO3 and KNO3, preferably, the content of KNO3 in the mixed salt bath is 80-100wt%, and the content of NaNO3 is 0-20wt%.

[0053] Optionally, the temperature of the single-step chemical strengthening is 380-480℃, and preferably, the ion exchange time of the single-step chemical strengthening is 1-10h.

[0054] Optionally, the multi-step chemical strengthening comprises 2-step chemical strengthening, wherein the first-step chemical strengthening employs a salt bath containing NaNO3, preferably, the content of NaNO3 is 30-100wt%; the second-step chemical strengthening employs a salt bath containing KNO3, preferably, the content of KNO3 is 60-100wt%.

[0055] Optionally, the first step of chemical strengthening is at a temperature of 380-480°C, preferably the first step of chemical strengthening is for a time of 1-10h; preferably, the second step of chemical strengthening is at a temperature of 380-480°C, preferably the second step of chemical strengthening is for a time of 5-120min.

[0056] Optionally, the surface CS of the non-exposed area of the strengthened curved photosensitive glass is above 300MPa, preferably above 350MPa, further preferably 350MPa-600MPa.

[0057] Optionally, the single bar static pressure strength of the strengthened curved photosensitive glass is above 100N, preferably 100N-400N, more preferably 200N-400N.

[0058] In a fourth aspect, there is provided a cover glass, which is a curved photosensitive glass prepared according to the method of preparing a curved photosensitive glass of any of the embodiments of the second aspect or a strengthened curved photosensitive glass of any of the embodiments of the third aspect.

[0059] In a fifth aspect, there is provided an electronic device, which comprises a curved photosensitive glass according to any of the embodiments of the first aspect or a curved photosensitive glass prepared according to the method of preparing a curved photosensitive glass of any of the embodiments of the second aspect or a strengthened curved photosensitive glass of any of the embodiments of the third aspect.

[0060] Optionally, the electronic device comprises a smart wearable device worn on the body, which comprises a housing having a top portion and a bottom portion, the bottom portion is designed to contact the skin of the user when worn, the housing of the bottom portion comprises a curved photosensitive glass according to any of the embodiments of the first aspect or a curved photosensitive glass prepared according to the method of preparing a curved photosensitive glass of any of the embodiments of the second aspect or a strengthened curved photosensitive glass of any of the embodiments of the third aspect.

[0061] Optionally, the electronic device further comprises a camera assembly located inside the housing, the housing comprises a camera protective cover plate, the camera protective cover plate covers the camera assembly, the camera protective cover plate comprises a curved photosensitive glass according to any of the embodiments of the first aspect or a curved photosensitive glass prepared according to the method of preparing a curved photosensitive glass of any of the embodiments of the second aspect or a strengthened curved photosensitive glass of any of the embodiments of the third aspect.

[0062] In a sixth aspect, there is provided a use of the above-mentioned curved photosensitive glass or a curved photosensitive glass prepared according to the method of preparing a curved photosensitive glass or a strengthened photosensitive glass in a component of a mobile phone, a wearable device, a camera module or a vehicle.

[0063] Compared with the prior art, one or more of the above technical solutions provided in the present application have the following advantages:

[0064] The present application meets the requirements of the fields of mobile phone cover plates, smart watches, etc. by making the curved photosensitive glass meet specific compositions, particularly controlling the content of CeO2, Sb2O3 and Ag2O to meet specific ranges, so that the exposed area of the curved photosensitive glass has good shielding performance, and after heat bending treatment, it shows uniform black, and the non-exposed area has good light transmittance. BRIEF DESCRIPTION OF DRAWINGS

[0065] In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings needed in the embodiments will be briefly introduced below. It should be understood that the following drawings only show some embodiments of the present application, and therefore should not be regarded as a limitation on the scope. For those skilled in the art, other related drawings can also be obtained without creative labor on the basis of these drawings.

[0066] Fig. 1 is a structural schematic diagram of a substrate glass after masking using shielding ink according to an embodiment of the present application.

[0067] Fig. 2 is a structural schematic diagram of a photosensitive glass according to an embodiment of the present application.

[0068] Fig. 3 is a topographic photograph of a photosensitive glass according to an embodiment of the present application, wherein a is the topography of a first perspective, and b is the topography of a second perspective.

[0069] Fig. 4 is a schematic diagram of the rear side structure of an electronic device according to an embodiment of the present application.

[0070] Fig. 5 is a schematic diagram of the structure of a smart watch according to an embodiment of the present application.

[0071] Fig. 6 is a comparison diagram of the transmittance curves of substrate glasses in the range of 240 nm-360 nm according to Example 4 and Comparative Example 2 of the present application.

[0072] Reference signs: 11 - light transmittance area; 12 - light shielding area; 21 - exposed area; 22 - non-exposed area; 31 - camera protective cover plate; 32 - camera assembly; 33 - rear cover; 41 - rear cover of a smart watch. DETAILED DESCRIPTION

[0073] The embodiments of the present application will be described in detail below with examples, but those skilled in the art will understand that the following examples are configured only to illustrate the present application, and should not be considered as limiting the scope of the present application. The specific conditions are not specified in the examples, and the conventional conditions or the conditions recommended by the manufacturer are used. The reagents or instruments used are not specified by the manufacturer, and are conventional products that can be obtained by commercial purchase.

[0074] The endpoints of the ranges and any values disclosed herein are not limited to the precise values stated. The endpoints of the ranges and the values are approximate values which are understood to include values approximately and near the end points. For numeric ranges, the endpoints between the various ranges, the endpoints between the various ranges and the individual point values, and the individual point values can be combined with each other to form one or more new numeric ranges which should be considered as specifically disclosed herein. Among them, the terms "optional" and "optional" mean that it can be included or not included (or can be included or not included). The "and / or" referred to herein is inclusive, for example, "A and / or B" means only A, or only B, or both A and B.

[0075] Term explanation and test method:

[0076] In the present application, the main surface refers to the surface with the largest surface area, such as the upper surface or the lower surface of the photosensitive glass sheet placed horizontally.

[0077] In the present application, the infrared wavelength range refers to 750 nm to 1000 nm.

[0078] In the present application, the thickness of the glass is tested by a micrometer.

[0079] In the present application, the size of the glass sheet is tested by a two-dimensional measuring machine (instrument model Miyu MY-YXCL-4030).

[0080] The surface CS is tested by FSM-6000 of Japan Moritomo. Test conditions: light source wavelength is 596 nm, SOC = 28.6 (nm / cm) / MPa, refractive index = 1.52. In the present application, the surface compressive stress of the tested glass is the CS of the non-exposed area, and the exposed area cannot be tested because the light wave cannot penetrate the glass.

[0081] In the present application, the crystalline phase and the crystal content of the glass are confirmed by XRD test as follows:

[0082] (1) XRD test: The photosensitive glass of the present application was crushed and ground into a sample with a particle size of less than 75 μm, and the ground sample was tested by an X-ray diffractometer to obtain an XRD diffraction peak curve and XRD diffraction data. The X-ray diffractometer used in the present application was Shimadzu XRD-6100, the target material was copper, 2θ = 10°-50°, the scanning speed was 6° / min, the working voltage was 40 kV, and the working current was 30 mA.

[0083] (2) Determination of crystal phase: The XRD diffraction data were analyzed by Jade software (JADE Standard 8.6) to determine the crystal phase in the sample.

[0084] (3) Determination of crystal content (also referred to as crystallinity): The test results of XRD (RAW format) were imported into the X-ray diffraction data Rietveld refinement software Jade for fitting and calculation, so as to determine the crystallinity of the sample. Specifically, the ratio of the peak area of the fitted crystal phase to the total peak area of the fitting was recorded as the crystal content of the sample. The average crystal content was obtained by testing the crystal content of different positions of the same glass in the present application.

[0085] In the present application, the transmittance of the exposed region and the non-exposed region of the glass to be tested was tested by an ultraviolet-visible spectrophotometer. The ultraviolet-visible spectrophotometer used in the present application was Shimadzu UV-2000 ultraviolet-visible spectrophotometer.

[0086] Specifically, the method for testing the exposed region of the glass to be tested was as follows: first, a jig with the same shape and size as the glass to be tested was used, and the same region corresponding to the exposed region of the glass to be tested was a hollow region, and the region corresponding to the non-exposed region of the glass to be tested was an opaque region, and the linking position of the hollow region and the opaque region was opaque. The jig was tested as a blank sample for calibration, and then the exposed region of the glass to be tested was cut into a sample with the same shape as the hollow region of the jig and placed into the hollow region of the jig for testing to obtain the transmittance. The transmittance of the exposed region of 5 pieces of glass to be tested in the same batch to different wavelengths of light was tested by an ultraviolet-visible spectrophotometer, and then the average value was taken as the transmittance result of the exposed region of the glass to be tested under the wavelength of light.

[0087] In addition, the transmittance of the non-exposed region of 5 pieces of glass to be tested in the same batch to different wavelengths of light was tested by an ultraviolet-visible spectrophotometer. The average value of the transmittance of the non-exposed region of 5 pieces of glass to be tested under different wavelengths of light was taken as the transmittance result of the non-exposed region of the glass to be tested under the wavelength of light.

[0088] In the present application, the single rod static pressure strength test can be as follows: the glass sample to be tested is placed on the bottom ring of a tensile testing machine (LT-850A), the test software is started, the moving speed of the extrusion rod (rod diameter 8 mm, indenter arc radius 10 mm) is set to 50 mm / min, the start test is clicked, and the extrusion rod will apply force to the center of the glass sample to be tested at the set moving speed until the glass sample cracks and breaks. The test software will automatically read the force (N) when the glass sample breaks as the test result. Ten glass samples in the same state are tested, and the average value of the test results is taken as the single rod static pressure strength of the glass sample to be tested.

[0089] In some embodiments of the present application, a curved photosensitive glass is provided, which comprises an exposed region and a non-exposed region, and comprises the following components in terms of 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%.

[0090] In the present application, SiO2 is a glass former oxide, which forms an irregular continuous network with silicon-oxygen tetrahedral structural units, and is the skeleton of the glass. In some embodiments of the present application, the content of SiO2 in the curved photosensitive glass is 65.00%-75.00% in terms of mass percentage of oxides, preferably 66.00%-74.60%, and more preferably 66.50%-74.00%.

[0091] In some embodiments of the present application, the content of SiO2 in the curved photosensitive glass 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% in terms of mass percentage of oxides, or a value within a value range constituted by any two of the above specific numerical values as endpoints. It should be understood that in the embodiments, any of the above ranges can be combined with any other range.

[0092] In the present application, Al2O3 is a glass network intermediate, which enters the glass network structure in the form of [AlO4] tetrahedron. Increasing Al2O3 can increase the T gTemperature, thermal stability is enhanced, and is conducive to inhibit the glass heat treatment process of phase separation, but too much will make the melting temperature of the glass. In some embodiments of the present application, the content of Al2O3 in the curved photosensitive glass is 5.00% to 10.00%, preferably 5.10% to 9.70%, more preferably 5.20% to 9.40%, in terms of mass percent of oxides.

[0093] In some embodiments of the present application, the content of Al2O3 in the curved photosensitive glass 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 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.

[0094] In some embodiments of the present application, the content of Li2O in the curved photosensitive glass is 7.00% to 15.00%, preferably 7.10% to 14.50%, more preferably 8.00% to 14.50%, in terms of mass percent of oxides.

[0095] In some embodiments of the present application, the content of Li2O in the curved photosensitive glass 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 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.

[0096] In some embodiments of the application, the curved photosensitive glass has a content of Na20 in a range from 1.00% to 4.00%, preferably from 1.00% to 3.80%, more preferably from 1.00% to 3.75%, in terms of mass percent of oxides. In some embodiments of the application, the curved photosensitive glass has a content of Na20 that 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%, 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 a value within a range formed by any two of the above specific values as endpoints. It should be appreciated that in embodiments, any of the above ranges can be combined with any other range.

[0097] In some embodiments of the application, the curved photosensitive glass has a content of K20 in a range from 1.00% to 4.00%, preferably from 1.40% to 3.90%, more preferably from 1.40% to 3.85%, in terms of mass percent of oxides. In some embodiments of the application, the curved photosensitive glass has a content of K20 that 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%, 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 a value within a range formed by any two of the above specific values as endpoints. It should be appreciated that in embodiments, any of the above ranges can be combined with any other range.

[0098] In some embodiments of the present application, the content of Zr02in the curved photosensitive glass is 5.00% to 8.00% by mass percentage of oxide, preferably 5.00% to 7.50%, more preferably 5.10% to 7.50%. In some embodiments of the present application, the content of Zr02in the curved photosensitive glass 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%, 6.70%, 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 a value within a 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.

[0099] In some embodiments of the present application, the content of Ag20 in the curved photosensitive glass is 0.15% to 0.80% by mass percentage of oxide, preferably 0.15% to 0.60%, more preferably 0.15% to 0.50%. In some embodiments of the present application, the content of Ag20 in the curved photosensitive glass 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% by mass percentage of oxide, or a value within a 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.

[0100] In the present application, Ce02is a photosensitizer, and is Ag + provides electrons, and when the content of Ce02is less than 0.05%, it cannot provide sufficient electrons to reduce Ag + is a silver atom 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%.

[0101] 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.

[0102] 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%.

[0103] 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.

[0104] 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.

[0105] The curved photosensitive glass is obtained by processing a base glass, and the processing includes radiation treatment and subsequent heat treatment and heat bending treatment. In some embodiments of the present application, the heat bending treatment is preferably performed at a temperature of 560-630°C. In some embodiments of the present application, the heat bending treatment can be performed at a temperature of 560°C, 570°C, 580°C, 590°C, 600°C, 610°C, 620°C or 630°C, or at a value within a range defined by any two of the above-mentioned specific values as endpoints. It should be understood that, in embodiments, any of the above-mentioned ranges can be combined with any other range.

[0106] In some embodiments of the present application, the base glass has the same or substantially the same composition as the curved photosensitive glass, as described above.

[0107] In some embodiments of the present application, the curved photosensitive glass and / or the photosensitive glass has no particular limitation on thickness, and for example, can have a thickness of 0.3-2.0 mm, preferably 0.3-1.0 mm. In some embodiments of the present application, the curved photosensitive glass and / or the photosensitive glass can have a thickness of 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 a range defined by any two of the above-mentioned specific values as endpoints. It should be understood that, in embodiments, any of the above-mentioned ranges can be combined with any other range.

[0108] In some embodiments of the present application, the exposed region has a low transmittance in the visible light and infrared wavelength range, and the non-exposed region has a high transmittance in the visible light and infrared wavelength range. The curved photosensitive glass satisfying the transmittance can ensure that the non-exposed region has good light transmittance and good transparency, while the exposed region has low light transmittance and good shielding effect, and is suitable for use in cover glass that needs to shield light sources. The "infrared wavelength range" herein refers to light with a wavelength of 750-1000 nm.

[0109] In some embodiments of the present application, when the curved photosensitive glass has a thickness of 0.30-1.00 mm, the exposed region of the curved photosensitive glass has a transmittance T1 of 0.00%-5.00% at a wavelength of 550 nm, preferably a transmittance T1 of 0.00%-3%.

[0110] In some embodiments of the application, the transmittance Tl of the exposed 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 having any two of these values as endpoints, when the curved photosensitive glass has a thickness of 0.30-1.00 mm. It will be appreciated that in embodiments, any of the above ranges can be combined with any other range.

[0111] In some embodiments of the application, the transmittance T2 of the non-exposed area of the curved photosensitive glass at a wavelength of 550 nm is 90% or more, when the curved photosensitive glass has a thickness of 0.30-1.00 mm. In some embodiments of the application, 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 having any two of these values as endpoints, when the curved photosensitive glass has a thickness of 0.30-1.00 mm. It will be appreciated that in embodiments, any of the above ranges can be combined with any other range.

[0112] In some embodiments of the application, the transmittance T3 of the exposed area of the curved photosensitive glass at a wavelength of 850 nm is 0.00%-10.00%, preferably 0.00%-8%, when the curved photosensitive glass has a thickness of 0.30-1.00 mm.

[0113] In some embodiments of the application, the transmittance T3 of the exposed 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 having any two of these values as endpoints, when the curved photosensitive glass has a thickness of 0.30-1.00 mm. It will be appreciated that in embodiments, any of the above ranges can be combined with any other range.

[0114] In some embodiments of the present 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 90% or more. In some embodiments of the present 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 numerical values as endpoints. It should be understood that in embodiments, any of the above ranges can be combined with any other range.

[0115] In some embodiments of the present application, when the thickness of the curved photosensitive glass is 0.30-1.00 mm, the transmittance T5 of the exposed area of the curved photosensitive glass at a wavelength of 900 nm is 0.00%-10.00%, preferably 0.00%-8%.

[0116] In some embodiments of the present application, when the thickness of the curved photosensitive glass is 0.30-1.00 mm, the transmittance T5 of the exposed 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 numerical values as endpoints. It should be understood that in embodiments, any of the above ranges can be combined with any other range.

[0117] In some embodiments of the present 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 90% or more. In some embodiments of the present 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 numerical values as endpoints. It should be understood that in embodiments, any of the above ranges can be combined with any other range.

[0118] In some embodiments of the present application, the crystalline phase of the exposed region of the curved photosensitive glass comprises one or more of lithium metasilicate, lithium disilicate, petalite, quartz, spodumene, eucryptite, zinc oxide, Ag nanocrystals, Cu nanocrystals, Au nanocrystals, Bi nanocrystals.

[0119] In some embodiments of the present application, the non-exposed region of the curved photosensitive glass is substantially free of crystalline phase or comprises one or more of lithium metasilicate, lithium disilicate, petalite, quartz, spodumene, eucryptite, zinc oxide, Ag nanocrystals, Cu nanocrystals, Au nanocrystals, Bi nanocrystals.

[0120] In some embodiments of the present application, the crystalline phase of the exposed region and the non-exposed region of the curved photosensitive glass is the same.

[0121] In some embodiments of the present application, a method for preparing the curved photosensitive glass as described above is provided, which comprises:

[0122] obtaining a substrate glass;

[0123] masking the first region of the substrate glass and leaving the second region unmasked to obtain a masked substrate glass;

[0124] processing the masked substrate glass to obtain a curved photosensitive glass having a non-exposed region and an exposed region, wherein the non-exposed region corresponds to the first region and the exposed region corresponds to the second region; the processing comprises radiation treatment and subsequent heat treatment and heat bending treatment.

[0125] In some embodiments of the present application, the composition of the substrate glass is the same or substantially the same as that of the curved photosensitive glass; the specific composition is as described above.

[0126] In the present application, the substrate glass can be prepared by using the forming methods in the prior art, and the present application does not have any limitation in this regard. For example, the forming method of the substrate glass can include but is not limited to float method, overflow method, calendering or casting process. For example, the components are mixed according to the formula, melted and formed, and then cooled and annealed to obtain the substrate glass.

[0127] 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.

[0128] 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.

[0129] In some embodiments of this application, the masking process includes masking using masking ink and / or a mask plate.

[0130] For example, a schematic diagram of the structure of the substrate glass after being masked with masking ink is shown in Figure 1. The composite circular hole has a light-transmitting area 11 with an inner diameter and a light-blocking area 12 other than the inner diameter. A schematic diagram of the structure of the corresponding photosensitive glass is shown in Figure 2. The position corresponding to the light-transmitting area 11 forms an exposure area 21, and the position corresponding to the light-blocking area 12 forms a non-exposure area 22.

[0131] 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.

[0132] In some embodiments of the application, the wavelength of the UV irradiation treatment is 300 nm, 302 nm, 305 nm, 308 nm, 310 nm, 312 nm, 315 nm, 317 nm, or 320 nm, or a value within a range defined by any two of the foregoing values as endpoints. In some embodiments of the application, the intensity of the UV irradiation treatment is 20 mw / cm 2 , 40 mw / cm 2 , 60 mw / cm 2 , 80 mw / cm 2 , 100 mw / cm 2 , 120 mw / cm 2 , 140 mw / cm 2 , 160 mw / cm 2 , 180 mw / cm 2 , 200 mw / cm 2 , 210 mw / cm 2 , 220 mw / cm 2 , 230 mw / cm 2 , 240 mw / cm 2 , 250 mw / cm 2 , 260 mw / cm 2 , 270 mw / cm 2 , 280 mw / cm 2 , 290 mw / cm 2 , 300 mw / cm 2 , 310 mw / cm 2 , 320 mw / cm 2 , 330 mw / cm 2 , 340 mw / cm 2 , 350 mw / cm 2 , or 360 mw / cm 2 , or a value within a range defined by any two of the foregoing values as endpoints. In some embodiments of the application, the time of the UV 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 a range defined by any two of the foregoing values as endpoints; so long as a photosensitive glass having the desired properties of the application is obtained. It should be understood that in specific embodiments, any of the foregoing ranges can be combined with any other range, so long as a photosensitive glass having the desired properties of the application is obtained.

[0133] In some embodiments of the present application, the heat treatment includes a nucleation treatment and a crystallization treatment. The nucleation treatment and the crystallization treatment are common processes in the art.

[0134] In some embodiments of the present application, the temperature increasing rate of the nucleation treatment is 1-10°C / min. In some embodiments of the present application, the temperature increasing rate of the nucleation treatment can be 1°C / min, 2°C / min, 3°C / min, 4°C / min, 5°C / min, 6°C / min, 7°C / min, 8°C / min, 9°C / min or 10°C / min, or a value within a range between any two of the foregoing specific numerical values as endpoints. In some embodiments of the present application, the temperature of the nucleation treatment can be 430-500°C. In some embodiments of the present application, the temperature of the nucleation treatment can be 430°C, 440°C, 450°C, 460°C, 470°C, 480°C, 490°C or 500°C, or a value within a range between any two of the foregoing specific numerical values as endpoints. In some embodiments of the present application, the time of the nucleation treatment is 30-360 min. In some embodiments of the present application, the time of the nucleation treatment 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 between any two of the foregoing specific numerical values as endpoints.

[0135] In some embodiments of the present application, the temperature increasing rate of the crystallization treatment is 1-10°C / min. In some embodiments of the present application, the temperature increasing rate of the crystallization treatment can be 1°C / min, 2°C / min, 3°C / min, 4°C / min, 5°C / min, 6°C / min, 7°C / min, 8°C / min, 9°C / min or 10°C / min, or a value within a range between any two of the foregoing specific numerical values as endpoints.

[0136] In some embodiments of the present application, the temperature of the one-step crystallization process can be 500°C to 800°C. In some embodiments of the present application, the temperature of the one-step crystallization process can be 500°C, 510°C, 520°C, 530°C, 540°C, 550°C, 560°C, 570°C, 580°C, 600°C, 650°C, 700°C, 750°C, or 800°C, or a value within a range between any two of the foregoing specific numerical values, endpoints included. In some embodiments of the present application, the time of the one-step crystallization process is 30 min to 480 min. In some embodiments of the present application, the time of the 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, 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 between any two of the foregoing specific numerical values, endpoints included.

[0137] In some embodiments of the present application, the multi-step crystallization process includes a two-step crystallization process. In some embodiments of the present application, the temperature of the first step of the two-step crystallization process is 500°C to 560°C, and the temperature of the second step of the two-step crystallization process is 560°C to 800°C. In some embodiments of the present application, the temperature of the first step of the two-step crystallization process can be 500°C, 510°C, 520°C, 530°C, 540°C, 550°C, or 560°C, or a value within a range between any two of the foregoing specific numerical values, endpoints included. In some embodiments of the present application, the temperature of the second step of the two-step crystallization process can be 560°C, 570°C, 580°C, 600°C, 650°C, 700°C, 750°C, or 800°C, or a value within a range between any two of the foregoing specific numerical values, endpoints included.

[0138] In some embodiments of the present application, the first crystallization treatment in the two-step crystallization treatment has a time period of 30 min to 240 min, and the second crystallization treatment has a time period of 30 min to 240 min. In some embodiments of the present application, the first crystallization treatment in the two-step crystallization treatment can have a time period of 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 defined by any two of the above-mentioned specific values as endpoints. In some embodiments of the present application, the second crystallization treatment in the two-step crystallization treatment can have a time period of 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 defined by any two of the above-mentioned specific values as endpoints.

[0139] Before and / or after the heat treatment, the skilled person can also perform other conventional steps to obtain a substrate glass or a curved photosensitive glass sample that meets the required specifications or requirements, such as shaping, cutting (e.g. using a multi-wire saw), CNC machining, thinning or polishing, etc. The size of the substrate glass or the curved photosensitive glass sample is not limited in the present application, and can be, for example, 50 mm x 50 mm x 0.7 mm, 300 mm x 120 mm x 0.7 mm, etc.

[0140] In some embodiments of the present application, a strengthened curved photosensitive glass having a thickness of t is provided, comprising a strengthened layer extending from the surface of the curved photosensitive glass body towards the interior, the thickness of the strengthened layer being 0-0.22t, the strengthened layer comprising, in terms of mass percentage of oxides: 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 content of Li2O being lower than the content of Li2O at the center;

[0141] The strengthened curved photosensitive glass comprises, at the center, the following components in mass percentage of oxides: SiO2: 65.00% to 75.00%, Al2O3: 5.00% to 10.00%, Li2O: 7.00% to 15.00%, Na2O: 1.00% to 4.00%, K2O: 1.00% to 4.00%, ZrO2: 5.00% to 8.00%, Ag2O: 0.15% to 0.80%, CeO2: 0.05% to 0.15%, and Sb2O3: 0.1% to 0.50%;

[0142] The strengthened curved photosensitive glass comprises a non-exposed region and an exposed region.

[0143] In some embodiments of the present application, a strengthened 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 method or the above method for preparing a curved photosensitive glass.

[0144] In some embodiments of the present application, the strengthened curved photosensitive glass comprises a strengthened layer, which comprises, in mass percentage of oxides, the following components: SiO2: 65.00% to 75.00%, Al2O3: 5.00% to 10.00%, Na2O: 5.00% to 20.00%, K2O: 2.00% to 6.00%, ZrO2: 5.00% to 8.00%, Ag2O: 0.15% to 0.80%, CeO2: 0.05% to 0.15%, and Sb2O3: 0.1% to 0.50%; and the content of Li2O is lower than that at the center.

[0145] In the present application, chemical strengthening can be performed by known methods; for example, the chemical strengthening comprises single-step chemical strengthening or multi-step chemical strengthening. In some embodiments of the present application, the single-step chemical strengthening uses a salt bath containing NaNO3; preferably, the content of NaNO3 is 30-100 wt%; preferably, the single-step chemical strengthening 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%.

[0146] In some embodiments of the present application, the temperature of the single-step chemical strengthening is 380-480℃, and preferably, the ion exchange time of the single-step chemical strengthening is 1-10 h.

[0147] In some embodiments of the present application, the multi-step chemical strengthening comprises 2-step chemical strengthening, wherein the first step chemical strengthening uses a salt bath containing NaNO3, preferably the content of NaNO3 is 30-100wt%; the second step chemical strengthening uses a salt bath containing KNO3, preferably the content of KNO3 is 60-100wt%.

[0148] In some embodiments of the present application, the temperature of the first step chemical strengthening is 380-480℃, preferably the time of the first step chemical strengthening is 1-10h; preferably, the temperature of the second step chemical strengthening is 380-480℃, preferably the time of the second step chemical strengthening is 5-120min.

[0149] In some embodiments of the present application, the strengthened curved photosensitive glass described above comprises one or more of strengthened 3D photosensitive glass, strengthened 4D photosensitive glass, strengthened 5D photosensitive glass, strengthened special-shaped photosensitive glass, and strengthened four-curved photosensitive glass.

[0150] In some embodiments of the present application, the thickness t of the strengthened glass described above is not particularly limited, for example, it can be 0.3-2.0mm; preferably, it is 0.3-1.0mm. In some embodiments of the present application, the thickness of the strengthened glass can be 0.3mm, 0.4mm, 0.5mm, 0.6mm, 0.7mm, 0.8mm, 0.9mm, 1.0mm, 1.1mm, 1.2mm, 1.3mm, 1.4mm, 1.5mm, or 2.0mm, 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.

[0151] In some embodiments of the present application, the surface CS of the non-exposed area of the strengthened curved photosensitive glass described above is above 300MPa, preferably above 350MPa, further preferably 350MPa-600MPa. In some embodiments of the present application, the surface CS of the non-exposed area of the strengthened curved photosensitive glass can be 350MPa, 351MPa, 395MPa, 438MPa, 385MPa, 391MPa, 398MPa, 402MPa, 422MPa, 450MPa, 480MPa, 500MPa, 530MPa, 550MPa, 580MPa, or 600MPa, 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 required properties of the present application can be obtained. It should be understood that in embodiments, any of the above ranges can be combined with any other range, as long as the photosensitive glass with the required properties of the present application can be obtained.

[0152] In some embodiments of the present application, the single bar static pressure strength of the strengthened curved photosensitive glass described above is above 100 N, preferably 100 N to 400 N, more preferably 200 N to 400 N. In some embodiments of the present application, the single bar static pressure strength of the strengthened curved photosensitive glass described above can be 294 N, 361 N, 392 N, 301 N, 314 N, 375 N, 376 N, 390 N or 400 N, or a value within a range defined by any two of the above values as endpoints; as long as the photosensitive glass with the desired properties of the present 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 desired properties of the present application can be obtained.

[0153] The curved photosensitive glass and / or strengthened curved photosensitive glass with excellent properties provided by the present application can be used in electronic devices, including but not limited to mobile phones, tablets, handheld game consoles, portable digital devices (such as digital cameras), smart home, smart wear (such as smart bracelet, smart watch, smart glasses), and can also be used in vehicles, aircraft or spacecraft, and can also be used in any desired curved photosensitive glass glassware. For example, it can be used for back cover glass of mobile phone, shell glass of smart watch, etc.; for example, it can be used for windshield of vehicle, aircraft or spacecraft, such as front windshield or side windshield.

[0154] For example, the curved photosensitive glass and / or strengthened curved photosensitive glass with excellent properties provided by the present application can be configured to manufacture cover glass, which can be the back cover of a mobile phone or the camera protection cover of an electronic device. For example, the curved photosensitive glass and / or strengthened curved photosensitive glass with excellent properties provided by the present application can be used in electronic devices. In some embodiments of the present application, an electronic device is provided, which can be a mobile phone (as shown in FIG. 4, the curved photosensitive glass and / or strengthened curved photosensitive glass can be used as the back cover of the mobile phone), a tablet computer, a smart wearable device (as shown in FIG. 5, the curved photosensitive glass and / or strengthened curved photosensitive glass can be used as the bottom shell of a smart watch), and other electronic products.

[0155] In some embodiments of the present application, the electronic device includes a smart wearable device worn on the body, which includes a shell having a top and a bottom, the bottom is designed to contact the user's skin when worn, and the bottom shell includes the curved photosensitive glass and / or strengthened curved photosensitive glass described above in the present application.

[0156] In some embodiments of the present application, as shown in FIG. 4, the electronic device further comprises a camera assembly 32 located inside the housing, and the housing can comprise a camera protective cover plate 31 configured to cover the camera assembly 32 to protect the camera assembly 32, and the camera protective cover plate 31 is made of the aforementioned curved photosensitive glass and / or reinforced curved photosensitive glass. In some embodiments of the present application, the camera protective cover plate 31 can be partially made of the aforementioned curved photosensitive glass and / or reinforced curved photosensitive glass, or can be entirely made of the aforementioned curved photosensitive glass and / or reinforced curved photosensitive glass. In some embodiments of the present application, the camera protective cover plate 31 can be located on the front side of the electronic device, or can be located on the back side of the electronic device, depending on the location of the camera assembly 32. In some embodiments of the present application, the camera protective cover plate 31 can be in a separate structure from the back cover 33. In some other embodiments of the present application, the camera protective cover plate 31 can be in an integrated structure with the back cover 33.

[0157] The technical solutions of the present application are further described in detail below in combination with embodiments. The embodiments of the present application described in detail below are exemplary and are configured to explain the present application, and cannot be understood as a limitation of the present application.

[0158] Embodiment 1

[0159] (1) The raw materials were prepared according to the proportions of each component in Table 1, and the total mass of the prepared raw materials was 2000g. Then, 10g of clarifying agent sodium chloride (NaCl) was added to the prepared raw materials, and then mixed for 30 minutes using a V-type mixer to obtain a raw material mixture with uniform mixing.

[0160] The uniformly mixed raw materials were transferred to a platinum crucible at 1450°C in small amounts and multiple times, with a 40-minute interval between each addition. After all the raw materials were added, the temperature was raised to 1500°C, and a platinum stirring rod was used to stir and clarify for a total of 10 hours. Subsequently, the glass was drawn into the required size of glass bricks. The glass bricks were placed in an annealing furnace at 450°C for 12 hours, and then naturally cooled to room temperature to obtain the substrate glass bricks.

[0161] After the obtained substrate glass bricks were subjected to cutting, CNC processing (the CNC instrument used in the present application is of the RCG500S type), and polishing, the substrate glass meeting the required specifications and requirements can be obtained. The size of the substrate glass is 50mm x 50mm x 0.7mm.

[0162] (2) The above glass substrate was sequentially ultrasonically cleaned in deionized water, anhydrous ethanol, propanol and deionized water for 10 min, and then dried in a drying oven; the photosensitive substrate glass after cleaning was coated with shielding ink on the local area of the upper and lower main surfaces, as shown in Fig. 1, the black area was the shielding area; then the glass was subjected to double-sided irradiation treatment under parallel ultraviolet light with a wavelength of 310 nm (UVH 800*850 drawer type) for a total of 20 min, and the irradiation light energy density was 200 mw / cm 2 ; the UV-irradiated glass was heat treated according to the heat treatment process of Table 1 to obtain a photosensitive glass; the heat treatment included nucleation treatment and crystallization treatment; the heating rate of the nucleation treatment and the crystallization treatment was 10 ℃ / min; the above photosensitive glass was sequentially subjected to cold processing such as laser cutting, cleaving, polishing and chamfering, and a photosensitive glass with a size of was obtained, as shown in Fig. 2.

[0163] (3) The above photosensitive glass was subjected to heat bending treatment to obtain a 3D photosensitive glass containing an exposed area and a non-exposed area, and the glass shape was as shown in Fig. 3.

[0164] The heat bending treatment process included 4 preheating stations, 3 hot pressing stations and 3 cooling stations; the specific heat bending process was as shown in Table 2.

[0165] The crystal phase and transmittance (transmittance T1 at 550 nm wavelength, transmittance T3 at 850 nm wavelength and transmittance T5 at 900 nm wavelength) of the exposed area of the 3D photosensitive glass were tested, and the crystal phase and transmittance (transmittance T2 at 550 nm wavelength, transmittance T4 at 850 nm wavelength and transmittance T6 at 900 nm wavelength) of the non-exposed area of the 3D photosensitive glass were tested, and the results were as shown in Table 3.

[0166] (4) The 3D photosensitive glass obtained in (3) was subjected to chemical strengthening treatment, and the chemical strengthening treatment was sequentially 100wt% NaNO3 salt bath chemical strengthening at 450 ℃ for 3 h and 100wt% KNO3 salt bath chemical strengthening at 430 ℃ for 15 min to obtain a strengthened 3D photosensitive glass.

[0167] The surface CS and single-bar static pressure strength of the non-exposed area of the strengthened 3D photosensitive glass were tested, and the results were as shown in Table 4.

[0168] Examples 2-7

[0169] Each of the examples was performed with reference to Example 1, except that the raw material composition, process parameters and corresponding test results of each example were as shown in Tables 1-4.

[0170] Comparative Examples 1-3

[0171] 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.

[0172] Table 1

[0173] Table 2

[0174] Table 3

[0175] Table 4

[0176] 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.

[0177] 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.

[0178] 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.

[0179] A comparison of Example 4 and Comparative Example 2 shows that in Comparative Example 2, excessive CeO2 content in the 3D photosensitive glass leads to a decrease in the penetration depth of ultraviolet light in the exposure area of ​​the glass, as shown in Figure 6. Insufficient CeO2 content results in a reduction in the penetration depth of ultraviolet light in the glass's exposure area. 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.

[0180] 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 , and further causes the shading effect of the exposure area to be unable to meet the requirement.

[0181] The above merely provides specific embodiments of the present application and is not intended to limit the present application. For those skilled in the art, the present application can have various modifications and changes. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application shall be included in the protection scope of the present application. Industrial applicability

[0182] In summary, the present application provides a curved photosensitive glass, which has a good shielding performance in the exposure area, and can meet the requirements of the fields of mobile phone cover plate, smart watch, etc.

Claims

A curved photosensitive glass, characterized in that, The curved photosensitive glass comprises the following components in 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%. The curved photosensitive glass according to claim 1, wherein, The curved photosensitive glass comprises the following components in mass percentage of oxides: The content of SiO2 is 66.00%-74.60%, preferably, the content of SiO2 is 66.50%-74.00%; and / or, The content of Al2O3 is 5.10%-9.70%, preferably, the content of Al2O3 is 5.20%-9.40%; and / or, The content of Li2O is 7.10%-14.50%, preferably, the content of Li2O is 8.00%-14.50%; and / or, The content of Na2O is 1.00%-3.80%, preferably, the content of Na2O is 1.00%-3.75%; and / or, The content of K2O is 1.40%-3.90%, preferably, the content of K2O is 1.40%-3.85%; and / or, The content of ZrO2 is 5.00%-7.50%, preferably, the content of ZrO2 is 5.10%-7.50%; and / or, The content of Ag2O is 0.15%-0.60%, preferably, the content of Ag2O is 0.15%-0.50%; and / or, The content of CeO2 is 0.05%-0.14%, preferably, the content of CeO2 is 0.07%-0.14%; and / or, The content of Sb2O3 is 0.20%-0.50%, preferably, the content of Sb2O3 is 0.20%-0.48%. The curved photosensitive glass according to claim 1 or 2, characterized in that, The curved photosensitive glass comprises one or more of 3D photosensitive glass, 4D photosensitive glass, 5D photosensitive glass, special-shaped photosensitive glass, and four-curved photosensitive glass. The curved photosensitive glass according to any one of claims 1-3, characterized in that, The curved photosensitive glass is obtained by processing a base glass, wherein the processing comprises radiation treatment and subsequent heat treatment, and heat bending treatment. The curved photosensitive glass according to claim 4, characterized in that, The composition of the base glass is the same as or substantially the same as that of the curved photosensitive glass. The curved photosensitive glass according to any one of claims 1-5, characterized in that, The thickness of the curved photosensitive glass is 0.3-2.0 mm, preferably 0.3-1.0 mm. The curved photosensitive glass according to any one of claims 1-6, characterized in that, When the thickness of the curved photosensitive glass is 0.30-1.00 mm, the transmittance T1 of the exposed area of the curved photosensitive glass at a wavelength of 550 nm is 0.00%-5.00%, preferably the transmittance T1 is 0.00%-3%; and / or, 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, when the thickness of the curved photosensitive glass is 0.30-1.00 mm, the transmittance T3 of the exposed area of the curved photosensitive glass at 850 nm wavelength is 0.00%-8.00%, preferably the transmittance T3 is 0.00%-5%; and / or, 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 850 nm wavelength is 90% or more; and / or, when the thickness of the curved photosensitive glass is 0.30-1.00 mm, the transmittance T5 of the exposed area of the curved photosensitive glass at 900 nm wavelength is 0.00%-10.00%, preferably the transmittance T5 is 0.00%-8%; and / or, 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 900 nm wavelength is 90% or more. The curved photosensitive glass according to any one of claims 1-7, characterized in that, The crystal phase of the exposed area of the curved photosensitive glass comprises one or more of lithium metasilicate, lithium disilicate, petalite, quartz, spodumene, eucryptite, zinc oxide, Ag nanocrystal, Cu nanocrystal, Au nanocrystal, and Bi nanocrystal. The curved photosensitive glass according to claim 8, characterized in that, The non-exposed area of the curved photosensitive glass is substantially free of crystal phase or comprises one or more of lithium metasilicate, lithium disilicate, petalite, quartz, spodumene, eucryptite, zinc oxide, Ag nanocrystal, Cu nanocrystal, Au nanocrystal, and Bi nanocrystal. The curved photosensitive glass according to claim 9, characterized in that, The crystal phase of the exposed area of the curved photosensitive glass is the same as that of the non-exposed area. A method for the production of a curved photosensitive glass according to any one of claims 1 to 10, characterized in that It comprises: obtaining a substrate glass; The substrate glass comprises a first area and a second area, the first area is subjected to a masking treatment, and the second area is not subjected to the masking treatment, to obtain a masked substrate glass; After processing the masked substrate glass, a curved photosensitive glass having 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, heat bending treatment. The method for preparing a curved photosensitive glass according to claim 11, wherein, The composition of the substrate glass is the same as or substantially the same as that of the curved photosensitive glass. The method for producing a curved photosensitive glass according to claim 11 or 12, wherein The thickness of the substrate glass is 0.3-2.0 mm; preferably 0.3-1.0 mm. The method for producing a curved photosensitive glass according to any one of claims 11 to 13, wherein The masking treatment includes masking using a shielding ink and / or a mask plate. The method for producing a curved photosensitive glass according to any one of claims 11 to 14, wherein The heat treatment includes nucleation treatment and crystallization treatment. The method for preparing a curved photosensitive glass according to claim 15, wherein, The temperature of the nucleation treatment is 430-500℃; and / or, The temperature of the nucleation treatment is 430-500℃; and / or, The temperature of the nucleation treatment is 430-500℃; and / or, The temperature of the nucleation treatment is 430-500℃; and / or, The temperature of the nucleation treatment is 430-500℃; and / or, The temperature of the nucleation treatment is 430-500℃; and / or, A strengthened curved photosensitive glass characterized in that, The thickness is t, which comprises a strengthening layer extending from the surface of the curved photosensitive glass body to the interior direction, the thickness of the strengthening layer is 0-0.22t, The strengthened curved photosensitive glass comprises, at the center, the following components in mass percentage of oxides: SiO2: 65.00% to 75.00%, Al2O3: 5.00% to 10.00%, Li2O: 7.00% to 15.00%, Na2O: 1.00% to 4.00%, K2O: 1.00% to 4.00%, ZrO2: 5.00% to 8.00%, Ag2O: 0.15% to 0.80%, CeO2: 0.05% to 0.15%, and Sb2O3: 0.1% to 0.50%; The strengthened layer comprises, in mass percentage of oxides, the following components: SiO2: 65.00% to 75.00%, Al2O3: 5.00% to 10.00%, Na2O: 5.00% to 20.00%, K2O: 2.00% to 6.00%, ZrO2: 5.00% to 8.00%, Ag2O: 0.15% to 0.80%, CeO2: 0.05% to 0.15%, and Sb2O3: 0.1% to 0.50%; the content of Li2O in the strengthened layer is lower than the content of Li2O at the center; The strengthened curved photosensitive glass comprises a non-exposed region and an exposed region. The strengthened curved photosensitive glass according to claim 17, wherein, The surface CS of the non-exposed region of the strengthened curved photosensitive glass is above 300 MPa, preferably above 350 MPa, and further preferably 350 MPa to 600 MPa. The strengthened curved photosensitive glass according to claim 17 or 18, characterized in that, The single-bar static pressure strength of the strengthened curved photosensitive glass is above 100 N, preferably 100 N to 400 N, and more preferably 200 N to 400 N. A cover glass characterized by The cover glass is made of the curved photosensitive glass according to any one of claims 1 to 10 or prepared by the method according to any one of claims 11 to 16 or the strengthened curved photosensitive glass according to any one of claims 17 to 19. An electronic device, characterized by comprising: The electronic device is made of the curved photosensitive glass according to any one of claims 1 to 10 or prepared by the method according to any one of claims 11 to 16 or the strengthened curved photosensitive glass according to any one of claims 17 to 19. The electronic device of claim 21, wherein The electronic device comprises a housing having a top and a bottom, and the bottom of the housing comprises the curved photosensitive glass according to any one of claims 1 to 10 or prepared by the method according to any one of claims 11 to 16 or the strengthened curved photosensitive glass according to any one of claims 17 to 19. The electronic device according to claim 21 or 22, wherein The electronic device further comprises a camera assembly, and the housing of the electronic device comprises a camera protective cover plate covering the camera assembly, and the camera protective cover plate comprises the curved photosensitive glass according to any one of claims 1 to 10 or prepared by the method according to any one of claims 11 to 16 or the strengthened curved photosensitive glass according to any one of claims 17 to 19. Use of the curved photosensitive glass according to any one of claims 1-10 or the curved photosensitive glass prepared according to any one of claims 11-16 or the strengthened curved photosensitive glass according to any one of claims 17-19 in a component configured into a mobile phone, a wearable device, a camera module, or a vehicle.

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