A colored glass-ceramics, its preparation method and application

Abstract

The present invention discloses a colored glass-ceramics, a preparation method thereof and an application. The colored glass-ceramics, in the form of oxides and by mass percentage, includes: a base component and a coloring component. The base component includes SiO2: 67% - 73%, R2O: 10% - 19%, Al2O3: 2% - 8%, B2O3: 0 - 0.5%, SnO2: 0 - 0.2%, ZrO2: 1.5% - 5%, RO: 0 - 3%, P2O5: 1.5% - 3.5%; the coloring component includes at least one of oxides of transition metals or rare earth elements, with a mass percentage of 0.02% - 6%; wherein, R2O is an alkali metal oxide; RO is an alkaline earth metal oxide. By adding a coloring component to the glass composition, the colored glass-ceramics presents the required color. By adjusting the proportion of each component, a glass melt with a low liquidus viscosity is obtained, and its forming temperature can be between 1060 - 1250°C, and the kinematic viscosity is 21000mm 2 / s - 57500mm 2 / s, which is applicable to the fusion leakage forming of platinum pipes or platinum forming devices.

Description

Technical Field

[0001] The present invention relates to the technical field of glass-ceramics, and particularly to a colored glass-ceramics, a preparation method thereof, and an application technical field. Background Art

[0002] The backplane glass is the rear glass cover of a mobile phone. Traditional backplanes are mainly made of metal and plastic. With the development and application promotion of 5G and wireless charging technologies, the shielding effect of metal backplanes on signals has become more prominent. Therefore, the backplane is gradually replaced by non-metallic materials, and glass and glass-ceramics will become the main alternative materials due to their excellent properties. With the wide popularization of smart phones, consumers' requirements for mobile phones are not only limited to performance and lifespan, but also have higher and higher requirements for visual effects and appearance personalization. The backplane does not need to have excellent transmittance like the front cover plate, and its appearance can be designed personalized. Therefore, the color selection and design of colored glass or glass-ceramics mobile phone back covers have become a research hotspot for terminal mobile phone manufacturers.

[0003] Currently, the color design of mobile phone back covers mainly adopts the film pasting process or electroplating and painting. Both of these two processes are processed on the transparent mobile phone glass cover plate, and the colors have developed from the earliest solid colors to the current popular gradient colors. The demand of terminal manufacturers for the colors of mobile phone back covers has gradually shifted from the development of film colors to the glass body, in order to achieve a three-dimensional and saturated color effect through the integration of the color of the glass body and the color of the film. Colored glass for mobile phone back covers can be divided into solid colors or multi-colors with texture patterns.

[0004] However, although there are many manufacturers of solid-color glass at present, most of them are used in traditional industries and are mostly of the soda-lime glass system. There are few high-aluminum glass or glass-ceramics series used for mobile phone back covers. Textured colored glass is commonly seen in art glass and architectural decorative glass-ceramics. Most art glasses are handmade products, and sintering methods are mostly used for architectural decorative glass-ceramics. Both processes are not suitable for the industrial production of electronic glass.

[0005] On the other hand, the personalized requirements of colored glass determine that it belongs to a small and beautiful product of a specific version or customized version. The traditional large-scale mass production method is not suitable, and a small-batch intermittent production process needs to be adopted. Currently, the more suitable method is the platinum pipe leakage forming method similar to the production of optical glass. However, the existing glass compositions suitable for electronic cover glass have problems such as high liquidus viscosity, high forming temperature, and inapplicability to fusion leakage forming. Summary of the Invention

[0006] The main object of the present invention is to propose a colored glass-ceramics, a preparation method thereof, and an application, aiming to solve the problems that the colored glass-ceramics in the prior art have high liquidus viscosity and high forming temperature during forming, and are not suitable for fusion leakage forming.

[0007] To achieve the above object, the present invention provides a colored glass-ceramics, which, in the form of oxides and calculated by mass percentage, comprises:

[0008] Base components: SiO2: 67% - 73%, R2O: 10% - 19%, Al2O3: 2% - 8%, B2O3: 0 - 0.5%, SnO2: 0 - 0.2%, ZrO2: 1.5% - 5%, RO: 0 - 3%, P2O5: 1.5% - 3.5%; and

[0009] Coloring components, including at least one of oxides of transition metals or rare earth elements, with a mass percentage of 0.02% - 6%; where

[0010] R2O is an alkali metal oxide;

[0011] RO is an alkaline earth metal oxide.

[0012] Optionally, the coloring components include at least one of TiO2, CeO2, Fe2O3, FeO, V2O5, V2O3, C r2 O3, CuO, Mn2O3, CoO, Co2O3, Er2O3, La2O3, Y2O3, Nd2O3, Pr2O3 and Pr6O 11 among others.

[0013] Optionally, RO includes at least one of MgO, ZnO and CaO.

[0014] Optionally, R2O includes Li2O.

[0015] Optionally, R2O further includes Na2O and K2O. The mass percentage of Na2O in the colored glass-ceramics is W(Na2O), and the mass percentage of K2O in the colored glass-ceramics is W(K2O), where 0% ≤ W(Na2O) + W(K2O) ≤ 3%, and the mass percentage of Li2O in the colored glass-ceramics is 10% - 16%.

[0016] Optionally, the mass percentage of Li2O in the colored glass-ceramics is W(Li2O), the mass percentage of SiO2 in the colored glass-ceramics is W(SiO2), and the mass percentage of P2O5 in the colored glass-ceramics is W(P2O5), where

[0017] 0.12 ≤ W(Li2O) / (W(SiO2) + 3W(P2O5)) ≤ 0.2.

[0018] Optionally, the mass percentage of R2O in the colored glass-ceramics is W(R2O), the mass percentage of RO in the colored glass-ceramics is W(RO), the mass percentage of B2O3 in the colored glass-ceramics is W(B2O3), the mass percentage of SiO2 in the colored glass-ceramics is W(SiO2), the mass percentage of Al2O3 in the colored glass-ceramics is W(Al2O3), and the mass percentage of ZrO2 in the colored glass-ceramics is W(ZrO2), where

[0019] 0.15 ≤ [W(R2O) + W(RO) + W(B2O3)] / [W(SiO2) + W(Al2O3) + 2W(ZrO2)] ≤ 0.3.

[0020] Optionally, the transmittance of the colored glass-ceramics in the light wavelength range of 380 - 1000 nm > 20%; and / or,

[0021] The brightness value of the colored glass-ceramics > 20.

[0022] Optionally, the thickness of the colored glass-ceramics is 0.2 - 2 mm.

[0023] Optionally, the colored glass-ceramics include at least one color.

[0024] Optionally, the color of the colored glass-ceramics includes any one of yellow, green, blue, purple, and pink.

[0025] Optionally, the color of the colored glass-ceramics includes any one of the alternating distribution of blue and gray-blue, blue-green, pink-purple, and cyan-green.

[0026] Optionally, the colors of the colored glass-ceramics are irregularly and alternately distributed inside the glass; and / or,

[0027] The colors of the colored glass-ceramics are irregularly and alternately distributed on the surface of the glass.

[0028] Optionally, the crystallinity of the colored glass-ceramics > 30%.

[0029] Optionally, the crystal phases of the colored glass-ceramics are at least two of cristobalite, lithium metasilicate, lithium disilicate, spodumene, and lithium phosphate.

[0030] Optionally, the thickness of the colored glass-ceramics is t, and the depth of the stress layer of the colored glass-ceramics is doc, where doc is 0.15*t - 0.24*t um; and / or,

[0031] The Vickers hardness of the colored glass-ceramics is at least 710 kgf / mm 2 ; and / or,

[0032] The four-point bending property of the colored glass-ceramics is 4PB, where the 4PB value is greater than or equal to 730 N / mm 2 .

[0033] The present invention also provides a method for preparing colored glass-ceramics. The colored glass-ceramics, in the form of oxides and calculated by mass percentage, include: a base component and a coloring component. The base component includes SiO2: 67% - 73%, R2O: 10% - 19%, Al2O3: 2% - 8%, B2O3: 0 - 0.5%, SnO2: 0 - 0.2%, ZrO2: 1.5% - 5%, RO: 0 - 3%, P2O5: 1.5% - 3.5%; the coloring component includes at least one of oxides of transition metals or rare earth elements, with a mass percentage of 0.02% - 6%; where R2O is an alkali metal oxide; RO is an alkaline earth metal oxide. The method for preparing the colored glass-ceramics includes the following steps:

[0034] Weigh the raw materials containing the base component and the raw materials containing the coloring component;

[0035] Melt the raw materials containing the base component to obtain a glass melt;

[0036] Mix the raw materials containing the coloring component with the glass melt to obtain a colored glass melt;

[0037] Fuse and shape the colored glass melt, and perform annealing treatment to obtain a colored glass product;

[0038] Perform crystallization treatment on the colored glass product to obtain colored glass-ceramics.

[0039] Optionally, in the step of "mixing the raw materials containing the base component and then melting to obtain a glass melt", the melting temperature is 1350 - 1500 °C.

[0040] Optionally, in the step of "fusing and shaping the colored glass melt, and performing annealing treatment to obtain a colored glass product",

[0041] the shaping temperature of the colored glass melt is 1060 - 1250 °C; and / or,

[0042] the kinematic viscosity of the colored glass melt is 21000 mm 2 / s - 57500 mm 2 / s; and / or,

[0043] the annealing treatment temperature of the colored glass melt is 440 - 520 °C.

[0044] Optionally, in the step of "mixing the coloring component raw material with the glass melt to obtain a colored glass melt", it includes: draining the glass melt through at least one runner, and adding at least one kind of colored glass melt obtained by mixing the coloring component raw material with the glass melt in the runner.

[0045] Optionally, in the step of "mixing the coloring component raw material with the glass melt to obtain a colored glass melt", the step includes: first melting, discharging, water quenching, and grinding the mixture of the basic component raw material and the coloring component raw material to form colored cullet powder, and melting the colored cullet powder and mixing it with the glass melt to obtain a colored glass melt.

[0046] Optionally, in the step of "fusing and shaping the colored glass melt and annealing to obtain a colored glass product", the shaping step includes: fusing and shaping at least one kind of colored glass melt by the fusing leakage forming method.

[0047] Optionally, before the step of "fusing and shaping the colored glass melt and annealing to obtain a colored glass product", it includes: stirring and mixing at least two kinds of colored glass melts.

[0048] Optionally, in the step of "crystallizing the glass product to obtain a colored glass-ceramic", the crystallization treatment includes a first crystallization treatment and a second crystallization treatment carried out in sequence;

[0049] The temperature of the first crystallization treatment is 520 - 640 °C, and the heat preservation time of the first crystallization treatment is 30 - 240 min; and / or,

[0050] The temperature of the second crystallization treatment is 670 - 800 °C, and the heat preservation time of the second crystallization treatment is 30 - 60 min.

[0051] Optionally, after the step of "crystallizing the glass product to obtain a colored glass-ceramic", it further includes:

[0052] Performing ion exchange on the colored glass-ceramic to obtain a chemically strengthened colored glass-ceramic;

[0053] Among them, the bath salts used for the ion exchange include 30 wt.% - 100 wt.% of sodium salts, 0 wt.% - 70 wt.% of potassium salts, and 0 wt.% - 0.2 wt.% of lithium salts.

[0054] Optionally, the ion exchange is one-step ion exchange or two-step ion exchange; and / or,

[0055] The temperature of the ion exchange is 450 - 520 °C; and / or,

[0056] The time of the ion exchange is 5 - 12 h.

[0057] The present invention also provides an electronic product, which includes a backplane. The material of the backplane includes the colored glass-ceramics described above. The colored glass-ceramics, in the form of oxides, by mass percentage, includes: a base component and a coloring component. The base component includes SiO2: 67% - 73%; the strengthening component includes R2O: 10% - 19%, Al2O3: 2% - 8%, B2O3: 0 - 0.5%, SnO2: 0 - 0.2%, ZrO2: 1.5% - 5%, RO: 0 - 3%, P2O5: 1.5% - 3.5%; the coloring component includes at least one of oxides of transition metals or rare earth elements, with a mass percentage of 0.02% - 6%; wherein, R2O is an alkali metal oxide; RO is an alkaline earth metal oxide.

[0058] Optionally, the electronic products in the electronic product include mobile phones, tablet computers, televisions, computer displays, and smart watches.

[0059] The present invention provides a colored glass-ceramics. By adding a coloring component to the glass composition, the colored glass-ceramics presents the required color. By adjusting the ratio of each component, a glass melt with a low liquidus viscosity is obtained, and its forming temperature can be between 1060 - 1250 °C, and the kinematic viscosity is 21000 mm 2 / s - 57500 mm 2 / s, which is more suitable for fusion leakage forming using platinum pipes or platinum shapers. Among them, adding the alkali metal oxide R2O can significantly reduce the viscosity during glass melting and forming, promote the melting and clarification of the glass melt, and significantly improve the fluidity of the glass; introducing 1.5% - 5% ZrO2 can inhibit the crystallization ability of the glass, facilitate fusion forming, and avoid deposition due to refractory; adding alkaline earth metal oxides can improve the chemical stability and mechanical strength of the glass. BRIEF DESCRIPTION OF THE DRAWINGS

[0060] In order to more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the following will briefly introduce the drawings required for use in the description of the embodiments or the prior art. Obviously, the following drawings are only some embodiments of the present invention. For those of ordinary skill in the art, without creative efforts, other drawings can be obtained based on the structures shown in these drawings.

[0061] Figure 1 It is a flowchart of the method for preparing the colored glass-ceramics provided in an embodiment of the present invention.

[0062] The realization, functional characteristics, and advantages of the object of the present invention will be further described in conjunction with the embodiments and with reference to the drawings. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0063] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. For those not specified in the embodiments, conventional conditions or conditions recommended by the manufacturer are followed. For reagents or instruments without indicating the manufacturer, they are all conventional products that can be obtained through commercial purchase. In addition, the meaning of "and / or" that appears throughout the text includes three parallel solutions. Taking "A and / or B" as an example, it includes solution A, or solution B, or a solution where both A and B are satisfied simultaneously. In addition, the technical solutions between the various embodiments can be combined with each other, but it must be based on what can be achieved by those of ordinary skill in the art. When the combination of technical solutions results in contradictions or cannot be achieved, it should be considered that such a combination of technical solutions does not exist and is not within the scope of protection required by the present invention. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts belong to the scope of protection of the present invention.

[0064] The present invention provides a colored glass-ceramics, which solves the problem in the prior art that the liquidus viscosity of colored glass-ceramics is high during forming, the forming temperature is high, and it is not suitable for leakage forming. Among them, Figure 1 is a flowchart of the preparation method of an embodiment of the present invention.

[0065] In the present invention, the colored glass-ceramics, in the form of oxides, calculated by mass percentage, include: a base component and a coloring component. The base component includes SiO2: 67% - 73%, R2O: 10% - 19%, Al2O3: 2% - 8%, B2O3: 0 - 0.5%, SnO2: 0 - 0.2%, ZrO2: 1.5% - 5%, RO: 0 - 3%, P2O5: 1.5% - 3.5%; the coloring component includes at least one of oxides of transition metals or rare earth elements, with a mass percentage of 0.02% - 6%; where R2O is an alkali metal oxide; RO is an alkaline earth metal oxide.

[0066] SiO2 is a network structure former inside the glass, which is the main structure of the glass and the glass after crystallization, and is also the main component constituting the crystal phase. If its content is too low, it is difficult to form the crystal phase, and the content of SiO2 should not be lower than 67 wt%. However, a higher content of SiO2 will increase the high-temperature viscosity of the glass melt, which has an adverse effect on fusion forming. The highest content of SiO2 is controlled below 73 wt.%. In some embodiments of the present invention, the content range of SiO2 is preferably 69 wt.% - 72 wt.%; in some embodiments of the present invention, the content of SiO2 can be 67 wt.%, 68 wt.%, 69 wt.%, 70 wt.%, 71 wt.%, 72 wt.%, 73 wt.%.

[0067] The colored glass-ceramics provided by the present invention contain 10 wt.% to 19 wt.% of alkali metal oxide R2O, which can significantly reduce the viscosity of glass melting, promote the melting and clarification of the glass melt, and significantly improve the fluidity of the glass. However, if the addition amount is too high, it is easy to cause the thermal expansion coefficient of the colored glass-ceramics to increase, resulting in changes in mechanical properties, and even seriously eroding refractory materials, requiring too high internal material requirements for the melting furnace. In some embodiments of the present invention, the content of alkali metal oxide R2O can be 10 wt.%, 11 wt.%, 12 wt.%, 13 wt.%, 14 wt.%, 15 wt.%, 16 wt.%, 17 wt.%, 18 wt.%, 19 wt.%.

[0068] Due to the relatively high content of R2O alkali metal, the performance of the colored glass-ceramics body is poor and not suitable for the application scenarios of electronic glass. Due to the high field strength of P ions in P2O5, it is easy to separate from the network, form crystal nuclei, promote phase separation of the base glass, reduce the nucleation activation energy, and facilitate glass crystallization. It has been found that when the introduction amount is less than 1.5 wt.%, crystallization is difficult to proceed; when P2O5 > 3.5 wt.%, the transparency of the glass product after crystallization is likely to decrease under the same conditions. After introducing 1.5 wt.% to 3.5 wt.% of the nucleating agent P2O5, the grain distribution in the glass-ceramics can effectively hinder the propagation of microcracks, which is beneficial to the overall improvement of the anti-scratch, anti-impact and anti-drop properties of the glass. In some embodiments of the present invention, the content of P2O5 can be 1.5 wt.%, 2.0 wt.%, 2.5 wt.%, 3.0 wt.%, 3.5 wt.%. 5+ The addition of Al2O3 can be used to increase the strength of the glass structure and improve the anti-scratch and anti-drop properties of the glass. In addition, the volume of Al2O3 in the glass structure is larger than that of the silicon-oxygen tetrahedron, which can provide a strengthening channel for the glass during the ion strengthening process and is conducive to promoting ion strengthening. Its content should not be less than 2 wt.%; however, Al2O3 is a refractory oxide, which can rapidly increase the high-temperature viscosity of the glass, reduce the fluidity of the glass, and affect the glass melting and forming. The addition amount is controlled not to be higher than 8 wt.%. In some embodiments of the present invention, the content of Al2O3 can be 2 wt.%, 3 wt.%, 4 wt.%, 5 wt.%, 6 wt.%, 7 wt.%, 8 wt.%.

[0069]

[0070] ​B2O3 belongs to network-forming oxides, which can reduce the viscosity of glass during high-temperature melting, improve the melting characteristics, and facilitate the fusion and shaping of glass. At the same time, B2O3 can form a tetrahedral structure at low temperatures, increasing the low-temperature viscosity, which is beneficial to avoiding color deposition caused by the reflow of the glass liquid injected into the mold. However, B2O3 is volatile and has an adverse effect on the melting furnace and the forehearth, so its addition amount needs to be limited to no higher than 0.5 wt.%. In some embodiments of the present invention, the B2O3 content can be 0 wt.%, 0.1 wt.%, 0.2 wt.%, 0.3 wt.%, 0.4 wt.%, 0.5 wt.%.

[0071] SnO2 is a chemical fining agent. The fining agent can decompose at high temperatures during the glass melting process, gasify to generate gas or promote the elimination or dissolution and absorption of bubbles in the glass liquid by reducing the viscosity of the glass liquid, so as to achieve a better melting effect. In the present invention, the viscosity of the glass liquid is relatively low, and it is very easy to discharge bubbles, and its addition amount is not higher than 0.2 wt.%. In some embodiments of the present invention, the SnO2 content can be 0 wt.%, 0.05 wt.%, 0.1 wt.%, 0.15 wt.%, 0.2 wt.%.

[0072] Due to the relatively low overall viscosity of the composition and the high content of R2O, it is extremely easy to crystallize during fusion and shaping, resulting in defects. Adding ZrO2 can inhibit the crystallization ability of the glass, facilitate fusion and shaping, and avoid defects. Secondly, ZrO2 can improve the toughness of the glass and can improve the brittleness of the formed glass block. However, ZrO2 belongs to an extremely refractory component and is easy to deposit, so its mass percentage is limited to 1.5 wt.% - 5 wt.%. In some embodiments of the present invention, the ZrO2 content can be 1.5 wt.%, 2.0 wt.%, 2.5 wt.%, 3.0 wt.%, 3.5 wt.%, 4.0 wt.%, 4.5 wt.%, 5.0 wt.%.

[0073] RO is an alkaline earth metal oxide, which can improve the chemical stability and mechanical strength of the glass. However, excessive RO will increase the overall brittleness of the glass and also increase the crystallization ability. Therefore, its total content is limited to 0 wt.% - 3 wt.%. In some embodiments of the present invention, the RO content can be 0 wt.%, 0.5 wt.%, 1.0 wt.%, 1.5 wt.%, 2.0 wt.%, 2.5 wt.%, 3.0 wt.%.

[0074] In the present invention, a coloring component needs to be introduced to form different color effects, and the colorant can be a transition metal or a rare earth element. A single colorant can be introduced to form a single color, or two or more coloring substances can be introduced for mixed coloring to form gorgeous gradient or mixed colors. Since the ionic field strengths of the colorants are relatively large, they will affect the crystallization mechanism of the glass body, and some will enter the crystal structure, affecting the mechanical properties. At the same time, an excessive amount of colorant will cause the backplane to be too dark in color and unable to combine with the film to show color. In the present invention, the total introduction amount of the colorant is controlled to be not more than 6 wt.%, and at the same time, considering that the thickness of the electronic glass backplane is relatively thin, which will weaken the presentation of the color, the total introduction amount of the colorant needs to be greater than 0.02 wt.%. In some embodiments of the present invention, the content of the coloring component can be 0.02 wt.%, 0.04 wt.%, 0.06 wt.%, 0.08 wt.%, 0.1 wt.%, 0.5 wt.%, 1.0 wt.%, 2.0 wt.%, 3.0 wt.%, 4.0 wt.%, 5.0 wt.%, 6.0 wt.%.

[0075] In the technical solution of the present invention, by adding a coloring component to the glass component, the colored glass-ceramics exhibit the required color. By adjusting the ratio of each component, a glass melt with a low liquidus viscosity is obtained, and its forming temperature can be between 1060 and 1250 °C, and the kinematic viscosity is 21000 mm 2 / s to 57500 mm 2 / s, which is more suitable for the fusion leakage forming of a platinum discharge tube or a platinum former. Among them, adding alkali metal oxide R2O can significantly reduce the viscosity during glass melting and forming, promote the melting and clarification of the glass melt, and significantly improve the fluidity of the glass; introducing 1.5 wt.% to 5 wt.% ZrO2 can inhibit the crystallization ability of the glass, facilitate the fusion forming, and avoid deposition due to refractory; adding alkaline earth metal oxide can improve the chemical stability and mechanical strength of the glass.

[0076] To obtain gorgeous colors, the coloring component includes at least one of TiO2, CeO2, Fe2O3, FeO, V2O5, V2O3, C r2 O3, CuO, Mn2O3, CoO, Co2O3, Er2O3, La2O3, Y2O3, Nd2O3, Pr2O3, and Pr6O 11 . Different colorants have different coloring degrees. For example, CoO / Co2O3, V2O5 / V2O3, or Cr2O3 has a strong coloring effect, and a small addition amount can result in a deeper color, so it needs to be introduced in a trace amount; for colorants such as TiO2 and CeO2, the coloring effect is weak, and their addition amount can be appropriately increased according to needs.

[0077] RO includes at least one of MgO, ZnO, and CaO, and MgO, ZnO, and CaO can improve the chemical stability and mechanical strength of the glass. Among them, Ca 2+ has a certain regulating effect on the glass viscosity, can reduce the glass viscosity, which is beneficial to the solidification of the glass liquid when it is just injected into the mold, avoids the full fusion of the colorant, and is conducive to the generation of texture.

[0078] R2O includes Li2O, and Li2O can significantly reduce the viscosity of glass melting, promote the melting and clarification of the glass liquid, significantly improve the fluidity of the glass, and is beneficial to the formation of the glass crystal phase.

[0079] R2O also includes Na2O and K2O. The mass percentage of Na2O in the colored glass-ceramics is W(Na2O), and the mass percentage of K2O in the colored glass-ceramics is W(K2O), 0% ≤ W(Na2O) + W(K2O) ≤ 3%, and the mass percentage of Li2O in the colored glass-ceramics is 10 wt.% to 16 wt.%. Na2O and K2O can significantly reduce the viscosity of glass melting, promote the melting and clarification of the glass liquid, and significantly improve the fluidity of the glass.

[0080] Excessive Li2O is extremely prone to crystallization, which affects the product quality. At the same time, it is also easy to cause blockage of the forming material pipe, seriously erodes the refractory material, and requires too high internal material quality for the melting furnace. Therefore, Li2O is controlled at 10 wt.% to 16 wt.% in the colored glass-ceramics. In some embodiments of the present invention, the content of Li2O can be 10 wt.%, 11 wt.%, 12 wt.%, 13 wt.%, 14 wt.%, 15 wt.%, 16 wt.%.

[0081] The mass percentage of Li2O in the colored glass-ceramics is W(Li2O), the mass percentage of SiO2 in the colored glass-ceramics is W(SiO2), and the mass percentage of P2O5 in the colored glass-ceramics is W(P2O5). Among them, 0.12 ≤ W(Li2O) / (W(SiO2) + 3W(P2O5)) ≤ 0.2. Within this range, the transmittance and crystallization characteristics are better balanced.

[0082] To obtain a glass melt with a low liquidus viscosity and meet the requirements of forming and color fusion, the mass percentage of R2O in the colored glass-ceramics is W(R2O), the mass percentage of RO in the colored glass-ceramics is W(RO), the mass percentage of B2O3 in the colored glass-ceramics is W(B2O3), the mass percentage of SiO2 in the colored glass-ceramics is W(SiO2), the mass percentage of Al2O3 in the colored glass-ceramics is W(Al2O3), and the mass percentage of ZrO2 in the colored glass-ceramics is W(ZrO2). Among them, 0.15 ≤ [W(R2O) + W(RO) + W(B2O3)] / [W(SiO2) + W(Al2O3) + 2W(ZrO2)] ≤ 0.3. In the research of the present invention, it is found that by limiting 0.15 ≤ [W(R2O) + W(RO) + W(B2O3)] / [W(SiO2) + W(Al2O3) + 2W(ZrO2)] ≤ 0.3, the kinematic viscosity of the glass melt within a suitable forming temperature range can be controlled to be 21000 mm 2 / s to 57500 mm 2 / s. Excessively high kinematic viscosity will lead to excessive liquid resistance and affect the flow rate under the condition of the same pipe diameter. At the same time, it is difficult for the high-viscosity glass melt to achieve the fusion of glass melts of different colors. Excessively low kinematic viscosity is prone to cause out-of-control of the flow rate and requires higher temperature control facilities for the equipment. On the other hand, the temperature of the glass melt it contains is too high, which seriously erodes the forming material pipe, affects the service life, and increases the cost.

[0083] The transmittance of the colored glass-ceramics in the 380 - 1000 nm light band is > 20%. Under this transmittance, when the colored glass-ceramics are used in combination with the diaphragm, the color rendering effect is the best.

[0084] The brightness value of the colored glass-ceramics is > 20. Under this brightness value, the transmittance of the colored glass-ceramics is better, and when used in combination with the diaphragm, the color rendering effect is the best.

[0085] The thickness of the colored glass-ceramics is 0.2 - 2 mm. Under this thickness, the transmittance of the colored glass-ceramics in the 380 - 1000 nm light band is better, and the brightness value is better. In some embodiments of the present invention, the thickness of the colored glass-ceramics can be 0.2 mm, 0.4 mm, 0.6 mm, 0.8 mm, 1.0 mm, 1.5 mm, 2.0 mm.

[0086] The colored glass-ceramics include at least one color, which can be a pure color or a mixture of multiple colors. When a single color is required, any one of yellow, green, blue, purple, and pink can be selected. In some embodiments of the present invention, it can also be other single colors.

[0087] The color of the colored microcrystalline glass includes colorful textures presented by different colors. The color of the colored microcrystalline glass includes any one of blue and gray-blue alternating distribution, blue-green alternating distribution, pink-purple alternating distribution, and cyan-green alternating distribution. It can also be presented as a mixture of other different colors.

[0088] The colorant of the colored microcrystalline glass is not only present on the external surface, but can also be distributed throughout the colored microcrystalline glass body. It can also be distributed in a gradient color, and can also present different colors at different surface positions and different thicknesses, gradually weakening from thick to thin.

[0089] In order to ensure the color rendering effect of the surface, the colors of the colored micro-ceramic glass are irregularly distributed on the surface to achieve a three-dimensional, saturated color effect.

[0090] In order to ensure the coloring effect inside the glass, the colors of the colored micro-ceramics are irregularly and alternately distributed inside the glass to achieve a three-dimensional, saturated color effect.

[0091] Specifically, the irregular distribution of the colors of the colored microcrystalline glass may include the alternating distribution of colors and colorless (containing no coloring components), or the alternating distribution of different colors, wherein the different colors include different shades and types of colors.

[0092] The present invention also provides a method for preparing colored microcrystalline glass, comprising the following steps:

[0093] Weigh the raw materials including the base component and the raw materials including the coloring component;

[0094] Melting raw materials containing basic components to obtain glass liquid;

[0095] Mixing a raw material containing a coloring component with glass liquid to obtain a colored glass liquid;

[0096] The colored glass liquid is melted, formed, and annealed to obtain colored glass products;

[0097] The colored glass product is subjected to crystallization treatment to obtain colored micro-ceramic glass.

[0098] In the technical solution of the present invention, a glass liquid is first melted containing raw materials of basic components, and then a raw material containing a coloring component is mixed with the glass liquid to obtain a colored glass liquid. After the glass liquid is formed and annealed, it is crystallized so that the strength, hardness and drop resistance of the colored microcrystalline glass meet the requirements.

[0099] Further, when the colored glass-ceramics is a pure color (including one color), the technical solution of the present invention can combine the steps of "melting the raw materials containing the basic components to obtain a glass melt" and "mixing the raw materials containing the coloring components with the glass melt to obtain a colored glass melt", that is, the technical solution can first melt the raw materials containing the basic components to obtain a glass melt, and then mix the raw materials containing the coloring components with the glass melt to obtain a colored glass melt; it can also melt and shape the raw materials containing the basic components and the raw materials containing the coloring components together to obtain a colored glass melt; it can also first melt the raw materials containing the basic components to obtain a glass melt, then melt the raw materials containing the coloring components, and then mix them with the glass melt to obtain a colored glass melt.

[0100] In the step of "mixing the raw materials containing the basic components and then melting them to obtain a glass melt"; the melting temperature is 1350 - 1500 °C. At this temperature, it can ensure that all components are fully melted, facilitating shaping.

[0101] In the step of "fusing and shaping the colored glass melt and annealing to obtain a colored glass product", the kinematic viscosity of the glass melt is 21000 mm 2 / s - 57500 mm 2 / s. Excessively high kinematic viscosity will lead to too large a liquid resistance, affecting the flow rate under the condition of the same pipe diameter. At the same time, it is difficult for the high-viscosity glass melt to achieve the mutual fusion of glass melts of different colors. Excessively low kinematic viscosity is likely to cause out-of-control of the flow rate, requiring higher temperature control facilities for the equipment. On the other hand, if the temperature of the glass melt it contains is too high, it will seriously erode the forming material pipe, affecting its service life and increasing the cost.

[0102] Due to the relatively high Li content in the glass composition, it is extremely easy to crystallize during glass forming. It is necessary to control its forming temperature higher than the upper limit temperature of crystallization. At the same time, it is also necessary to meet the requirement that the kinematic viscosity of the glass melt is 21000 mm 2 / s - 57500 mm 2 / s, and control the forming temperature of the glass melt to be 1060 - 1250 °C.

[0103] In addition, the annealing temperature of the glass melt is 440 - 520 °C, which can better eliminate stress and improve the anti-drop performance of the glass-ceramics.

[0104] Further, in the step of "mixing the raw materials containing the coloring components with the glass melt to obtain a colored glass melt", it includes: draining through at least one runner, and adding at least one colored glass melt obtained by mixing the raw materials containing the coloring components with the glass melt in the runner. Specifically, using runner drainage makes the basic components of the colored glass-ceramics the same, facilitating the better fusion of different colored glass melts.

[0105] Furthermore, in the step of "mixing the raw material containing the coloring component with the glass liquid to obtain the colored glass liquid", the step includes: firstly mixing the raw material containing the basic component and the raw material containing the coloring component, melting them, discharging them, quenching them in water, and grinding them to obtain colored cullet powder, and then melting the colored cullet powder and mixing it with the glass liquid to obtain the colored glass liquid. Specifically, a multi-channel drainage can be set up, and colored cullet powder can be added at each channel, wherein the colored cullet powder is mixed with the raw material containing the basic component and the raw material containing the coloring component, melting them, discharging them, quenching them in water, and grinding them, so as to facilitate the control of the trace introduction of the coloring component. After clarifying and stirring the molten glass through the channel, the molten glass is obtained, and the molten glass is cooled to 1060-1250°C and enters the platinum discharge pipeline or the platinum former for fusion molding.

[0106] Furthermore, in the step of "melting the colored glass liquid into a mold and annealing it to obtain a colored glass product", the molding step includes: melting and molding at least one colored glass liquid by a fusion leakage molding method. The coloring component and the glass liquid mixture are molded by a platinum pipe or a platinum former through a multi-channel fusion leakage molding method. On the one hand, platinum has a high melting point and good stability, and is not easy to react with the glass component. The multi-channel fusion leakage molding method can make the glass liquid fuse with the coloring component after cooling, and avoid high temperature causing the coloring component to change color or fade; on the other hand, the multi-channel fusion leakage molding method can control different combinations of channels to obtain a variety of different colored microcrystalline glass, and can also control the glass liquid of different channels to be mixed according to different dosage ratios, and can also control the glass liquid of different channels to be mixed in different orders, so that the colored microcrystalline glass presents a colorful texture.

[0107] Furthermore, in the step of "melting the colored glass liquid into a shape and annealing it to obtain a colored glass product", before the step of melting the colored glass liquid into a shape, the step includes: stirring and mixing at least two colored glass liquids. Specifically, the at least two colored glass liquids can be at least one colored glass liquid and glass liquid (without a colored component), or at least two colored glass liquids of different colors, wherein the different colors include different shades of color and different types. Specifically, the stirring and mixing can be uniform stirring or uneven stirring.

[0108] In the step of "crystallizing the colored glass product to obtain colored microcrystalline glass", the crystallization treatment includes a first crystallization treatment and a second crystallization treatment performed in sequence. Specifically, the annealed glass composition sample can be placed in a common crystallization furnace or a box furnace with an atmosphere for heat treatment, and the atmosphere can be a reducing atmosphere or an oxidizing atmosphere. Through the two crystallization treatments, the crystallinity in the colored microcrystalline glass can be greater than 30%, and the crystal phase after crystallization can be a combination of two or more of cristobalite, lithium metasilicate, lithium disilicate, petalite, and lithium phosphate.

[0109] The temperature of the first crystallization treatment is 520 - 640 °C. Through the temperature of 520 - 640 °C, the crystallinity of crystallization can be made > 30%.

[0110] The heat preservation time of the first crystallization treatment is 30 - 240 min. Through the heat preservation time of 30 - 240 min, the crystallinity of crystallization can be made > 30%.

[0111] The temperature of the second crystallization treatment is 670 - 800 °C. Through the temperature of 670 - 800 °C, the crystal phases after crystallization can be two or more combinations of cristobalite, lithium metasilicate, lithium disilicate, spodumene, and lithium phosphate.

[0112] The heat preservation time of the second crystallization treatment is 30 - 60 min. Through the heat preservation time of 30 - 60 min, the crystal phases after crystallization can be two or more combinations of cristobalite, lithium metasilicate, lithium disilicate, spodumene, and lithium phosphate.

[0113] After two crystallization treatments, the crystallinity of the colored glass-ceramics > 30%.

[0114] After the step of "crystallizing the colored glass product to obtain colored glass-ceramics", it further includes: performing ion exchange on the colored glass-ceramics to obtain chemically strengthened colored glass-ceramics; wherein, the bath salts used for ion exchange include 30 wt.% - 100 wt.% of sodium salts, 0 wt.% - 70 wt.% of potassium salts, and 0 wt.% - 0.2 wt.% of lithium salts. The ion exchange can be a one-step or two-step method; the composition of the bath salts used is a mixture of potassium, sodium, and lithium ions. Among them, to ensure the sodium-lithium exchange efficiency, the proportion of sodium content needs to be ≥ 30%; without being limited to theory, it is found through research that introducing lithium into the bath salts makes the stress curve distribution of the sample relatively smooth, which has a good effect on improving the anti-drop performance of the colored glass-ceramics.

[0115] The ion exchange is one-step ion exchange or two-step ion exchange, and the temperature of the ion exchange is 450 - 520 °C. At this temperature, the ion exchange efficiency is the best.

[0116] The time of the ion exchange is 5 - 12 h. At this time, the ion exchange effect is the best.

[0117] For the strengthened colored glass-ceramics treated by the ion exchange bath, the stress layer depth is 0.15*t - 0.24*t um (t is the thickness of the colored glass-ceramics). To ensure the color rendering effect and anti-drop performance, the thickness of the colored glass-ceramics should not be too thick or too thin; its Vickers hardness can reach 710 kgf / mm 2 above, with good hardness; the average value of its 4PB test is greater than 730 N / mm 2 and has good flexural properties.

[0118] The present invention also provides an electronic product, which includes a backplane. The material of the backplane includes the colored microcrystalline glass described above. The electronic product includes all the technical solutions of the colored microcrystalline glass, so it also has all the beneficial effects brought by the above technical solutions, which will not be elaborated here one by one. The electronic products include mobile phones, tablet computers, televisions, computer displays, and smart watches.

[0119] The technical solutions of the present invention will be further described in detail below in conjunction with specific embodiments and drawings. It should be understood that the following embodiments are only used to explain the present invention and are not used to limit the present invention.

[0120] The specific embodiments of the present invention are shown in Table 1, Table 2, and Table 3. Among them, Examples 1-10 are monochromatic colored microcrystalline glass, and Examples 11-14 are polychromatic colored microcrystalline glass. The formulations and parameters of Examples 1 to 10 are shown in Table 1.

[0121] The preparation method is as follows: First, select the corresponding raw materials according to the oxides of each basic component, weigh and mix them evenly according to their purity, moisture content, and proportion range to obtain a meltable mixture. Put the uniform mixture into a glass furnace and melt it in the temperature range of 1350-1500°C. Add the corresponding raw materials selected according to the oxides of the coloring components. After clarification in the forehearth and stirring and homogenization, a colored glass liquid is obtained. Cool the colored glass liquid to 1060-1250°C and enter a platinum discharging pipeline or a platinum forming device for forming. Put the formed colored glass products into an annealing furnace at 440-520°C for stress relief. After annealing is completed, cool them to room temperature with the furnace and take them out to obtain processable colored glass products.

[0122] Cut the colored glass products into sheets and put them into a crystallization furnace for crystallization heat treatment. The process conditions are as follows in the table to obtain colored (pure color) microcrystalline glass products.

[0123] Table 1 Formulations and parameters of Examples 1 to 10

[0124]

[0125]

[0126]

[0127] Examples 1-10 are chemically strengthened. Among them, Examples 1, 3, 5, and 8 adopt a two-step ion exchange method for chemical strengthening, and Examples 2, 4, 6, 7, 9, and 10 adopt a one-step ion exchange method for chemical strengthening. The ion exchange treatment conditions of Examples 1-10 are shown in Table 2:

[0128] The preparation method of ion exchange is as follows: after the prepared colored glass-ceramics are ground and polished, ion exchange strengthening treatment is further carried out. The steps are as follows: place the sheet sample (0.6 mm) in a preheating furnace for heat preservation, then place the product in molten salt. The process parameters are shown in the following table. After completion, place the product in a muffle furnace for rapid cooling; clean the surface residues of the colored glass-ceramics with hot water for subsequent testing.

[0129] Table 2 Ion exchange treatment conditions for Examples 1-10

[0130]

[0131]

[0132] Examples 11-14 are multicolor colored glass-ceramics, and their formulas and parameters are shown in Table 3.

[0133] The preparation method is as follows: select the corresponding raw materials according to the oxides of each basic component, weigh and mix them evenly according to their purity, moisture content and proportion range to obtain a fusible mixture. Put the weighed and evenly mixed mixture (without coloring agent components) into a glass melting furnace and melt it into glass liquid in the temperature range of 1350-1500 °C. Set multiple channels (2 in the example) for drainage, and add the corresponding raw materials selected according to the oxides of each coloring component at each channel. After clarification and stirring homogenization in the channels, colored glass liquid is obtained. Cool the colored glass liquid to 1060-1250 °C and enter a platinum discharge pipe or a platinum former for fusion molding. Put the formed colored glass products into an annealing furnace at 440-520 °C for stress relief. After annealing is completed, cool them in the furnace to room temperature and take them out to obtain processable colored glass products.

[0134] Cut the colored glass products into sheets and put them into a crystallization furnace for crystallization heat treatment. The process conditions are as follows in the table to obtain colored (multicolor) glass-ceramics.

[0135] Table 3 Formulas and parameters of Examples 11 to 14

[0136]

[0137]

[0138]

[0139] Examples 11-14 are chemically strengthened, and the ion exchange treatment conditions for Examples 11-14 are shown in Table 4:

[0140] The preparation method of ion exchange is as follows: after the prepared colored glass-ceramic products are ground and polished, ion exchange strengthening treatment is further carried out. The steps are as follows: place the sheet sample (0.6 mm) in a preheating furnace for heat preservation, then place the product in molten salt. The process parameters are shown in the following table. After completion, place the product in a muffle furnace for rapid cooling; clean the surface residues of the colored glass-ceramic products with hot water for subsequent testing.

[0141] Table 4 Ion bath treatment conditions for Examples 11 - 14

[0142]

[0143]

[0144] Performance testing

[0145] Perform color, crystal phase, transparency, crystallinity, transmittance (%) in the range of 380 - 1000 mm, brightness value, hardness, depth of stress layer (DOC (μm)), and flexural strength (4PB (N / mm 2 )) measurements on the colored glass-ceramics prepared in Examples 1 - 14.

[0146] Among them, the crystallinity and phase are determined by comparing the XRD diffraction peaks with the database spectra to determine the crystal phase, and the proportion of the diffraction intensity of the crystalline phase in the overall spectrum intensity is calculated by the Rietveld method to obtain the crystallinity and amorphous content; the transmittance is tested with a UV-visible spectrophotometer; the Vickers hardness is measured with a Vickers hardness tester, the loading force is 200 g, and the loading time is 15 s; the brightness value L* is tested with a UV-visible spectrophotometer; the depth of stress layer DOC represents the depth where the stress in the glass-ceramic changes from compression to tension, and is tested with an SLP-2000 surface stress meter; the four-point bending performance 4PB is tested with a universal testing machine. The measurement results are shown in Table 5:

[0147] For the colored glass-ceramics of Examples 1 - 10 before the ion bath, measure their color, crystal phase, transparency, transmittance (%) in the range of 380 - 1000 mm, and crystallinity. The results are shown in Table 5:

[0148] Table 5 Performance test results of colored glass-ceramics in Examples 1 - 10 (I)

[0149]

[0150]

[0151] Perform performance testing on the colored glass-ceramics of Examples 1 - 10 after the ion bath, and measure their hardness (kgf / mm 2 ), DOC (μm), 4PB (N / mm 2) The results are shown in Table 6.

[0152] Table 6 Performance Test Results of Color Microcrystalline Glass in Examples 1-10 (Part II)

[0153]

[0154] For the color microcrystalline glass of Examples 11-14 before the ion bath, its color, crystal phase, transparency, transmittance (%) in the range of 380-1000 mm, and crystallinity were measured. The results are shown in Table 7:

[0155] Table 7 Performance Test Results of Color Microcrystalline Glass in Examples 11-14 (Part I)

[0156]

[0157]

[0158] Performance tests were carried out on the color microcrystalline glass of Examples 11-14 after the ion bath, and its hardness (kgf / mm 2 ), DOC (um), 4PB (N / mm 2 ) were measured. The results are shown in Table 8

[0159] Table 8 Performance Test Results of Color Microcrystalline Glass in Examples 11-14 (Part II)

[0160] Performance Example 11 Example 12 Example 13 Example 14 <![CDATA[Hardness (kgf / mm 2 )]]> 745 750 748 755 DOC(um) 118 120 117 118 <![CDATA[4PB (N / mm 2 )]]> 736 752 741 744

[0161] As can be seen from Tables 5-8 above, the color microcrystalline glass prepared in Examples 1-14 all meet the usage requirements.

[0162] The above are only the preferred embodiments of the present invention, and do not limit the patent scope of the present invention. For those skilled in the art, the present invention can have various changes and modifications. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included within the patent protection scope of the present invention.

Claims

1. A colored glass-ceramics, characterized in that, In oxide form, by mass percentage, it includes: Base components, including: SiO2: 67% - 73%, R2O: 10% - 19%, Al2O3: 2% - 8%, B2O3: 0 - 0.5%, SnO2: 0 - 0.2%, ZrO2: 1.5% - 5%, RO: 0.5% - 3%, P2O5: 1.5% - 3.5%; and Coloring components, including at least one of oxides of transition metals or rare earth elements, with a mass percentage of 0.02% - 6%; where R2O is an alkali metal oxide; RO is an alkaline earth metal oxide, and RO includes CaO; The mass percentage of R2O in the colored glass-ceramics is W(R2O), the mass percentage of RO in the colored glass-ceramics is W(RO), the mass percentage of B2O3 in the colored glass-ceramics is W(B2O3), the mass percentage of SiO2 in the colored glass-ceramics is W(SiO2), the mass percentage of Al2O3 in the colored glass-ceramics is W(Al2O3), and the mass percentage of ZrO2 in the colored glass-ceramics is W(ZrO2), where 0.15 ≤ [W(R2O) + W(RO) + W(B2O3)] / [W(SiO2) + W(Al2O3) + 2W(ZrO2)] ≤ 0.

3.

2. The colored glass-ceramics according to claim 1, wherein The coloring component includes at least one of TiO2, CeO2, Fe2O3, FeO, V2O5, V2O3, Cr2O3, CuO, Mn2O3, CoO, Co2O3, Er2O3, La2O3, Y2O3, Nd2O3, Pr2O3, and Pr6O 11 in 3. The colored glass-ceramics according to claim 1, wherein RO also includes MgO and / or ZnO.

4. The colored glass-ceramics according to claim 1, characterized in that, R2O includes Li2O.

5. The colored glass-ceramics according to claim 4, wherein R2O also includes Na2O and K2O. The mass percentage of Na2O in the colored glass-ceramics is W(Na2O), the mass percentage of K2O in the colored glass-ceramics is W(K2O), 0% ≤ W(Na2O) + W(K2O) ≤ 3%, and the mass percentage of Li2O in the colored glass-ceramics is 10% - 16%.

6. The colored glass-ceramics according to claim 4, wherein The mass percentage of Li2O in the colored glass-ceramics is W(Li2O), the mass percentage of SiO2 in the colored glass-ceramics is W(SiO2), and the mass percentage of P2O5 in the colored glass-ceramics is W(P2O5), where 0.12 ≤ W(Li2O) / (W(SiO2) + 3W(P2O5)) ≤ 0.

2.

7. The colored glass-ceramics according to claim 1, wherein, The transmittance of the colored glass-ceramics in the 380 - 1000 nm light band > 20%; and / or The brightness value of the colored glass-ceramics > 20.

8. The colored glass-ceramics according to claim 1, characterized in that, The thickness of the colored glass-ceramics is 0.2 - 2 mm.

9. The colored glass-ceramics according to claim 1, wherein, The colored glass-ceramics include at least one color.

10. The colored glass-ceramics according to claim 9, wherein, The color of the colored glass-ceramics includes any one of yellow, green, blue, purple, and pink.

11. The colored glass-ceramics according to claim 9, characterized in that, The color of the colored glass-ceramics includes any one of blue and gray-blue distributed alternately, blue-green distributed alternately, pink-purple distributed alternately, and blue-green distributed alternately.

12. The colored glass-ceramics according to claim 9, characterized in that, The colors of the colored glass-ceramics are distributed alternately without regularity inside the glass; and / or The colors of the colored glass-ceramics are distributed alternately without regularity on the glass surface.

13. The colored glass-ceramics according to claim 1, wherein, The crystallinity of the colored glass-ceramics > 30%.

14. The colored microcrystalline glass according to claim 1, wherein, The crystal phases of the colored glass-ceramics are at least two of cristobalite, lithium metasilicate, lithium disilicate, spodumene, and lithium phosphate.

15. The colored glass-ceramics according to claim 1, wherein The thickness of the colored glass-ceramics is t, and the depth of the stress layer of the colored glass-ceramics is doc, where doc is 0.15*t to 0.24*t; and / or, The Vickers hardness of the colored glass-ceramics is at least 710 kgf / mm 2 ; and / or, The four-point bending property of the colored glass-ceramics is 4PB, where the 4PB value is greater than or equal to 730 N / mm 2 .

16. A method for preparing a colored glass-ceramics according to any one of claims 1 to 15, characterized in that, It includes the following steps: Weigh the raw materials containing basic components and the raw materials containing coloring components; Melt the raw materials containing basic components to obtain a glass melt; Mix the raw materials containing coloring components with the glass melt to obtain a colored glass melt; Fuse and shape the colored glass melt and perform annealing treatment to obtain a colored glass product; the shaping temperature of the colored glass melt is 1060 - 1250 °C; Perform crystallization treatment on the colored glass product to obtain colored glass-ceramics.

17. The preparation method of the colored glass-ceramics according to claim 16, characterized in that, In the step of "melting the raw materials containing basic components after mixing to obtain a glass melt", The melting temperature is 1350 - 1500 °C.

18. The method for preparing the colored glass-ceramics according to claim 16, wherein, In the step of "fusing and shaping the colored glass melt and performing annealing treatment to obtain a colored glass product", The kinematic viscosity of the colored glass liquid is 21000 mm 2 / s to 57500 mm 2 / s; and / or, The annealing temperature of the colored glass melt is 440 - 520 °C.

19. The method for preparing the colored glass-ceramics according to claim 16, characterized in that, In the step of "mixing the raw materials containing coloring components with the glass melt to obtain a colored glass melt", it includes: Drain the glass melt through at least one runner, and add at least one kind of colored glass melt obtained by mixing the raw materials containing coloring components with the glass melt in the runner.

20. The method for preparing the colored glass-ceramics according to claim 16, characterized in that, In the step of "mixing the raw materials containing coloring components with the glass melt to obtain a colored glass melt", the step includes: First, mix the raw materials containing basic components and the raw materials containing coloring components, melt them, discharge the molten material, quench it with water, grind it to make colored broken glass powder, and melt the colored broken glass powder and mix it with the glass melt to obtain a colored glass melt.

21. The method for preparing the colored glass-ceramics according to claim 16, characterized in that, In the step of "fusing and shaping the colored glass melt and performing annealing treatment to obtain a colored glass product", the shaping step includes: Fuse and shape at least one kind of colored glass melt by the method of fusing and leaking material for shaping.

22. The method for preparing the colored glass-ceramics according to claim 21, wherein, Before the step of "fusing and shaping the colored glass melt and performing annealing treatment to obtain a colored glass product", Stir and mix at least two kinds of colored glass melts.

23. The preparation method of the colored glass-ceramics according to claim 16, wherein, In the step of "performing crystallization treatment on the colored glass product to obtain colored glass-ceramics", the crystallization treatment includes the first crystallization treatment and the second crystallization treatment carried out in sequence; The temperature of the first crystallization treatment is 520 - 640 °C, and the heat preservation time of the first crystallization treatment is 30 - 240 min; and / or, The temperature of the second crystallization treatment is 670 - 800 °C, and the heat preservation time of the second crystallization treatment is 30 - 60 min.

24. The method for preparing the colored glass-ceramics according to claim 16, characterized in that, After the step of "performing crystallization treatment on the colored glass product to obtain colored glass-ceramics", it further includes: Perform ion exchange on the colored glass-ceramics to obtain chemically strengthened colored glass-ceramics; Among them, the bath salt used for the ion exchange includes 30 wt.% - 100 wt.% of sodium salt, 0 wt.% - 70 wt.% of potassium salt, and 0 wt.% - 0.2 wt.% of lithium salt.

25. The preparation method of the colored glass-ceramics according to claim 24, characterized in that, The ion exchange is one-step ion exchange or two-step ion exchange; and / or, The temperature of the ion exchange is 450 - 520 °C; and / or, The time of the ion exchange is 5 - 12 h.

26. An electronic product, characterized in that, The electronic product includes the colored glass-ceramics as described in any one of claims 1 to 15.

Images