Method for preparing photosensitive glass and use of photosensitive glass

Abstract

A method for preparing photosensitive glass and a use of photosensitive glass. A process for preparing photosensitive glass is controlled and improved, masking treatment is performed on two opposite main surfaces of a first region of a substrate glass comprising the first region and a second region, and the second region is not subjected to the masking treatment, so as to obtain double-sided masked substrate glass having the same structure; and radiation treatment is performed on the two main surfaces of the double-sided masked substrate glass having the same structure, such that an edge halo phenomenon of an exposed area of the photosensitive glass can be significantly improved, and good light shielding performance of the exposed area can be achieved.

Description

Method for producing and use of a photosensitive glass

[0001] Cross-reference to Related Applications

[0002] This application claims priority to the Chinese patent application No. 202410975705.9, filed on July 19, 2024, entitled “Method for producing and use of a photosensitive glass”, the content of which is incorporated herein by reference in its entirety. TECHNICAL FIELD

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

[0004] In recent years, smartwatches have developed rapidly, with more and more diversified functions. They can not only detect the number of steps, but also measure body fat, blood oxygen, body temperature, heart rate, etc. The implementation of these functions all depends on the LED of the smartwatch back cover emitting light of the corresponding wavelength to the skin, converting the reflected light into an electrical signal, and then converting it into a digital signal through the corresponding receiver. However, in order to pursue better texture, the smartwatch back cover usually adopts glass material. However, due to the lack of light shielding performance, the light emitted by the LED will interfere with each other, forming a light interference phenomenon, which affects the accuracy of the detection data.

[0005] Photosensitive glass is a Li-Al-Si glass containing a photosensitizer. Compared with ordinary glass materials, after ultraviolet treatment and heat treatment, the photosensitive glass can form an opaque region in the exposed area, and the light transmittance of the exposed area relative to the non-exposed area is greatly reduced, which has the performance of light shielding. It is expected to replace ordinary glass and be applied to the back cover of a smartwatch. However, although there are many reports on the preparation of photosensitive glass, it is still difficult for conventional photosensitive glass to meet the light shielding performance requirements of the smartwatch back cover.

[0006] In addition, during the ultraviolet treatment process of the photosensitive glass, due to the difficulty of perpendicular irradiation of the ultraviolet light source, there will be a certain inclination angle, which causes uncontrollable light to irradiate into other areas except the exposed area, expands the range of the exposed area of the glass, and causes the edge of the exposed area to appear a halo phenomenon.

[0007] It should be noted that this part of the application only provides background technology related to the application, and does not necessarily constitute prior art or public knowledge.

[0008] SUMMARY

[0009] The purpose of the present application is to provide a method for producing a photosensitive glass, which can improve the halo phenomenon at the edge of the exposed area of the photosensitive glass, and at the same time ensure that the exposed area has good light shielding performance.

[0010] To achieve the above object, the present application provides the following technical solutions.

[0011] In a first aspect, a method for preparing a photosensitive glass is provided, comprising:

[0012] obtaining a substrate glass;

[0013] The substrate glass comprises a first region and a second region, both main surfaces opposite to the first region are subjected to a masking treatment, and the second region is not subjected to the masking treatment, thereby obtaining a substrate glass with the same structure after double-side masking;

[0014] The two main surfaces of the substrate glass with the same structure after double-side masking are subjected to a radiation treatment and then a heat treatment, thereby obtaining a photosensitive glass with 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.

[0015] Optionally, the radiation treatment comprises an ultraviolet irradiation treatment.

[0016] Optionally, the wavelength of the ultraviolet irradiation treatment is 300 nm-320 nm, the intensity of the ultraviolet irradiation treatment is 20 mw / cm 2 -360 mw / cm 2 , and the time of the ultraviolet irradiation treatment is 5 min-60 min.

[0017] Optionally, the conditions of the double-side radiation treatment are the same.

[0018] Optionally, the conditions of the double-side ultraviolet irradiation treatment are the same.

[0019] Optionally, the masking treatment comprises masking using a shielding ink and / or a mask plate.

[0020] Optionally, the shielding ink is used to mask both main surfaces opposite to the first region.

[0021] Optionally, the heat treatment comprises a nucleation treatment and a crystallization treatment.

[0022] Optionally, the temperature of the nucleation treatment is 450℃-590℃; and / or,

[0023] the temperature of the nucleation treatment is 450℃-590℃; and / or,

[0024] the time of the nucleation treatment is 30 min-240 min; and / or,

[0025] the temperature of the crystallization treatment is 450℃-590℃; and / or,

[0026] the temperature of the crystallization treatment is higher than the temperature of the nucleation treatment, and the temperature of the crystallization treatment is 590-800°C; and / or

[0027] the time of the crystallization treatment is 30-360 minutes.

[0028] Optionally, the composition of the substrate glass comprises, in mass percent of oxides: SiO2: 65.00-75.00%, Al2O3: 5.00-10.00%, Li2O: 7.00-13.00%, Na2O: 2.00-4.00%, K2O: 2.00-4.00%, ZrO2: 5.00-7.00%, X: 0.05-0.80%, CeO2: 0.05-0.18%, and Sb2O3: 0.05-0.51%;

[0029] wherein X is Ag (silver), Cu (copper), Au (gold), Bi (bismuth), and / or oxides thereof, respectively.

[0030] Optionally, the composition of the photosensitive glass comprises, in mass percent of oxides: SiO2: 65.00-75.00%, Al2O3: 5.00-10.00%, Li2O: 7.00-13.00%, Na2O: 2.00-4.00%, K2O: 2.00-4.00%, ZrO2: 5.00-7.00%, X: 0.05-0.80%, CeO2: 0.05-0.18%, and Sb2O3: 0.05-0.51%;

[0031] wherein X is Ag (silver), Cu (copper), Au (gold), Bi (bismuth), and / or oxides thereof, respectively.

[0032] Optionally, the composition of the photosensitive glass comprises, in mass percent of oxides:

[0033] the content of SiO2is 73.02%, 69.80%, or 72.40%; and / or,

[0034] the content of Al2O3is 7.35%, 8.06%, or 5.87%; and / or,

[0035] the content of Li2O is 7.33%, 9.77%, or 9.80%; and / or,

[0036] the content of Na2O is 2.41%, 2.32%, or 2.84%; and / or,

[0037] the content of K2O is 2.15%, 3.34%, or 2.34%; and / or,

[0038] ZrO2is 6.71%, 5.54% or 5.77%; and / or,

[0039] Ag2O is 0.43%, 0.48% or 0.43%; and / or,

[0040] CeO2is 0.13%, 0.18% or 0.12%; and / or,

[0041] Sb2O3is 0.47%, 0.50% or 0.43%.

[0042] In a second aspect, there is provided a photosensitive glass prepared by the method of any embodiment of the first aspect.

[0043] Optionally, when the photosensitive glass has a thickness of 0.40-1.00 mm, the exposed region of the photosensitive glass has a transmittance T1 of 0.00%-5.00% at a wavelength of 850 nm, preferably a transmittance T1 of 0.00%-3%; and / or,

[0044] when the photosensitive glass has a thickness of 0.40-1.00 mm, the exposed region of the photosensitive glass has a transmittance T2 of 0.00%-5.00% at a wavelength of 550 nm, preferably a transmittance T2 of 0.00%-2%; and / or,

[0045] when the photosensitive glass has a thickness of 0.40-1.00 mm, the non-exposed region of the photosensitive glass has a transmittance T3 of 90% or more at a wavelength of 850 nm, and / or,

[0046] when the photosensitive glass has a thickness of 0.40-1.00 mm, the non-exposed region of the photosensitive glass has a transmittance T4 of 90% or more at a wavelength of 550 nm.

[0047] In a third aspect, there is provided a cover glass, the cover glass being made of the photosensitive glass of any embodiment of the second aspect.

[0048] In a fourth aspect, there is provided an electronic device, the electronic device comprising the photosensitive glass of any embodiment of the second aspect.

[0049] Optionally, the electronic device comprises a housing assembled on the outside of the electronic device, the housing comprising the photosensitive glass of any embodiment of the second aspect.

[0050] Optionally, the electronic device further comprises a camera assembly located inside the housing, the housing comprising a camera protective cover plate covering the camera assembly, the camera protective cover plate comprising the photosensitive glass of any embodiment of the second aspect.

[0051] In a fifth aspect, there is provided a use of the photosensitive glass according to any of the embodiments of the second aspect in a component for a mobile phone, a smart watch, a wearable device, a camera module, or a vehicle.

[0052] Compared with the prior art, one or more of the technical solutions provided in the present application have the following advantages:

[0053] The present application improves the preparation process of the photosensitive glass by controlling the preparation process of the photosensitive glass, by double masking treatment of the first region of the substrate glass and no masking treatment of the second region, and then performing radiation treatment on the two main surfaces. The halo phenomenon of the photosensitive glass can be significantly improved. In addition, by controlling the time and intensity of the radiation treatment, the hollow transparent region in the exposed region of the photosensitive glass can be inhibited. Further, the photosensitive glass with good light shielding performance in the exposed region can be prepared. BRIEF DESCRIPTION OF DRAWINGS

[0054] 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.

[0055] Figure 1 is a structural schematic diagram of the substrate glass after masking using masking ink according to the present application.

[0056] Figure 2 is a structural schematic diagram of the photosensitive glass according to the present application.

[0057] Figure 3 is a structural schematic diagram of the back side of the electronic device according to the present application.

[0058] Figure 4 is a structural schematic diagram of the electronic device according to the present application, which is a smart watch.

[0059] Figure 5(b) is a schematic diagram of the production process according to the present application, and (a) is a schematic diagram of the production process according to Comparative Example 1.

[0060] Figure 6 is a schematic diagram of the production process according to Comparative Example 2 of the present application.

[0061] Figure 7 is a schematic diagram of the cross section of the photosensitive glass after cutting according to Example 3 of the present application.

[0062] Figure 8 is a schematic diagram of the cross section of the photosensitive glass after cutting according to Comparative Example 1 of the present application.

[0063] Figure 9 is a schematic diagram of the cross section of the photosensitive glass after cutting according to Comparative Example 3 of the present application.

[0064] FIG. 10 is a vignetting diagram of the main surface observed by a polarizing microscope of Comparative Example 1 of the present application.

[0065] Reference numerals: 11 - light transmission area; 12 - light shielding area; 21 - exposed area; 22 - non-exposed area; 31 - camera protective cover plate; 32 - camera assembly; 33 - back cover; 41 - back cover of smart watch; 51 - mask plate; 51 - upper main surface mask plate; 61 - upper main surface shielding ink; 62 - lower main surface shielding ink; 71 / 81 / 91 - exposed area cross section. DETAILED DESCRIPTION

[0066] 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.

[0067] The endpoints of the ranges and any values disclosed herein are not limited to the precise values stated. The endpoints of the ranges and any values are understood to be approximate values. For ranges comprising numerical values, the endpoints of the ranges, the endpoints of the ranges and the individual points, and the individual points can be combined with one another to form one or more new ranges, which are to be understood as being specifically disclosed herein. The terms "optional" and "optional" mean that the element can or can not be included (or can or can not be present). The term "and / or" is inclusive, for example, "A and / or B" means only A, or only B, or both A and B.

[0068] Terminology and test methods:

[0069] 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 substrate glass placed horizontally.

[0070] In the present application, the thickness of the glass is tested by a micrometer.

[0071] In the present application, the size of the glass sheet is tested by a two-dimensional measuring machine (instrument model Miyu MY-YXCL-4030).

[0072] In the present application, the transmittance of the exposed area and the non-exposed area of the photosensitive glass is tested by a UV-Vis spectrophotometer. The UV-Vis spectrophotometer used in the present application is Shimadzu UV-2000 UV-Vis spectrophotometer.

[0073] The method for testing the exposure area of the photosensitive glass is as follows: first, using a jig with the same size as the photosensitive glass and the same area as the exposure area of the photosensitive glass, the hollow area corresponds to the non-exposure area of the photosensitive glass, and the link position of the hollow area and the opaque area is the opaque jig as a blank sample for testing correction, then the exposure area of the photosensitive glass is cut into a sample with the same shape as the hollow area of the jig, and the sample is placed in the hollow area of the jig for testing to obtain the transmittance. The transmittance of the exposure area of 5 photosensitive glasses in the same batch to light of different wavelengths is tested by using a UV-visible spectrophotometer, and then the average value is taken as the transmittance result of the exposure area of the photosensitive glass under the light of the wavelength.

[0074] In addition, the transmittance of the non-exposure area of 5 photosensitive glasses in the same batch to light of different wavelengths is tested by using a UV-visible spectrophotometer. The average value of the transmittance of the non-exposure area of the 5 photosensitive glasses under the light of different wavelengths is taken as the transmittance result of the non-exposure area of the photosensitive glass under the light of the wavelength.

[0075] In the present application, the exposure area edge of the photosensitive glass appears obvious halo phenomenon, which is called halo edge, see Figure 10.

[0076] In some embodiments of the present application, a method for preparing a photosensitive glass is provided, which comprises:

[0077] obtaining a substrate glass;

[0078] The substrate glass comprises a first region and a second region, both main surfaces of the first region are subjected to masking treatment, and the second region is not subjected to masking treatment, thereby obtaining a substrate glass with the same structure after double-sided masking;

[0079] The two main surfaces of the substrate glass with the same structure after double-sided masking are subjected to radiation treatment and then heat treatment, thereby obtaining a photosensitive glass with a non-exposure area and an exposure area; wherein the non-exposure area corresponds to the first region, and the exposure area corresponds to the second region. In the present application, the substrate glass with the same structure after double-sided masking refers to the structure of the substrate glass after double-sided masking being the same.

[0080] In the present application, the substrate glass can be prepared by using the existing forming method, and the present application does not have any limitation thereon, 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 uniformly according to the formula, melted and formed, and then cooled and annealed, thereby obtaining the substrate glass.

[0081] For example, the raw materials (industrial conventional raw materials) are proportioned according to the formula, a clarifying agent is added, and then mixed for a period of time to obtain a raw material mixture with uniform mixing. The raw material mixture is placed in a platinum crucible, heated to 1250°C-1680°C, preferably the melting temperature is 1480°C-1680°C, and preferably kept at this temperature for 3-12 h, and then poured into a forming mold to cool and form, preferably cooled to 750°C-1000°C, and then placed in an annealing furnace for annealing treatment, preferably the annealing temperature is 400°C-650°C, and preferably the annealing time is 10-48 h; and then cooled to room temperature in the furnace, to obtain the base material glass. The person skilled in the art can select the type and amount of clarifying agent according to the needs, without the need for creative labor. Further, the clarifying agent can 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 can be 0wt%-1wt% of the total amount of raw materials.

[0082] In some embodiments of the present application, the radiation treatment includes ultraviolet irradiation treatment.

[0083] In the present application, the intensity of the ultraviolet irradiation treatment and the time of the ultraviolet irradiation treatment are not particularly limited, and depend on the composition of the photosensitive glass and the light-blocking effect of the exposure area, as long as the photosensitive glass of the present application is satisfied. In some embodiments of the present application, the wavelength of the ultraviolet irradiation treatment is 300nm-320nm, the intensity of the ultraviolet irradiation treatment is 20mw / cm 2 -360mw / cm 2 , and the time of the ultraviolet irradiation treatment is 5min-60min.

[0084] In some embodiments of the present application, the conditions of the double-sided radiation treatment are the same.

[0085] In some embodiments of the present application, the conditions of the double-sided ultraviolet irradiation treatment are the same.

[0086] In some embodiments of the present application, the wavelength of the ultraviolet irradiation treatment is 300nm, 302nm, 305nm, 308nm, 310nm, 312nm, 315nm, 317nm, or 320nm, or a value within a numerical range constituted by any two of the above specific numerical values as end points. In some embodiments of the present application, the intensity of the ultraviolet irradiation treatment is 20mw / cm 2 , 40mw / cm 2 , 60mw / cm 2 , 80mw / cm 2 , 100mw / cm 2 , 120mw / cm 2 , 150mw / cm 2 , 180mw / cm2 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 within a range bounded by any two of the foregoing specific values. In some embodiments of the application, the time of the 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 within a range bounded by any two of the foregoing specific values. It should be understood that any of the foregoing ranges can be combined with any other range to obtain a photosensitive glass having the desired properties of the application.

[0087] In some embodiments of the application, the masking treatment comprises masking using a masking ink and / or a mask plate.

[0088] For example, the structure of the substrate glass after masking using a masking ink is shown in FIG. 1, which has a composite circular hole with a light transmission region 11 of the inner diameter and a light shielding region 12 other than the inner diameter; the structure of the photosensitive glass formed accordingly is shown in FIG. 2, which has an exposed region 21 corresponding to the light transmission region 11 and a non-exposed region 22 corresponding to the light shielding region 12. In some embodiments of the application, the heat treatment comprises a nucleation treatment and a crystallization treatment.

[0089] In some embodiments of the application, the nucleation treatment temperature can be 450°C to 590°C. In some embodiments of the application, the nucleation treatment temperature can be 450°C, 480°C, 500°C, 520°C, 540°C, 550°C, 560°C, 570°C, 580°C, or 590°C, or a value within a range having a lower limit of any two of these values and an upper limit of any two of these values. In some embodiments of the application, the nucleation treatment time is 30 min to 240 min. In some embodiments of the 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, or 240 min, or a value within a range having a lower limit of any two of these values and an upper limit of any two of these values. In some embodiments of the application, the nucleation treatment ramp rate is 1°C / min to 10°C / min. In some embodiments of the application, the nucleation treatment ramp rate 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 having a lower limit of any two of these values and an upper limit of any two of these values. It is understood that in embodiments, any of the above ranges can be combined with any other range to obtain a photosensitive glass having the desired properties of the application.

[0090] In some embodiments of the application, the crystallization treatment temperature is 590°C to 800°C and / or the crystallization treatment time is 30 min to 360 min. In some embodiments of the application, the crystallization treatment temperature can be 590°C, 600°C, 620°C, 640°C, 650°C, 660°C, 670°C, 680°C, 700°C, 720°C, 740°C, 760°C, 780°C, or 800°C, or a value within a range having a lower limit of any two of these values and an upper limit of any two of these values. In some embodiments of the application, the crystallization treatment time can be 30 min, 50 min, 60 min, 80 min, 90 min, 100 min, 120 min, 140 min, 160 min, 180 min, 200 min, 240 min, 260 min, 280 min, 300 min, 320 min, or 360 min, or a value within a range having a lower limit of any two of these values and an upper limit of any two of these values. It is understood that in embodiments, any of the above ranges can be combined with any other range.

[0091] Before and / or after the heat treatment, the skilled person can also perform other conventional steps to obtain a photosensitive glass sample that meets the required specifications or requirements, for example, the sample can be subjected to shaping, cutting (e.g. using a multi-wire saw), computer numerical control (CNC) machining, thinning or polishing, etc. The size of the substrate glass or the photosensitive glass is not limited in the present application, for example, it can be 50 mm x 50 mm x 1.0 mm, 300 mm x 120 mm x 0.7 mm, etc.

[0092] In some embodiments of the present application, a photosensitive glass is provided, which is prepared by the above method.

[0093] In some embodiments of the present application, the composition of the substrate glass is the same or substantially the same as that of the photosensitive glass, in terms of mass percentage of oxides.

[0094] In some embodiments of the present application, the substrate glass or the photosensitive glass comprises the following components, in terms of mass percentage of oxides: SiO2: 65.00%-75.00%; Al2O3: 5.00%-10.00%; Li2O: 7.00%-13.00%; Na2O: 2.00%-4.00%; K2O: 2.00%-4.00%; ZrO2: 5.00%-7.00%; CeO2: 0.05%-0.18%; Sb2O3: 0.05%-0.51%; and X: 0.05%-0.80%;

[0095] wherein X is Ag (silver), Cu (copper), Au (gold), Bi (bismuth) and / or their respective oxides. It should be noted that X being Ag, Cu, Au, Bi and / or their respective oxides means that X is at least one of Ag, Cu, Au, Bi, Ag2O, CuO, Au2O3, Bi2O3.

[0096] In the present application, Si02is a glass former oxide, forming an irregular continuous network with structural units of silicon-oxygen tetrahedra, and is the backbone of the glass. In some embodiments of the present application, the content of Si02in the base glass or photosensitive glass is 65.00% to 75.00% by mass of oxide; preferably 65.00% to 73.00%. In some embodiments of the present application, the content of Si02in the base glass or photosensitive glass can be 65.00%, 66.00%, 67.00%, 68.00%, 69.00%, 70.00%, 71.00%, 72.00%, 73.00%, 74.00%, or 75.00% by mass of oxide, or a value within a range bounded by any two of the foregoing specific values as endpoints. It should be understood that in embodiments, any of the foregoing ranges can be combined with any other range.

[0097] In some embodiments of the present application, the content of Al203in the base glass or photosensitive glass is in the range of 5.00% to 10.00% by mass of oxide. In some embodiments of the present application, the content of Al203in the base glass or photosensitive glass can be 5.00%, 6.00%, 7.00%, 8.00%, 9.00%, or 10.00% by mass of oxide, or a value within a range bounded by any two of the foregoing specific values as endpoints. It should be understood that in embodiments, any of the foregoing ranges can be combined with any other range.

[0098] In some embodiments of the present application, the content of Li20 in the base glass or photosensitive glass is 7.00% to 13.00% by mass of oxide. In some embodiments of the present application, the content of Li20 in the base glass or photosensitive glass can be 7.00%, 7.50%, 8.00%, 8.50%, 9.00%, 10.00%, 10.50%, 11.00%, 11.50%, 12.00%, 12.50%, or 13.00% by mass of oxide, or a value within a range bounded by any two of the foregoing specific values as endpoints. It should be understood that in embodiments, any of the foregoing ranges can be combined with any other range.

[0099] In some embodiments of the application, the substrate glass or photosensitive glass has a content of Na20 in the range of 2.00-4.00% by mass of oxide. In some embodiments of the application, the substrate glass or photosensitive glass can have a content of Na20 in the range of 2.00%, 2.50%, 3.00%, 3.50%, or 4.00% by mass of oxide, or a value within a range bounded by any two of the foregoing specific values as endpoints. It is to be understood that in embodiments, any of the foregoing ranges can be combined with any of the other ranges.

[0100] In some embodiments of the application, the substrate glass or photosensitive glass has a content of K20 in the range of 2.00-4.00% by mass of oxide. In some embodiments of the application, the substrate glass or photosensitive glass can have a content of K20 in the range of 2.00%, 2.50%, 3.00%, 3.50%, or 4.00% by mass of oxide, or a value within a range bounded by any two of the foregoing specific values as endpoints. It is to be understood that in embodiments, any of the foregoing ranges can be combined with any of the other ranges.

[0101] In some embodiments of the application, the substrate glass or photosensitive glass has a content of Zr02in the range of 5.00-7.00% by mass of oxide. In some embodiments of the application, the substrate glass or photosensitive glass can have a content of Zr02in the range of 5.00%, 5.50%, 6.00%, 6.50%, or 7.00% by mass of oxide, or a value within a range bounded by any two of the foregoing specific values as endpoints. It is to be understood that in embodiments, any of the foregoing ranges can be combined with any of the other ranges.

[0102] In some embodiments of the application, the substrate glass or photosensitive glass has a content of X in the range of 0.05-0.80% by mass of oxide; X is Ag, Cu, Au, Bi, and / or an oxide thereof, respectively. In some embodiments of the application, the substrate glass or photosensitive glass can have a content of X in the range of 0.05%, 0.10%, 0.15%, 0.20%, 0.25%, 0.30%, 0.40%, 0.50%, 0.60%, 0.70%, or 0.80% by mass of oxide, or a value within a range bounded by any two of the foregoing specific values as endpoints. It is to be understood that in embodiments, any of the foregoing ranges can be combined with any of the other ranges.

[0103] In some embodiments of the application, the base glass or photosensitive glass has a content of Ce02in the range of 0.05% to 0.18% by mass of oxide. In some embodiments of the application, the base glass or photosensitive glass can have a content of X in the range of 0.05%, 0.10%, 0.15%, or 0.18% by mass of oxide; or a value within a range bounded by any two of the foregoing specific values as endpoints. It is to be understood that in embodiments, any of the foregoing ranges can be combined with any of the other ranges.

[0104] In some embodiments of the application, the base glass or photosensitive glass has a content of Sb203in the range of 0.05% to 0.51% by mass of oxide. In some embodiments of the application, the base glass or photosensitive glass can have a content of Sb203in the range of 0.05%, 0.10%, 0.15%, 0.20%, 0.25%, 0.30%, 0.35%, 0.40%, 0.45%, 0.50%, or 0.51% by mass of oxide; or a value within a range bounded by any two of the foregoing specific values as endpoints. It is to be understood that in embodiments, any of the foregoing ranges can be combined with any of the other ranges.

[0105] In some embodiments of the application, the photosensitive glass has a transmittance Tl in the exposed region at a wavelength of 850 nm in the range of 0.00% to 5.00%, preferably in the range of 0.00% to 3.00%, when the photosensitive glass has a thickness in the range of 0.40 to 1.00 mm. In some embodiments of the application, the photosensitive glass can have a transmittance Tl in the exposed region at a wavelength of 850 nm in the range of 0.00%, 0.21%, 0.50%, 0.70%, 0.90%, 1.00%, 1.25%, 1.35%, 1.50%, 1.70%, 2.00%, 2.51%, 3.00%, 3.50%, 4.00%, 4.50%, 4.80%, or 5.00%; or a value within a range bounded by any two of the foregoing specific values as endpoints. It is to be understood that in embodiments, any of the foregoing ranges can be combined with any of the other ranges.

[0106] In some embodiments of the application, when the photosensitive glass has a thickness of 0.40-1.00 mm, the transmittance T2 of the exposed region of the photosensitive glass at a wavelength of 550 nm is 0.00-5.00%, preferably 0.00-2.00%. In some embodiments of the application, when the photosensitive glass has a thickness of 0.40-1.00 mm, the transmittance T2 of the exposed region of the photosensitive glass at a wavelength of 550 nm can be 0.00%, 0.20%, 0.50%, 0.70%, 0.90%, 1.00%, 1.35%, 1.50%, 1.70%, 2.00%, 2.50%, 3.00%, 3.50%, 4.00%, 4.20%, 4.50%, 4.90%, or 5.00%; or a value within a range bounded by any two of the foregoing specific values as endpoints. It should be understood that in embodiments, any of the foregoing ranges can be combined with any other range.

[0107] In some embodiments of the application, when the photosensitive glass has a thickness of 0.40-1.00 mm, the transmittance T3 of the non-exposed region of the photosensitive glass at a wavelength of 850 nm is 90% or more. In some embodiments of the application, when the photosensitive glass has a thickness of 0.40-1.00 mm, the transmittance T3 of the non-exposed region of the photosensitive glass at a wavelength of 550 nm can be 90.00%, 90.50%, 91.00%, 91.47%, 91.49%, 91.66%, 92.00%, 91.75%, 91.39%, 92.08%, or 95.00%; or a value within a range bounded by any two of the foregoing specific values as endpoints. It should be understood that in embodiments, any of the foregoing ranges can be combined with any other range.

[0108] In some embodiments of the application, when the photosensitive glass has a thickness of 0.40-1.00 mm, the transmittance T4 of the non-exposed region of the photosensitive glass at a wavelength of 550 nm is 90% or more. In some embodiments of the application, when the photosensitive glass has a thickness of 0.40-1.00 mm, the transmittance T4 of the non-exposed region of the photosensitive glass at a wavelength of 550 nm can be 90.00%, 90.50%, 91.00%, 91.47%, 91.49%, 91.66%, 92.00%, 91.75%, 91.39%, 92.08%, 93.00%, or 95.00%; or a value within a range bounded by any two of the foregoing specific values as endpoints. It should be understood that in embodiments, any of the foregoing ranges can be combined with any other range.

[0109] In some embodiments of the present application, the photosensitive glass of the present application has no particular limitation on thickness, for example, it can be 0.4-2.0 mm; preferably, it is 0.4-1.0 mm. In some embodiments of the present application, the photosensitive glass of the present application can have a thickness of 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 numerical range formed 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.

[0110] In a second aspect, there is provided a strengthened glass, which is chemically strengthened from the photosensitive glass prepared by the preparation method as above.

[0111] In the present application, the chemical strengthening can be carried out by the methods known in the art; for example, the chemical strengthening includes single-step chemical strengthening or multi-step chemical strengthening.

[0112] In some embodiments of the present application, the single-step chemical strengthening uses a salt bath containing NaNO3; preferably, the content of NaNO3 in the salt bath is 30wt%-100wt%; 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 80-100wt%, and the content of NaNO3 is 0-20wt%.

[0113] In some embodiments of the present application, the temperature of the single-step chemical strengthening is 380°C-480°C; preferably, the ion exchange time of the single-step chemical strengthening is 5h-10h.

[0114] In some embodiments of the present application, the multi-step chemical strengthening includes two-step chemical strengthening, wherein the first-step chemical strengthening uses a salt bath containing NaNO3, preferably, the content of NaNO3 is 30wt%-100wt%; the second-step chemical strengthening uses a salt bath containing KNO3, preferably, the content of KNO3 is 60wt%-100wt%.

[0115] In some embodiments of the present application, the temperature of the first-step chemical strengthening is 380°C-480°C, preferably, the time of the first-step chemical strengthening is 3h-10h; and / or, the temperature of the second-step chemical strengthening is 380°C-480°C, preferably, the time of the second-step chemical strengthening is 1h-5h.

[0116] The photosensitive glass and the strengthened glass provided by the present application can be used in electronic devices, including but not limited to mobile phones, tablet computers, handheld game consoles, portable digital devices (such as digital cameras), smart homes, smart wear (such as smart bracelets, smart watches, smart glasses), and can also be used in vehicles, aircraft or vessels, and can also be used in any required photosensitive glass glassware. For example, it can be used in the back cover glass of a mobile phone, the back cover glass of a smart watch, etc.; for example, it can be used in the windshield of a vehicle, aircraft or vessel, such as the front windshield or side windshield. For example, the photosensitive glass provided by the present application can be used to manufacture glassware. The glassware referred to herein can be regular or irregular, and those skilled in the art can manufacture it according to requirements.

[0117] For example, the photosensitive glass provided by the present application can be used to manufacture cover glass, which can be the back cover of a mobile phone or the camera protection cover glass. For example, the photosensitive glass provided by the present application with excellent performance can be used in electronic devices. Referring to FIGS. 3 and 4, in some embodiments of the present application, an electronic device, which can be a mobile phone (as shown in FIG. 3, the photosensitive glass can be used as the back cover of the mobile phone), a tablet computer, a smart wearable device (as shown in FIG. 4, the photosensitive glass can be used as the back cover 41 of a smart watch), etc., includes the photosensitive glass. In some embodiments of the present application, as shown in FIG. 3, the electronic device further includes a camera assembly 32 located inside the shell, the shell can include a camera protection cover glass 31, the camera protection cover glass 31 is configured to cover the camera assembly 32 to protect the camera assembly 32, and the camera protection cover glass 31 is made of the aforementioned photosensitive glass. In some embodiments of the present application, the camera protection cover glass 31 can be partially made of the aforementioned photosensitive glass, or can be entirely made of the aforementioned photosensitive glass. In some embodiments of the present application, the camera protection cover glass 31 can be located on the front side of the electronic device, or can be located on the back side of the electronic device. In some embodiments of the present application, the camera protection cover glass 31 can be in a separate structure from the back cover 33. In another embodiment of the present application, the camera protection cover glass 31 can be in an integrated structure with the back cover 33.

[0118] The technical solutions of the present application are further described in detail below in combination with examples. The examples 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.

[0119] Example 1

[0120] A method for preparing a photosensitive glass, including the following steps:

[0121] Step 1: Prepare each raw material (industrial conventional raw material) according to the proportion of each component in Table 1, the total mass of the prepared raw material is 2000g, and then add 10g of clarifying agent sodium chloride to the prepared raw material, and then mix for 30 minutes with a V-type mixer to obtain a uniformly mixed raw material mixture;

[0122] Transfer the raw material mixture to a melting furnace, melt at a temperature of 1450℃, stir the molten material with a platinum-gold stir bar, and the melting time is 10h, then draw and form into a glass brick of the required specification. The glass brick is quickly placed in an annealing furnace at 500℃ for 6h, and then naturally cooled to room temperature to obtain the base glass brick;

[0123] After the obtained base glass brick is sequentially subjected to cutting, CNC processing (the CNC instrument used in the present application is of RCG500S type), and polishing, a base glass with a size of 50mm x 50mm x 1.0mm can be obtained.

[0124] Step 2: The obtained base glass is sequentially subjected to ultrasonic cleaning in deionized water, anhydrous ethanol, propanol, and deionized water for 10min, and then dried in a drying oven;

[0125] The base glass after cleaning is coated with a shielding ink on the same local area of the upper and lower main surfaces, as shown in FIG. 1, and the black area is the masking area; then subjected to double-sided irradiation treatment under parallel ultraviolet light with a wavelength of 310nm (UVHX800*850 drawer type) for a total of 25min, and the irradiation treatment intensity is 120mw / cm 2 ;

[0126] The glass after UV irradiation is subjected to heat treatment according to the heat treatment process of Table 1 to obtain a photosensitive glass; the heat treatment includes nucleation treatment and crystallization treatment; the heating rate of the nucleation treatment and the crystallization treatment is 10℃ / min; the photosensitive glass is sequentially subjected to laser cutting, fracturing, polishing, and chamfering, and other cold processing treatments to obtain a photosensitive glass with a size of φ30*1.0mm, as shown in the actual photograph of FIG. 2.

[0127] Example 2

[0128] Refer to Example 1, the difference is that the raw material composition and the masking treatment method and the ultraviolet irradiation treatment time of Example 2 are different, as shown in Table 1.

[0129] Example 3

[0130] Refer to Example 1, the difference is that the raw material composition and the ultraviolet irradiation treatment time of Example 3 are different, as shown in Table 1.

[0131] Example 4

[0132] Example 1 was referred to, except that the raw material composition of Example 4 and the process parameters of ultraviolet irradiation were different as shown in Table 1.

[0133] Comparative Example 1-2

[0134] Example 3 was referred to, except that the masking treatment method of Comparative Example 1-2 and the ultraviolet irradiation treatment area were different as shown in Table 1-2.

[0135] Comparative Example 3-4

[0136] Example 3 was referred to, except that the process parameters of ultraviolet irradiation of Comparative Example 3-4 were different as shown in Table 1-2.

[0137] Among them, the process flow chart of Examples 1-4 and Comparative Example 3-4 is shown in part (b) of FIG. 5, the process flow chart of Comparative Example 1 is shown in part (a) of FIG. 5, and the process flow chart of Comparative Example 2 is shown in FIG. 6. Among them, 61 represents the upper main surface shielding ink; 62 represents the lower main surface shielding ink, and 51 represents the upper main surface mask.

[0138] The relevant performance tests were carried out on Examples 1-4 and Comparative Examples 1-4, and the results are shown in Table 1-2.

[0139] Examples 3, Comparative Example 1 and Comparative Example 3 were cut by a laser cutting machine respectively, wherein the cross-sectional view of Example 3 is shown in FIG. 7, the cross-sectional view 71 of the exposure area of Example 3 is solid and the outline is micro-arc; the cross-sectional view of Comparative Example 1 is shown in FIG. 8; the cross-sectional view 81 of the exposure area of Comparative Example 1 is solid but the outline is trapezoidal; the cross-sectional view of Comparative Example 3 is shown in FIG. 9, and the cross-sectional view 91 of the exposure area of Comparative Example 3 is partially hollow but the outline of the solid part is micro-arc.

[0140] FIG. 10 is a halo diagram of the main surface of the Comparative Example 1 observed by a polarizing microscope, and it can be seen that the halo is generated in Comparative Example 1.

[0141] Table 1

[0142] Table 2

[0143] According to the comparison of Example 3 and Comparative Examples 1-4, it can be known that the ultraviolet irradiation treatment on the two main surfaces can solve the problem of halo appearing at the edge of the exposure area of the photosensitive glass; in addition, the light shielding performance of the exposure area of the photosensitive glass can be adjusted by controlling the conditions of the ultraviolet irradiation treatment.

[0144] The above merely provides specific examples 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 modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present application shall be included in the protection scope of the present application. Industrial applicability

[0145] In summary, the present disclosure provides a preparation method of photosensitive glass, which can improve the phenomenon of halo appearing at the edge of the exposure area of the photosensitive glass, and at the same time ensure that the exposure area has good light shielding performance.

Claims

1. A method for the production of a photosensitive glass, characterized in that Comprising: obtaining a substrate glass; the substrate glass comprises a first region and a second region, both main surfaces of the first region are subjected to a masking treatment, the second region is not subjected to the masking treatment, obtaining a double-side masked substrate glass with the same structure; subjecting the double-side masked substrate glass with the same structure to a radiation treatment and then to a heat treatment, obtaining a photosensitive glass with 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.

2. The production method according to claim 1, characterized by, The radiation treatment includes ultraviolet irradiation treatment.

3. The production method according to claim 2, characterized by, The wavelength of the ultraviolet irradiation treatment is 300 nm-320 nm, the intensity of the ultraviolet irradiation treatment is 20 mw / cm 2 -360 mw / cm 2 , and the time of the ultraviolet irradiation treatment is 5 min-60 min.

4. The production method according to any one of claims 1 to 3, characterized by, The masking treatment includes masking using shielding ink and / or a mask plate.

5. The production method according to any one of claims 1 to 4, characterized by, The heat treatment includes nucleation treatment and crystallization treatment.

6. The production method according to claim 5, characterized by, The nucleation treatment has a temperature increasing rate of 1-10 ℃ / min; and / or, The nucleation treatment has a temperature of 450-590 ℃; and / or, The nucleation treatment has a time of 30-240 min; and / or, The crystallization treatment has a temperature increasing rate of 1-10 ℃ / min; and / or, The crystallization treatment has a temperature higher than that of the nucleation treatment, and the temperature of the crystallization treatment is 590-800 ℃; and / or, The crystallization treatment has a time of 30-360 min.

7. The production method according to any one of claims 1 to 6, characterized by, The substrate glass has a composition comprising, in mass percent of oxides, SiO2: 65.00-75.00%, Al2O3: 5.00-10.00%, Li2O: 7.00-13.00%, Na2O: 2.00-4.00%, K2O: 2.00-4.00%, ZrO2: 5.00-7.00%, X: 0.05-0.80%, CeO2: 0.05-0.18%, and Sb2O3: 0.05-0.51%; X is Ag, Cu, Au, Bi, and / or their respective oxides.

8. The production method according to any one of claims 1 to 7, characterized by, The photosensitive glass has a composition comprising, in mass percent of oxides, SiO2: 65.00-75.00%, Al2O3: 5.00-10.00%, Li2O: 7.00-13.00%, Na2O: 2.00-4.00%, K2O: 2.00-4.00%, ZrO2: 5.00-7.00%, X: 0.05-0.80%, CeO2: 0.05-0.18%, and Sb2O3: 0.05-0.51%; X is Ag, Cu, Au, Bi, and / or their respective oxides.

9. A photosensitive glass, characterized by, Obtained by the preparation method of any one of claims 1-8.

10. The photosensitive glass according to claim 9, characterized in that, When the photosensitive glass has a thickness of 0.40-1.00 mm, the exposed region of the photosensitive glass has a transmittance T1 of 0.00-5.00% at a wavelength of 850 nm, preferably a transmittance T1 of 0.00-3.00%; and / or, when the thickness of the photosensitive glass is 0.40-1.00 mm, the transmittance T2 of the exposed region of the photosensitive glass at a wavelength of 550 nm is 0.00%-5.00%, preferably the transmittance T2 is 0.00%-2.00%; and / or, when the thickness of the photosensitive glass is 0.40-1.00 mm, the transmittance T3 of the non-exposed region of the photosensitive glass at a wavelength of 850 nm is 90% or more; and / or, when the thickness of the photosensitive glass is 0.40-1.00 mm, the transmittance T4 of the non-exposed region of the photosensitive glass at a wavelength of 550 nm is 90% or more.

11. A cover glass, characterized by The cover glass comprises the photosensitive glass according to any one of claims 9-10.

12. An electronic device, comprising: The electronic device comprises the photosensitive glass according to any one of claims 9-10.

13. The electronic device of claim 12, wherein, The electronic device comprises a housing comprising the photosensitive glass according to any one of claims 9-10.

14. The electronic device of claim 13, wherein, The electronic device further comprises a camera assembly, the housing comprises a camera protective cover plate covering the camera assembly, the camera protective cover plate comprises the photosensitive glass according to any one of claims 9-10.

15. Use of the photosensitive glass according to any one of claims 9-10 for components in a mobile phone, a smart watch, a wearable device, a camera module or a vehicle.

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