A microcrystalline glass display screen and a method of manufacturing the same

Abstract

The present application relates to a kind of microcrystalline glass display screen and its preparation method, the film-coated glass is the microcrystalline glass or glass ceramic containing hydrophobic and oleophobic composite coating on its surface, it is characterized in that, from the surface of glass, it includes: hydrophobic and oleophobic layer, intermediate layer, primer layer and microcrystalline glass or glass ceramic, wherein, the intermediate layer is the intermediate layer formed by containing lattice energy 700-3000kJ / mol ionic crystal, the primer layer includes the compound containing Si-O bond or mixed silicon oxide layer.By the present application, even if there is little Si-O structure in the film-coated interface of microcrystalline glass, a firm, durable, excellent performance hydrophobic and oleophobic coating can also be formed, whether high crystallinity glass has been ion exchanged or not, excellent hydrophobic and oleophobicity can be achieved.

Description

[0001] This application is a divisional application of the Chinese patent application with application number 202110128889.1, invention name “A coated microcrystalline glass with improved hydrophobicity and oleophobicity, its preparation method and application”, and application date January 29, 2021. Technical Field

[0002] The present invention relates to a coated glass with hydrophobic and oleophobic properties, a preparation method and application thereof, and in particular to a microcrystalline glass having a hydrophobic and oleophobic composite coating on its surface with high crystallinity, and particularly to a microcrystalline glass display screen and a preparation method thereof. Background Art

[0003] Glass generally has a high surface activity, resulting in poor water and oil repellency, meaning it easily clings to dirt, making it difficult to clean. In many applications, such as stoves, range hoods, mobile phones, tablets, and touchscreen human-computer interaction windows, a "water-repellent" film is applied to the glass surface to reduce its surface activity, enhance its water and oil repellency, and improve its hydrophobicity. This increased hydrophobicity results in a noticeable increase in "sliding" when a finger touches the glass surface. This increased hydrophobicity reduces the coefficient of sliding friction, which improves the user experience for touch interfaces.

[0004] In the prior art, to improve the hydrophobic and oleophobic properties of glass surfaces, a method of directly coating the glass surface is commonly used. The coating material is typically PFPE (perfluoropolyether, a type of fluoropolyether silicon oxide). The structure of the fluoropolyether silicon oxide (e.g., alkoxysilicide) is shown in the following formula (1):

[0005]

[0006] Among them, R can be carbon, hydrogen or silicon; Y can be an ether bond, a sulfur-containing hydrocarbon group, a sulfur-containing alkoxy group, a nitrogen-containing hydrocarbon group, a nitrogen-containing alkoxy group, an epoxyalkyl group, an acyloxyalkyl group, a hydrocarbon group, a thiol group, etc.

[0007] The process of connecting PFPE to glass is a chemical reaction process, PFPE hydrolysis (PFPE-Si-OR+H2O->PFPE-Si-OH+ROH), coupled with dehydration condensation reaction (such as Figure 1 As shown, PFPE-Si-OH+HO-Si→H2O+PFPE-Si-O-Si-), the PFPE film is finally connected to the Si-O structure on the glass interface by valence bonds, rather than relying on the van der Waals force between molecules like most vacuum coatings.

[0008] The conventional coating methods are generally described as follows. Given the large amount of Si-O structures in glass, PFPE is able to react directly with glass to form a film. However, the SiO2 mass fraction in glass typically does not exceed 70%. To improve coating quality and durability, the following two coating methods are generally used:

[0009] a) Dry method: also known as vacuum coating method, a layer of SiO2 coating is coated on the glass surface in a vacuum to increase the Si-O ratio, and then a layer of PFPE is coated in a vacuum environment;

[0010] b) Wet method: also known as spray coating method, the glass surface is first bombarded with plasma in the atmosphere, which on the one hand cleans the glass surface and on the other hand roughens the glass surface, increasing the glass surface area under the microscopic level and indirectly increasing the Si-O ratio. Then a layer of PFPE solution is sprayed.

[0011] Existing patent CN208747932U discloses the structure of an antifouling coating on the surface of a transparent microcrystalline glass, characterized in that a colorless and transparent antifouling layer (11) with a thickness of 4-30 nm is attached to the outer surface of the microcrystalline glass body (1), and the antifouling layer (11) is a fluorine-silicon hydrolyzed compound. The patent describes a microcrystalline glass device characterized in that a silicon dioxide layer with a thickness of 3-20 nm is provided below the antifouling layer (11).

[0012] However, the patent focuses on the glass-ceramic characteristic that "the mass ratio of the crystalline phase to the glass phase in the glass-ceramic body is 0.25-1.2," which is considered a glass-ceramic with medium to low crystallinity. The glass phase in the glass-ceramic body is uniformly wrapped around the crystal phase, and the glass phase contains alkali metal ions such as sodium, lithium, and potassium. The mass of the alkali metal oxide in the glass phase divided by (the mass of the aluminum oxide plus the mass of the silicon dioxide) is 6%-30%. The crystallinity of the glass-ceramic is 20-54.54%, and the Si-O structure in the glass phase is still sufficient to support the formation of a good valence bond between PFPE and the glass-ceramic. However, the invention does not mention the relevant issues regarding high-crystallinity glass-ceramics.

[0013] Existing patent CN106715352A addresses the problem of poor adhesion and durability of amphiphobic or anti-fingerprint coatings on prestressed glass surfaces produced by ion exchange: "It has been found that chemical prestressing significantly reduces the durability of amphiphobic or anti-fingerprint coatings. This is shown, for example, by shorter durability in corresponding tests, such as the neutral salt spray test, which is specifically described in WO 2012 / 163946 and WO 2012 / 163947." The patent discloses its solution as follows: The present invention is therefore based on the following object, namely, to overcome the shortcomings of the prior art and provide a glass substrate that is chemically prestressed and has an amphiphobic coating that has sufficient long-term durability. A method for producing a coated and chemically prestressed glass substrate should also be provided. The above object is achieved in a surprising manner, namely, chemically prestressing the glass substrate through all layers on the glass by ion exchange, subsequently activating the functional coating present on the glass substrate, and then applying the amphiphobic coating that acts as an anti-fingerprint coating. "That is to say, first, a "functional coating" is applied to the glass that has not undergone ion exchange, and then "ion exchange" is performed, followed by "activation of the functional coating", and then "amphiphobic coating". Among them, the patent mentions that it is found to be particularly advantageous that the functional layer, especially the uppermost functional layer, preferably includes one or more Si compounds, and particularly preferably one or more silicon oxide compounds, which can be selected from silicon oxides, for example. Preferably, they are: silicon oxide SiOx, where x is less than or equal to 2; SiOC; SiON; SiOCN and Si3N4; and hydrogen that can be combined with SiOx (x is less than or equal to 2), SiOC, SiON and SiOCN in any amount. In a preferred embodiment, the functional layer, especially the uppermost functional layer, is a silicon mixed oxide layer. Therefore, the patent discloses that the "functional coating" is mainly composed of inorganic components containing Si-O structure. The patent points out that "the long-term stability of the amphiphobic coating is generally weakened by chemical prestressing. This defect is eliminated according to the present invention. According to the present invention, after chemical prestressing, the surface of at least one functional layer is activated so that the surface of the functional layer interacts with the amphiphobic coating to be applied. The patent states that the accumulation of potassium ions on the surface of the topmost functional layer reduces the number of effective bonding sites, such as Si-OH groups in the Si-containing functional layer, thereby hindering covalent bonding to the amphiphobic coating, resulting in poor adhesion and low long-term stability of the amphiphobic coating. Furthermore, the surface of the topmost functional layer is often loaded with organic and inorganic contaminants that interfere with the desired interaction. Therefore, the patent adjusts the order of ion exchange and uses surface activation to activate Si-O to increase the bonding capacity of the amphiphobic coating. In other words, the patent is entirely a technical optimization for glass rich in Si-O structure and functional primer rich in Si-O structure. Summary of the Invention

[0014] The present invention targets the principle of glass coating in the prior art, which is based on a hydrophobic and oleophobic coating on an inorganic glass substrate. Generally speaking, the hydrophobic and oleophobic effect can be achieved: the initial water drop angle test is above 110° and around 115°, and after 5,000 frictions, the water drop angle can still reach above 100°; but for high-crystallinity microcrystalline glass with a crystallinity greater than 60%, the effect is very poor when it is done according to the principles and practices of the prior art (using surface activation to activate Si-O to increase the absorption capacity of the amphiphobic coating). The initial water drop angle can generally only reach around 100°, and after 2,500 frictions, the water drop angle is only around 60°. Microcrystalline glass is also a type of glass, and the Si-O content in its composition is no less than that of ordinary inorganic glass, but why is there such a big difference? It can be understood that traditional practices are all hydrophobic and oleophobic coating solutions formulated for interfaces rich in Si-O structures. These solutions cannot work effectively in the case of high crystallinity or the lack of glass phase or Si-O structure on the interface.

[0015] In order to solve the above-mentioned prior art problems, the present invention provides the following technical solutions:

[0016] A microcrystalline glass having a hydrophobic and oleophobic composite coating on its surface, characterized in that, starting from the outermost surface of the microcrystalline glass, it includes: a hydrophobic and oleophobic layer, an intermediate layer and a base layer in sequence, wherein the intermediate layer is an ionic crystal intermediate layer containing a lattice energy of 700-3000 kJ / mol, and the base layer includes a compound containing Si-O bonds or a mixed silicon oxide layer.

[0017] Preferably, for any of the aforementioned glass-ceramics, its crystallinity may be greater than 60%; or greater than 70%; or greater than 80%.

[0018] Preferably, for any of the aforementioned glass-ceramics, the intermediate layer is an intermediate layer formed by an ionic crystal having a lattice energy of 725-3000 kJ / mol, more preferably 770-3000 kJ / mol as the original coating material;

[0019] Alternatively, a compound with a lattice energy of 9400-11400 kJ / mol, preferably a fluorosilicon compound, is used as the original coating material to form the fluoride intermediate layer.

[0020] Preferably, for any of the aforementioned glass-ceramics, the intermediate layer contains alkali metal fluoride or alkaline earth metal fluoride compounds; or the intermediate layer is formed by using ionic crystals selected from alkali metal fluorides and alkaline earth metal fluorides as the original coating material.

[0021] Preferably, for any of the aforementioned glass-ceramics, the intermediate layer is an ionic crystal intermediate layer having a lattice energy of less than 1050 kJ / mol, preferably less than 940 kJ / mol.

[0022] Preferably, for any of the aforementioned glass-ceramics, the intermediate layer is a crystal formed by at least one ionic crystal of LiF, NaF and / or KF as the original coating material; or an intermediate layer formed by at least one of MgF2, CaF2, SrF2 or BaF2 as the original coating material; or a fluoride intermediate layer formed by coating at least one of Li2SiF6, Na2SiF6, K2SiF6, Rb2SiF6, Cs2SiF6, BeSiF6, MgSiF6, CaSiF6, SrSiF6, or BaSiF6 as the original coating material; preferably, the intermediate layer is formed by NaF or KF ionic crystals as the original coating material.

[0023] Preferably, for any of the aforementioned glass-ceramics, the intermediate layer is a polar or non-polar compound; preferably a polar compound.

[0024] Preferably, for any of the aforementioned glass-ceramics, the thickness of the intermediate layer is 1-5 nm, preferably 1-2 nm.

[0025] Preferably, for any of the aforementioned glass-ceramics, the thickness of the base layer is 3-15 nm, preferably 5-10 nm, and more preferably 5-8 nm.

[0026] Preferably, for any of the aforementioned glass-ceramics, the thickness of the hydrophobic and oleophobic layer is not less than 10 nm, preferably not less than 15 nm, and can be 10 nm-25 nm.

[0027] Preferably, for any of the above-mentioned glass-ceramics, in the case where the bottom layer is multi-layer, the compound containing Si-O bonds or the mixed silicon oxide layer is used as the outermost bottom layer, and the mixed silicon oxide is silicon oxide SiO x A mixture with at least one oxide of an element other than silicon and / or magnesium fluoride, wherein x is less than or equal to 2;

[0028] Preferably, the other elements are elements selected from aluminum, tin, magnesium, phosphorus, cerium, zirconium, titanium, cesium, barium, strontium, niobium, zinc or boron; more preferably, the mixed silicon oxide is silicon oxide SiO x A mixture of aluminum oxide.

[0029] Preferably, for any of the aforementioned glass-ceramics, the compound containing Si-O bonds is SiOx, where x is less than or equal to 2; or it is any one of SiOC, SiON, SiOCN and / or Si3N4, or a hydrogen bond combined with any one of SiOx, SiOC, SiON and / or SiOCN in any proportion, where x is less than or equal to 2.

[0030] Preferably, for any of the aforementioned glass-ceramics, the hydrophobic and oleophobic layer is a fluorine-based polymer layer, preferably a fluorine-containing polyether silicon oxide layer with a molecular weight of not less than 2000; and the coating thickness is preferably not less than 10 nm.

[0031] Preferably, for any of the above-mentioned glass-ceramics, the glass-ceramics composition contains the following mol% ratios of oxides:

[0032] SiO2: 40-75%, preferably 45-72%;

[0033] Al2O3: 2-20%, preferably 4-15%;

[0034] B2O3: 0-20%, preferably 0.4-1.6%;

[0035] P2O5: 0-10%, preferably 0.8-1.5%;

[0036] ZrO2+TiO2: 0-15%, preferably 0.9-4%;

[0037] MgO: 0-5%, preferably 0.1-2%;

[0038] ZnO: 0-4%, preferably 0.9-3.0%;

[0039] Rare earth oxides: 0-5%, preferably 0.01-1%;

[0040] Na2O: 0-5.5%;

[0041] K2O: 0-4%;

[0042] Li2O: 2-34%, preferably 10-34%; and

[0043] Na2O+K2O+Li2O: 4-40%, preferably 15-40%.

[0044] Preferably, for any of the aforementioned microcrystalline glasses, the rare earth oxides are selected from one or more or two or more of CeO2, Y2O3, La2O3, Ta2O3, Tm2O5 and Nd2O5.

[0045] Preferably, for any of the aforementioned microcrystalline glasses, the microcrystalline glass may further contain a coloring additive; preferably, the coloring additive is selected from one or more of Nd2O3, Fe2O3, CoO, NiO, V2O5, MnO2, TiO2, CuO and Cr2O3.

[0046] Preferably, for any of the aforementioned microcrystalline glasses, the molar content of the coloring additive relative to the overall glass components is preferably no more than 5%; preferably, the coloring additive contains more than 0.5 mol% of CoO and / or Cr2O3 relative to the molar content of the overall glass components, and preferably contains more than 1 mol% of any one selected from Fe2O3, NiO or MnO2.

[0047] Preferably, for any of the above-mentioned glass-ceramics, the glass-ceramics contains a clarifier; preferably, the clarifier is selected from As2O3, Sb2O3, SnO2, chloride, fluoride, SO3 - Compounds, and NO3 - One or more compounds, preferably selected from SnO2, SO3 - Compounds, chlorides, and NO3 - One or more compounds; preferably the clarifier content is 0-2 mol%.

[0048] Preferably, for any of the above-mentioned microcrystalline glasses, the main crystal phase of the microcrystalline glass is selected from one or more of β-quartz solid solution, β-spodumene solid solution, β-eucryptite, spinel, rutile, mullite, olivine, enstatite, cordierite, petalite, lithium silicate, lithium disilicate, quartz, zirconium oxide, and magnetite; the average grain size is preferably less than 100 nm, more preferably less than or equal to 50 nm, and particularly preferably less than or equal to 30 nm.

[0049] Preferably, for any of the aforementioned glass-ceramics, the glass-ceramics is ion-exchanged or non-ion-exchanged glass.

[0050] Also preferably, for any of the above-mentioned glass-ceramics, the glass-ceramics is a glass ceramic with a crystallinity lower than 60%.

[0051] The present invention also provides a method for preparing any of the above-mentioned glass-ceramics, comprising the following steps:

[0052] 1) coating the glass-ceramics with an oxide layer containing Si—O or a mixed silicon oxide layer to form a base layer on the surface of the glass-ceramics;

[0053] 2) plating an intermediate layer on the surface of the base layer obtained in step 1);

[0054] 3) A hydrophobic and oleophobic layer is plated on the surface of the intermediate layer obtained in step 2).

[0055] Preferably, in the aforementioned preparation method, the plating is performed by a vacuum evaporation method.

[0056] Preferably, in any of the above-mentioned preparation methods, the glass-ceramics is glass-ceramics that has undergone ion exchange.

[0057] Preferably, for any of the above-mentioned preparation methods, the glass-ceramics is fired by a method comprising the following steps before coating the primer layer, the intermediate layer and the hydrophobic and oleophobic layer:

[0058] (I) melting the glass raw materials at 1600±50° C. and then annealing them at 400-650° C. to obtain a homogenized plain glass plate;

[0059] (II) obtaining a shaped plain glass sheet by an overflow down-draw method, a float method or a rolling method on the plain glass sheet; and

[0060] (III) The formed plain glass plate is microcrystallized through a secondary heat treatment to obtain a microcrystalline glass preform, which is then subjected to ion exchange or directly used as a raw material for microcrystalline glass without ion exchange, and is used to sequentially coat the required base layer, intermediate layer and hydrophobic and oleophobic layer on its surface, wherein the first heat treatment temperature is 500-1000°C, and the second heat treatment temperature is 550-1100°C.

[0061] Preferably, any of the aforementioned microcrystalline glasses or the microcrystalline glasses obtained by any of the aforementioned preparation methods are used in mobile phone displays, tablet computer displays, laptop computer displays, handheld game consoles, portable digital devices, car displays, windshields or camera displays.

[0062] In another preferred embodiment, the present invention also proposes the following technical solution.

[0063] A glass-ceramic display screen is made of glass-ceramic having a hydrophobic and oleophobic composite coating on its surface, and is characterized in that, starting from the outermost surface of the glass-ceramic, it comprises: a hydrophobic and oleophobic layer, an intermediate layer and a primer layer, wherein the intermediate layer is an intermediate layer formed by containing ionic crystals with a lattice energy of 725-3000 kJ / mol as the original coating material, or is a fluoride intermediate layer formed by using fluorosilicones with a lattice energy of 9400-11400 kJ / mol as the original coating material, and the intermediate layer contains alkali metal fluorides or alkaline earth metal fluorides compounds or an intermediate layer formed by using ionic crystals selected from alkali metal fluorosilicones and alkaline earth metal fluorosilicones as the original coating material; and the primer layer comprises a compound containing Si-O bonds or a mixed silicon oxide layer.

[0064] Preferably, according to the aforementioned glass-ceramic display screen, its crystallinity may be greater than 60%; or greater than 70%; or greater than 80%.

[0065] Also preferably, according to the aforementioned glass-ceramic display screen, the intermediate layer is an intermediate layer formed by an ionic crystal with a lattice energy of 770-3000 kJ / mol as the original coating material;

[0066] Alternatively, a fluoride silicon compound with a lattice energy of 9400-11400 KJ / mol is used as the original coating material to form the fluoride intermediate layer.

[0067] Also preferably, according to any of the above-mentioned glass-ceramic display screens, the intermediate layer is an ionic crystal intermediate layer having a lattice energy of less than 1050 kJ / mol, preferably less than 940 kJ / mol.

[0068] Also preferably, according to the aforementioned glass-ceramic display, the intermediate layer is a crystal formed by using at least one ionic crystal of LiF, NaF and / or KF as a raw coating material; or an intermediate layer formed by using at least one ionic crystal of MgF2, CaF2, SrF2 or BaF2 as a raw coating material; or a fluoride intermediate layer formed by using at least one ionic crystal of Li2SiF6, Na2SiF6, K2SiF6, Rb2SiF6, Cs2SiF6, BeSiF6, MgSiF6, CaSiF6, SrSiF6 or BaSiF6 as a raw coating material for coating;

[0069] The intermediate layer is preferably formed of NaF or KF ionic crystals as the original coating material.

[0070] Also preferably, according to any of the above-mentioned glass-ceramic display screens, the intermediate layer is a polar or non-polar compound; preferably a polar compound.

[0071] Also preferably, according to any of the above-mentioned glass-ceramic display screens, the thickness of the intermediate layer is 1-5 nm, preferably 1-2 nm.

[0072] Also preferably, according to any of the above-mentioned glass-ceramic display screens, the thickness of the base layer is 3-15 nm, preferably 5-10 nm, and more preferably 5-8 nm.

[0073] Also preferably, according to any of the above-mentioned glass-ceramic display screens, the hydrophobic and oleophobic layer has a thickness of not less than 10 nm, preferably not less than 15 nm, and can be 10 nm-25 nm.

[0074] Also preferably, according to any of the above-mentioned glass-ceramic display screens, in the case where the base layer is multi-layered, the compound containing Si-O bonds or the mixed silicon oxide layer is the outermost base layer, and the mixed silicon oxide is silicon oxide SiO x A mixture with at least one oxide of an element other than silicon and / or magnesium fluoride, wherein x is less than or equal to 2;

[0075] Preferably, the other elements are elements selected from aluminum, tin, magnesium, phosphorus, cerium, zirconium, titanium, cesium, barium, strontium, niobium, zinc or boron; more preferably, the mixed silicon oxide is silicon oxide SiO x A mixture of aluminum oxide.

[0076] Also preferably, according to the aforementioned glass-ceramic display, the compound containing Si-O bonds is SiOx, where x is less than or equal to 2; or is any one of SiOC, SiON, SiOCN and / or Si3N4, or a hydrogen bond combined with any one of SiOx, SiOC, SiON and / or SiOCN in any proportion, where x is less than or equal to 2.

[0077] Also preferably, according to any of the above-mentioned glass-ceramic display screens, the hydrophobic and oleophobic layer is a fluorine-based polymer layer, preferably a fluorine-containing polyether silicon oxide layer with a molecular weight of not less than 2000; and the coating thickness is preferably not less than 10 nm.

[0078] Also preferably, according to any of the above-mentioned glass-ceramic display screens, the glass-ceramic composition contains the following oxides in mol ratio:

[0079] SiO2: 40-75%, preferably 45-72%;

[0080] Al2O3: 2-20%, preferably 4-15%;

[0081] B2O3: 0-20%, preferably 0.4-1.6%;

[0082] P2O5: 0-10%, preferably 0.8-1.5%;

[0083] ZrO2+TiO2: 0-15%, preferably 0.9-4%;

[0084] MgO: 0-5%, preferably 0.1-2%;

[0085] ZnO: 0-4%, preferably 0.9-3.0%;

[0086] Rare earth oxides: 0-5%, preferably 0.01-1%;

[0087] Na2O: 0-5.5%;

[0088] K2O: 0-4%;

[0089] Li2O: 2-34%, preferably 10-34%; and

[0090] Na2O+K2O+Li2O: 4-40%, preferably 15-40%.

[0091] Also preferably, according to any of the above-mentioned glass-ceramic display screens, the rare earth oxides are selected from one or more or two or more of CeO2, Y2O3, La2O3, Ta2O3, Tm2O5 and Nd2O5.

[0092] Also preferably, according to any of the above-described microcrystalline glass display screens, the microcrystalline glass may further contain coloring additives; preferably, the coloring additives are selected from one or more of Nd2O3, Fe2O3, CoO, NiO, V2O5, MnO2, TiO2, CuO and Cr2O3.

[0093] Also preferably, according to any of the foregoing items, the microcrystalline glass display screen, wherein the molar content of the coloring additive relative to the overall glass composition does not exceed 5%; preferably, the coloring additive contains more than 0.5 mol% of CoO and / or Cr2O3 relative to the molar content of the overall glass composition, and further preferably contains more than 1 mol% of any one selected from Fe2O3, NiO or MnO2.

[0094] Also preferably, according to the microcrystalline glass display screen described in any of the above items, the main crystal phase of the microcrystalline glass is selected from one or more of β-quartz solid solution, β-spodumene solid solution, β-eucryptite, spinel, rutile, mullite, olivine, enstatite, cordierite, petalite, lithium silicate, lithium disilicate, quartz, zirconium oxide, and magnetite; the average grain size is preferably less than 100 nm, more preferably less than or equal to 50 nm, and particularly preferably less than or equal to 30 nm.

[0095] Also preferably, according to any of the above-mentioned glass-ceramic display screens, the glass-ceramic is ion-exchanged or non-ion-exchanged glass.

[0096] Also preferably, according to the aforementioned glass-ceramic display screen, the glass-ceramic is glass ceramic with a crystallinity lower than 60%.

[0097] In addition, a method for preparing the glass-ceramic display screen described in any of the above items is also provided, which comprises the following steps:

[0098] 2) coating the glass-ceramics with an oxide layer containing Si—O or a mixed silicon oxide layer to form a base layer on the surface of the glass-ceramics;

[0099] 2) plating an intermediate layer on the surface of the base layer obtained in step 1);

[0100] 3) A hydrophobic and oleophobic layer is plated on the surface of the intermediate layer obtained in step 2).

[0101] Preferably, according to the aforementioned preparation method, the plating adopts a vacuum evaporation method.

[0102] It is also preferred that the glass-ceramic display described in any of the above items or the glass-ceramic display obtained by the above-described preparation method is used as a mobile phone glass-ceramic display, a tablet computer glass-ceramic display, a laptop computer glass-ceramic display, a handheld game console, a portable digital device, a car glass-ceramic display, a windshield or a camera glass-ceramic display.

[0103] The present invention can form a strong, durable, and high-performance hydrophobic and oleophobic coating on the coating interface of the microcrystalline glass or glass ceramic of the microcrystalline glass display even if there is very little Si-O structure. Regardless of whether the high-crystallinity glass has undergone ion exchange, it can achieve excellent hydrophobic and oleophobic properties. BRIEF DESCRIPTION OF THE DRAWINGS

[0104] Figure 1 This is a diagram of the reaction process of connecting the PFPE hydrolysis product with glass. DETAILED DESCRIPTION

[0105] The composition of glass-ceramics is very similar to that of ordinary inorganic glass, mostly SiO2

[0106] <70wt%, suggesting that conventional coating methods should yield excellent hydrophobic and oleophobic coatings. However, due to the large number of crystals within glass-ceramics, SiO2 typically enters the crystals during formation, altering the structure and preventing the Si-O from being properly released and integrated into the hydrophobic and oleophobic coating. These tiny crystals typically account for 20-100% of the total volume. This means that when the crystal ratio is high, the glass phase in the glass-ceramics decreases, significantly reducing the Si-O at the interface and leading to poor quality hydrophobic and oleophobic coatings. The present invention provides a solution to this "rootless" problem.

[0107] Specifically, the present invention provides the following technical solutions:

[0108] A composite coating design for a hydrophobic and oleophobic film on the surface of highly crystalline microcrystalline glass or glass ceramics is formed in sequence from the surface: a hydrophobic and oleophobic layer → an intermediate layer → a base layer on the glass. That is, the base layer is inside the microcrystalline glass or glass ceramic, while the hydrophobic and oleophobic layer is on the outside.

[0109] That is to say, the method of the present invention realizes the formation of a hydrophobic and oleophobic film when the crystallinity of the microcrystalline glass or glass ceramic is as high as 60% or more. The crystallinity of the microcrystalline glass or glass ceramic can be greater than 60%, greater than 70%, and especially greater than 80%; of course, since the present invention solves the hydrophobic and oleophobic problem of microcrystalline glass or glass ceramic with a crystallinity of as high as 60% or more, which is difficult to form a hydrophobic and oleophobic film, of course, for microcrystalline glass or glass ceramic with a crystallinity lower than 60%, the method of the present invention can also form an excellent hydrophobic and oleophobic film composite coating thereon.

[0110] Among them, preferably, the intermediate layer is an ionic crystal with a lattice energy of 700-3000 kJ / mol (according to the size of the lattice energy, the composition of the ionic crystal layer serving as the intermediate layer is preferably limited to alkali metal fluorides and alkaline earth metal fluorides), preferably greater than or equal to 725 kJ / mol, and more preferably greater than or equal to 770 kJ / mol (excluding radioactive substances).

[0111] Lattice energy of some common ionic crystals / (kJ·mol -1 ) is shown in Table A below.

[0112] Table A Lattice energy of ionic crystals (kJ·mol -1 )

[0113] <![CDATA[F - ]]> <![CDATA[Cl - ]]> <![CDATA[Br - ]]> <![CDATA[I - ]]> <![CDATA[Li + ]]> 1036 853 807 757 <![CDATA[Na + ]]> 923 786 747 704 <![CDATA[K + ]]> 821 715 682 649 <![CDATA[Rb + ]]> 785 689 660 630 <![CDATA[Cs + ]]> 740 659 631 604

[0114] Among them, preferably, the lattice energy of the ionic crystal is preferably less than 1050 kJ / mol (preferably, the ionic crystal layer is basically limited to alkali metal fluorides, LiF\NaF\KF), and more preferably less than 940 kJ / mol (preferably, the ionic crystal layer is basically limited to NaF\KF);

[0115] Alkali metal fluorides such as Li2SiF6, Na2SiF6, and K2SiF6, as well as alkaline earth metal fluorides can also be used as the intermediate layer.

[0116] Wherein, preferably, the intermediate layer is a polar and non-polar compound (preferably alkali metal fluorides - non-polar, and alkaline earth metal fluorides - polar);

[0117] Among them, further preferably, the compound is a non-polar compound (preferably narrowed down to alkali metal fluorides - non-polar);

[0118] Wherein, preferably, the thickness of the intermediate layer is 1-5 nm, preferably 1-2 nm;

[0119] Wherein, preferably, the primer layer contains or consists of a Si compound, and the Si compound is preferably selected from:

[0120] - SiOx, where x is less than or equal to 2, wherein, in the case of a multilayer, at least the outermost or uppermost layer comprises silicon oxide or consists of silicon oxide;

[0121] - SiOC, SiON, SiOCN and Si3N4, and hydrogen bonds with SiOx, SiOC, SiON and SiOCN in any proportion, where x is less than or equal to 2 (herein, "hydrogen bond" refers to a hydrogen bond formed by any component of air, such as moisture, with the silicon oxide of the glass), where x is less than or equal to 2; or

[0122] - mixed silicon oxides consisting of silicon oxide SiOx and at least one oxide of another element other than silicon and / or magnesium fluoride, wherein the other element is preferably at least one selected from the group consisting of aluminum, tin, magnesium, phosphorus, cerium, zirconium, titanium, cesium, barium, strontium, niobium, zinc and boron; particularly preferably a mixture of silicon oxide SiOx and at least one oxide of the element aluminum, where x is less than or equal to 2;

[0123] Wherein, preferably, the total thickness of the primer layer is 3-15 nm, preferably 5-10 nm, and more preferably 5-8 nm.

[0124] The hydrophobic and oleophobic layer is also referred to as an AF layer (anti-fingerprint layer). The AF layer is formed of a fluorine-based polymer. The fluorine-based polymer can be selected from perfluoropolyether, vinylidene fluoride polymer, tetrafluoroethylene polymer, hexafluoropropylene polymer, chlorotrifluoroethylene polymer, and combinations thereof, preferably perfluoropolyether (PFPE). More preferably, the hydrophobic and oleophobic layer is PFPE with a molecular weight of not less than 2000, and the coating thickness is not less than 10 nm, preferably not less than 15 nm, and can range from 10 nm to 25 nm.

[0125] In addition, preferably, the above-mentioned microcrystalline glass is transparent or opaque, before or after ion exchange, that is, with or without prestress.

[0126] In addition, preferably, the method according to at least one of the above technical solutions is characterized in that the glass-ceramics has the following glass composition or consists of glass (in mol%):

[0127] SiO2: 40-75%, preferably 45-72%;

[0128] Al2O3: 2-20%, preferably 4-15%;

[0129] B2O3: 0-20%, preferably 0.4-1.6%;

[0130] P2O5: 0-10%, preferably 0.8-1.5%;

[0131] ZrO2+TiO2: 0-15%, preferably 0.9-4%;

[0132] MgO: 0-5%, preferably 0.1-2%;

[0133] ZnO: 0-4%, preferably 0.9-3.0%;

[0134] Rare earth oxides: 0-5%, preferably 0.01-1%;

[0135] Na2O: 0-5.5%;

[0136] K2O: 0-4%;

[0137] Li2O: 2-34%, preferably 10-34%; and

[0138] Na2O+K2O+Li2O: 4-40%, preferably 15-40%.

[0139] Wherein, the rare earth oxide is selected from one or more of CeO2, Y2O3, La2O3, Ta2O3, Tm2O5 and Nb2O5.

[0140] In addition, in some preferred embodiments, the above glass composition may contain: coloring oxide additives such as Nd2O3, Fe2O3, CoO, NiO, V2O5, MnO2, TiO2, CuO and Cr2O3; rare earth oxides in an amount of 0-5 mol% or 0-5 mol% for "black glass"; and fining agents in an amount of 0-2 mol%, such as one or more of As2O3, Sb2O3, SnO2, Cl-containing compounds, F-containing compounds, SO3-containing compounds, and NO3-containing compounds.

[0141] In addition, in some preferred embodiments, the method according to at least one of the above technical solutions is characterized in that the preferred main crystal phase of the microcrystalline glass is selected from one or more of β-quartz solid solution, β-spodumene solid solution, β-eucryptite, spinel, rutile, mullite, olivine, enstatite, cordierite, petalite, lithium silicate, lithium disilicate, quartz, zirconium oxide, and magnetite; wherein the average grain size is preferably less than 100 nm, particularly preferably less than or equal to 50 nm, and very particularly preferably less than or equal to 30 nm.

[0142] The present invention uses a base layer such as a SiO2 layer or a SiOx layer or a mixture layer containing silicon oxides (collectively referred to as a "silicon oxide layer," SiO2 is used as an example here, but is not limited to SiO2) + an intermediate layer (referred to as an "RF layer," NaF is used as an example) + a hydrophobic and oleophobic layer such as PFPE in combination: wherein the SiO2 layer cannot be too thick, approximately 5nm, not more than 15nm. SiO2 has a network or chain structure at the microscopic level. A 5nm SiO2 coating is very thin, and the SiO2 coating can still retain the mesh in its structure (if the coating is too thick, the mesh will disappear due to the overlapping of the SiO2 coatings); then an even thinner intermediate layer RF is coated. RF is a compound with a relatively low lattice energy, especially a non-polar compound. RF is selected from compounds with relatively low lattice energy, and RF easily reacts with water in the atmosphere to form R + 、F - 、H + OH - :

[0143]

[0144] Because there are cavities in the base layer, R + 、F - 、H + OH- can easily penetrate into the interface of micro-glass and react with the Si-O-Si structure in the crystal, opening up the Si-O in the crystal structure and forming a basis for better reaction with the hydrophobic and oleophobic layer and film formation:

[0145] ≡Si-O-Si≡+R + +OH-→≡Si-OH+RO-Si≡

[0146] ≡Si-O-Si≡+H + +F - →SiF4+H2O→H2SiO3+H2SiF6

[0147] When enough Si-O is generated in the glass-ceramic interface and the base layer, which is closely connected to the glass-ceramic base, sufficient valence bonds will be generated when reacting with the top hydrophobic and oleophobic layer PFPE, thereby greatly increasing the performance and wear resistance of the hydrophobic and oleophobic layer.

[0148] An intermediate layer with a more appropriate lattice energy is the key to the working principle of the present invention. If the lattice energy is slightly lower, the intermediate layer is active and easy to react. Only when the lattice energy is moderate can the material be kept stable. The intermediate layer of the present invention requires a certain lattice energy range. The hydrolysis and activity of the intermediate layer material within this lattice energy range are still relatively high. It has certain corrosiveness after hydrolysis, so it cannot be plated very thickly, otherwise it will be as bad as too little. Generally speaking, it cannot exceed 5nm. If it is too thick, the reaction products cannot be consumed in the entire reaction process, and will corrode into the glass, causing serious corrosion points on the glass surface and also causing the weather resistance of the coating layer to decrease.

[0149] Regarding the term "glass-ceramic or glass-ceramic":

[0150] In the present invention, the terms "glass-ceramics" and "glass-ceramics" are synonymous, referring to glass with a crystalline phase, as opposed to glass without a crystalline phase or amorphous form. Therefore, the terms "glass-ceramics or glass-ceramics," "glass-ceramics," or "glass-ceramics" throughout this specification are synonymous.

[0151] About Lattice Energy:

[0152] Lattice energy refers to the energy absorbed when an ionic crystal is transformed into gaseous positive and negative ions under standard conditions. It is a parameter that measures lattice stability. Factors that affect the lattice energy include ionic radius, ionic charge, and the ion's electron layer configuration. Referring to the method for calculating lattice energy in the paper "Topological Studies on Lattice Energy and Magnetic Susceptibility of Alkaline Earth Metal Halides" by Qin Zhenglong and Liu Changjun, the formula obtained by fitting is as follows:

[0153] U=1129.1-441.8 0 F+3600.5 1 F

[0154] n F=∑(E i ×E j ×E k ×…) -0.5 .

[0155] n F is the topological index and E is the valence electron energy level value.

[0156] The fluoride lattice energy (KJ / mol) calculated using this method is shown in Table B below.

[0157] Table B Lattice Energy of Fluoride (KJ / mol)

[0158]

[0159] The regression equation obtained by fitting using this method has good correlation and is also suitable for calculating the lattice energy of fluorosilicon compounds. The results are shown in Table C below.

[0160] Table C Lattice Energy of Fluorosilicon Compounds (KJ / mol)

[0161]

[0162] It's important to note that the starting material for the coating and the material ultimately formed on the base layer at the glass interface aren't necessarily the same thing. For example, the alkali metal fluorosiliconate R2SiF6 calculated above is typically a relatively stable solid at room temperature. However, when heated to around 300°C during coating, it decomposes: R2SiF6 --> 2RF + SiF4 (gas). While this material may appear to have a high lattice energy, the key components of the coating have actually undergone a qualitative change after film formation, bringing their lattice energies within the optimal operating range claimed by this invention. For example, sodium fluorosiliconate Na2SiF6 is an odorless, tasteless white granule or crystalline powder; upon heating (above 300°C), it decomposes into sodium fluoride NaF and silicon tetrafluoride SiF4.

[0163] Based on the principles described above, whether or not the interface of the coated glass-ceramics undergoes ion exchange has no impact on the implementation and effectiveness of the present invention. Small ions in the glass must be in a state where ion mobility can occur before they can exchange with larger ions in the external salt bath. Temperature is a key factor in achieving ion mobility. Generally speaking, ion mobility in the glass phase is easier at relatively low temperatures (e.g., starting at the strain point temperature of around 200°C, such as 360°C). However, alkali metal elements in the microcrystalline phase are part of the crystal structure before becoming mobile ions. They require higher energy to break free of the crystal structure and become freely exchangeable ions. This temperature is typically closer to the softening point of the glass (e.g., above 600°C). Therefore, ion exchange typically occurs primarily in the glass phase. Even at extremely high salt bath temperatures, ion exchange occurs primarily in the glass phase, followed by the crystals.

[0164] The high-crystallinity glass-ceramics targeted by the present invention have very few glass phases. Even if a rare glass phase exists and ion exchange occurs, the ions that enter the glass phase are very few, and their ability to change the Si-O structure and coordination in the glass phase is negligible and very local. Therefore, the influence on the formation of the coating valence bond described in the present invention is very small. In other words, regardless of whether the high-crystallinity glass has undergone ion exchange, its interface lacks Si-O structure. The present invention is an invention and creation for this application scenario; if high temperature is used, the ions in the crystal participate in the ion exchange, that is, the crystal is destroyed, and the Si-O in the crystal will open, which will only help the formation of the coating valence bond described in the present invention. The present invention precisely solves the problem of how to form a strong, durable, and high-performance hydrophobic and oleophobic coating when there is very little Si-O structure at the coating interface. Regardless of whether the high-crystallinity glass has undergone ion exchange, it will not be difficult to implement the present invention.

[0165] The preparation method of the microcrystalline glass or glass ceramic having a hydrophobic and oleophobic composite coating on its surface according to the present invention is described in detail as follows.

[0166] Glass with the following composition is fired according to the following method to obtain microcrystalline glass or glass ceramics.

[0167] SiO2: 40-75%, preferably 45-72%;

[0168] Al2O3: 2-20%, preferably 4-15%;

[0169] B2O3: 0-20%, preferably 0.4-1.6%;

[0170] P2O5: 0-10%, preferably 0.8-1.5%;

[0171] ZrO2+TiO2: 0-15%, preferably 0.9-4.0%;

[0172] MgO: 0-5%, preferably 0.1-2%;

[0173] ZnO: 0-4%, preferably 0.9-3.0%;

[0174] Rare earth oxides: 0-5%, preferably 0.01-1%;

[0175] Na2O: 0-5.5%;

[0176] K2O: 0-4%

[0177] Li2O: 2-34%, preferably 10-34%; and

[0178] Na2O+K2O+Li2O: 4-40%; preferably 15-40%.

[0179] The microcrystalline glass or glass ceramic is obtained by firing a method comprising the following steps:

[0180] (I) melting the glass raw materials at 1600±50° C. and then annealing them at 400° C. to 650° C. to obtain a homogenized plain glass plate;

[0181] (II) processing the plain glass sheet by an overflow down-draw method, a float method, or a rolling method to obtain a shaped plain glass sheet; and (III) processing the shaped plain glass sheet by a secondary heat treatment to crystallize the shaped plain glass sheet to obtain a glass-ceramic preform, wherein the first heat treatment is performed at a temperature of 500-1000° C. for 0.5-5 hours, and the second heat treatment is performed at a temperature of 550-1100° C. for 0.5-6 hours; and then

[0182] (IV) performing ion exchange on the glass-ceramic preform or directly using it for coating the required primer layer, intermediate layer and hydrophobic and oleophobic layer on its surface in sequence without performing ion exchange.

[0183] The ion exchange can be carried out by conventional methods, for example, a mixed molten salt containing 10-75 wt% NaNO3 and 25-90 wt% KNO3 by weight can be used to carry out ion exchange at a temperature range of 380-500°C for 5-10 hours.

[0184] Specifically, the firing method includes the following steps: weighing glass raw materials and melting them at a high temperature, such as 1600±50°C. Then, annealing the glass at approximately 400°C to 650°C homogenizes the glass to form a glass-ceramic matrix. The glass-ceramic matrix, also known as a plain glass plate, is a glass plate that has not undergone a crystallization process and does not contain crystals. Depending on its high-temperature viscosity and material properties, the glass can be formed using methods such as overflow downdraw, float glass, and calendering. The resulting plain glass plate has a thickness ranging from 0.1 to 5 mm. Alternatively, the glass can be formed into a block, annealed, and then cut into sheets.

[0185] After the glass-ceramic matrix is ​​formed, it is subjected to a secondary heat treatment for microcrystallization to produce a glass-ceramic preform. The first heat treatment is carried out at a temperature of about 500-1000°C for 0.5-5 hours, and the second heat treatment is carried out at a temperature of about 550-1100°C for 0.5-6 hours. After crystallization, the desired glass-ceramic or glass-ceramic is formed. Then, after ion exchange or without ion exchange, it directly enters the vacuum coating machine PVD, sets the coating parameters, and coats the base layer, middle layer, and hydrophobic and oleophobic layer in sequence. The process in the vacuum coating machine is: glass is put on the shelf - vacuum pumping - plasma cleaning - evaporation - hollowing (releasing the vacuum to atmospheric pressure) - unloading.

[0186] The following examples illustrate in detail how to prepare the chemically strengthened glass of the present invention and the stress performance characteristics of the chemically strengthened glass of the present invention.

[0187] Part I Examples: Glass Preparation Examples

[0188] Taking Example 1 as an example, how to prepare a glass substrate is described:

[0189] (1) The materials of Example 1 shown in Table 1 below were mixed and placed in a platinum crucible. The mixture was melted in a high-temperature lifting furnace at 1600°C for 5 hours. The mixture was then cast into a preheated stainless steel mold and placed in an annealing furnace at 580°C for 24 hours to anneal the mold to eliminate the internal stress of the glass. The annealed glass bricks were cut on six sides to obtain glass bricks. The bricks were then finely cut, flat-ground, and edge-brushed using a wire cutting machine, a CNC engraving machine, a flat grinder, and a polisher to obtain plain glass plates with dimensions of 155 mm × 78 mm × 0.65 mm.

[0190] Among them, the instrument models used in the above process are described as follows:

[0191] Multi-wire cutting machine: ch5625, Taizhou Chenhong CNC Equipment Manufacturing Co., Ltd.

[0192] CNC machine tool engraving machine: CN-650, Shandong China CNC Equipment Co., Ltd.,

[0193] Surface grinding machine: YJ-13B6LD, Hunan Ningjing Machinery Co., Ltd., and

[0194] Polishing machine: YJ-13B6PD, Hunan Ningjing Machinery Co., Ltd.

[0195] (2) First, a plain glass plate was subjected to a first heat treatment at 650°C for 3 hours in a high-temperature lifting furnace to form crystal nuclei; then a second heat treatment was carried out at 730°C for 3 hours to precipitate crystals, thereby producing glass ceramics. The glass ceramics were subjected to crystal analysis, including crystallinity, crystal type, i.e., main crystalline phase and secondary crystalline phase type, as well as the ratio of main crystalline phase to secondary crystalline phase, and average grain size. At the same time, the Vickers hardness, fracture toughness, average visible light transmittance, and haze of the glass ceramics (hereinafter also referred to as "glass ceramics without ion exchange") were tested.

[0196] (3) The glass ceramics are subjected to ion exchange, and the molten salt is a mixed salt bath of 40 wt% NaNO3 and 60 wt% KNO3. The strengthening temperature (i.e., ion exchange temperature) is 380°C, and the strengthening time is 9 hours. After the strengthening is completed, the glass ceramics are taken out and cleaned to obtain strengthened glass ceramics (hereinafter also referred to as "glass ceramics subjected to ion exchange").

[0197] (4) The obtained strengthened glass-ceramics were subjected to corresponding characterization tests, including tests on haze, average visible light transmittance, surface compressive stress, compressive stress depth, and Young's modulus. The specific test results are shown in Table 3.

[0198] Among them, the definitions and test methods of crystallinity, primary crystalline phase, secondary crystalline phase, average grain size, Vickers hardness, fracture toughness, average visible light transmittance, haze, surface compressive stress, compressive stress depth and Young's modulus are specifically described as follows:

[0199] The surface compressive stress here refers to the fact that after the glass is chemically strengthened, the alkali metal ions with smaller radius on the surface are replaced by alkali metal ions with larger radius. Due to the crowding effect of the alkali metal ions with larger radius, compressive stress is generated on the glass surface, which is called surface compressive stress.

[0200] Crystallinity: The diffraction peak curve was obtained by XRD diffractometer analysis, wherein the incident angle range was 2Theta = 10 to 50 degrees and the scanning speed was 6 degrees / min. The equipment used in this example was Shimadzu XRD-6000. The crystallinity was calculated according to formula (1-1):

[0201]

[0202] Where I c The integrated diffraction intensity of the crystallized part of the glass-ceramic sample 2Theta = 10 to 50 degrees;

[0203] I a The integrated diffraction intensity of the amorphous part of the glass-ceramic sample 2Theta = 10~50;

[0204] K is the relative scattering factor per unit mass of the crystalline and amorphous parts of the glass-ceramic sample 2Theta=10~50.

[0205] Main crystalline phase ratio: The crystalline phase with the highest percentage by weight relative to other crystalline phases in glass-ceramics.

[0206] Proportion of secondary crystalline phase: In addition to the primary crystalline phase, one or more other crystalline phases may also exist in the ceramic portion of the glass ceramic, with the secondary crystalline phase accounting for less than the weight % of the primary crystalline phase.

[0207] Average Grain Size: The average grain length of the glass-ceramics observed at a magnification of 100,000-1,000,000x. Measured using a transmission electron microscope (ThermoFisher Scientific (formerly FEI) Talos F200S). This measurement is equivalent to taking a magnified photograph of a specific grain area. The magnified photograph contains a limited number of grains, with their sizes marked on a scale, and then the average is calculated. In the embodiments of the present invention, the magnification used for measurement is 500,000x.

[0208] Vickers hardness: The Vickers hardness was tested using a Vickers hardness tester in accordance with the standard "GB / T 37900-2019 Ultra-thin glass hardness and fracture toughness test method - Small load Vickers hardness indentation method". In this embodiment, the device used was a digital display small load Vickers hardness tester VTD405 (Beijing Wowei Technology Co., Ltd.).

[0209] Fracture toughness: Indicates the indentation measurement result. After the test sample is polished, the cone-shaped diamond indenter on the Vickers hardness tester is pressed on the sample with a load p of 300N for 10 seconds to make an indentation. In this way, a corresponding crack will be generated at the top of the indentation. The fracture toughness value K is calculated based on the indentation load P and the crack extension length C. IC The specific fracture toughness calculation is obtained according to the standard test calculation of "GB / T37900-2019 Ultra-thin glass hardness and fracture toughness test method small load Vickers hardness indentation method".

[0210] Surface compressive stress (MPa): The surface compressive stress of the glass to be tested was measured using a waveguide optical stress meter FSM-6000LE manufactured by ORIHARA, Japan.

[0211] Compressive stress depth (μm): the distance from the surface of the glass to be tested to the position where the compressive stress is zero;

[0212] Haze: The percentage of transmitted light intensity that deviates from the incident light by more than 2.5° to the total transmitted light intensity. Measured using a colorimeter (model CM-3600A).

[0213] Visible light transmittance: within the visible light band, the ratio of the radiant energy projected and transmitted through the object to the total radiant energy projected onto the object during the process of the incident light flux leaving from the illuminated surface or the incident surface of the medium to the other side.

[0214] Average Visible Light Transmittance: Within a specific wavelength range, the transmittance at each wavelength is measured at 10nm intervals. The sum of the measured transmittances at each wavelength is divided by the number of transmittances measured at each wavelength. For example, the average transmittance for a wavelength range of 360-400nm is calculated as follows: The transmittances at wavelengths of 360nm, 370nm, 380nm, 390nm, and 400nm are measured. The number of transmittances measured for the wavelength range of 360-400nm is 5. The sum of these transmittances is divided by 5 to obtain the average transmittance for a wavelength range of 360-400nm.

[0215] Young's modulus (GPa): The Young's modulus of the sample was measured by an acoustic wave method using an IET-1600P high-temperature elastic modulus tester.

[0216] Examples 2 to 15

[0217] The preparation method steps are the same as those in Example 1, with the differences being detailed in Tables 1, 2, and 3. That is, the specific raw material compositions of the glass material, the heat treatment process conditions of step (2), and the performance test results of the obtained glass-ceramic, and the ion exchange process conditions of step (3), and the performance test results of the obtained strengthened glass-ceramic, are detailed in Tables 1, 2, and 3.

[0218] Table 1 Raw materials for preparing glass (mol%)

[0219]

[0220] Table 2 Treatment conditions of plain glass (unreinforced glass ceramics) and performance parameters of glass ceramics after heat treatment

[0221]

[0222]

[0223] As can be seen from Table 2 above, the glass-ceramics obtained from the plain glass obtained by the present invention after heat treatment have a crystallinity ranging from a minimum of 61.2% to a maximum of 90.35%, a visible light transmittance between 89% and 92%, an average grain size between 15.7 nm and 25.5 nm, a haze between 0.09% and 0.20%, a Vickers hardness between 718 and 796 HV, and a fracture toughness between 1.4 and 1.9 MPa·m 1 / 2 .

[0224] Table 3 Conditions for ion exchange of plain glass and performance parameters of strengthened glass obtained by ion exchange

[0225]

[0226] As can be seen from the above glass composition, rare earth oxides can be contained in the glass formula. Specifically, in the present invention, any one or more selected from CeO2, Y2O3, La2O3, Ta2O3, Tm2O5, and Nb2O5 can be added. The content of these rare earth oxides usually does not exceed 5 mol%. In addition, colorants and clarifiers can be added as appropriate. Specifically, in the above glass composition, Nb2O3 acts as a colorant. In the present invention, in addition to Nb2O3, any one or more of the following substances can be added as colorants: Nd2O3, Fe2O3, CoO, NiO, V2O5, MnO2, TiO2, CuO, CeO2, and Cr2 After adding colorants, the visible light transmittance of the glass decreases. The more colorants added, the lower the transmittance. Generally speaking, the addition ratio should not exceed 5 mol%. Adding more than 1 mol% will significantly change the overall color and transmittance of the glass. Adding too much colorant (for example, about 5 mol%) will affect the crystallinity and crystal size of the microcrystalline glass. In the present invention, adding 1 mol% of any combination of Fe2O3, NiO, MnO2, and other colorants in any proportion to the overall composition of the above embodiment will make the glass black. Adding more than 0.5 mol% of any combination of CoO, Cr2O3, and other colorants in any proportion will make the glass black with a bluish tint. Using no more than 5 mol% of colorant will not affect other properties of the glass.

[0227] In the glass of the present invention, a clarifier can be used alone or in combination according to the actual melting conditions. The clarifier is selected from As2O3, Sb2O3, SnO2, SO3 - One or more of the following: compounds, fluorides or salts, chlorides or salts, and nitrates. As2O3 and Sb2O3 have good clarification effects as clarifiers, but they are not preferred due to their toxicity. Fluorides can also be used as clarifiers, but they are not preferred due to their corrosiveness. Usually SnO2, SO3 (such as Na2SO4), chlorides (such as NaCl), and NO3 - A single substance or combination of compounds (such as NaNO3) is a commonly used clarifier, generally not exceeding 1 mol%.

[0228] Part II Example: Example of Preparation of Hydrophobic and Oleophobic Composite Coating

[0229] 1. The glass ceramics without ion exchange and ion exchange in Example 4 were used as glass substrates to form composite coatings

[0230] Composite coatings including the SiO2, NaF and AF films were formed on the plain glass obtained by Example 4 of the first part, i.e., a batch of glass ceramics that were not ion-exchanged as glass substrates (i.e., the ion exchange treatment of step (3) was not performed) (numbered #4-A1 to 4-A15, respectively) and the glass ceramics that were ion-exchanged (i.e., the ion exchange treatment of step (3) was performed) as glass substrates (numbered #4-B1 to 4-B15, respectively). In addition, composite coatings only including SiO2 and AF films were formed on the above-mentioned glass ceramics that were not ion-exchanged (numbered #4-A16 to 4-A18, respectively) and the glass ceramics that were ion-exchanged (numbered #4-B16 to 4-B18, respectively) as glass substrates. Specifically, the vacuum coating apparatus described in Table 4-1 and the coating conditions described in Table 4-2 are used (Note: in each embodiment, the coating time is controlled according to the target coating thickness, and the coating is stopped when the target thickness is reached), and the composite coating is formed according to the following method: the surfaces of the glass substrates are cleaned respectively by ultrasonic cleaning (or a flat brush cleaning); after the surface of the glass substrate is cleaned, a substantially uniform film layer is formed on the surface of the substrate in sequence by vacuum coating; wherein the vacuum coating process is as follows: the glass sample to be plated is placed on an umbrella-shaped coating rack, and then the umbrella-shaped coating rack is placed in the machine workpiece rack, SiO2 and NaF coating materials are placed separately in two electron gun crucibles of the vacuum coating machine (using the equipment Hanyi Vacuum 2050 electron gun vacuum coating machine) without mixing, so that the materials fill the crucible and are level with the crucible mouth surface, and a film for forming an AF film (AF film (Anti-Fingerprint Glass, anti-fingerprint film)) AF film material (600ml AF liquid is dripped into the crucible filled with steel wool, and the crucible after the AF liquid is dried is called AF film material), the vacuum chamber is closed and vacuuming is started; when the background vacuum degree reaches the vacuum degree specified in Table 4-2 of the set process, Ar gas is automatically introduced into the equipment, and the Ar gas volume is 28sccm; run Hanyi's homemade IonBeam Source Hall ion source is used to bombard the sensitized glass surface with ions and clean it. Then the process vacuum, ion source voltage, ion source current, neutralization current, Ar and O2 gas ratio, electron gun working current, film forming rate, coating thickness and other specific conditions are controlled as shown in Table 4-2. According to these conditions, SiO2 and NaF are plated in turn (the raw materials SiO2 and NaF are both granular). Then the process vacuum, evaporation resistance working current, film forming rate, coating thickness and other specific conditions are controlled as shown in Table 4-2. According to these conditions, AF is plated. Among them, the SiO2 film uses L5 type SiO2 from Merck, Germany as the coating material.

[0231] The NaF film uses NaF provided by Nanyang Yingfukang Optoelectronic Materials Co., Ltd. as the coating material; the AF film (Anti-Fingerprint Glass) uses KyY1905-1 fluorinated polyether manufactured by Shin-Etsu Chemical Co., Ltd. of Japan as the AF main agent (manufactured by Shin-Etsu Chemical Co., Ltd.) coating material (referred to as "PFPE" film).

[0232] After the coating is completed, the contact angle test is performed on the outer surface of the glass ceramics that have not undergone ion exchange and the glass ceramics that have undergone ion exchange. The test results of the thickness of each film layer and the contact angle of the film layer of the SiO2, NaF and AF films formed are shown in Table 5-1 and Table 5-2.

[0233] After coating, the water contact angle, oleic acid contact angle and water drop angle after wear resistance on the coating surface were measured to examine the coating quality and durability.

[0234] The water contact angle (°) of the AF film surface was measured by a method in accordance with JIS R 3257 (1999).

[0235] Among them, the method for determining the contact angle of oleic acid on the surface of the AF film is as follows: a 7 μL droplet is placed on a horizontally coated sample and its cut angle is measured.

[0236] Hexadecane was used instead of water to drop onto glass-ceramics that had not undergone ion exchange to test the contact angle of oleic acid. The test results for glass-ceramics #4-A10, #4-A11, and #4-A12 were as follows:

[0237]

[0238] Wear test: at 1cm 2 A Korean minoan solid eraser (6 mm in diameter, type A) (manufactured by MIRAESCIENCE, minoan) is used as a wear-resistant indenter. Under an applied load of 1 kgf, the surface of the AF film formed on the surface of the glass substrate is rubbed back and forth 2500 (or more) times at a stroke amplitude of 40 mm and a speed of 40 mm / second. Then, a cloth [manufactured by Ozu Sangyo Co., Ltd., DUSPER (registered trademark)] is used to dry-erase and clean the surface of the AF film. Then, the water contact angle (°) is measured at three positions on the surface after the AF film wear resistance test. The measurement at each position is repeated three times, and the average water contact angle (°) at a total of 9 positions is measured.

[0239] Table 4-1 Instrument models used in vacuum coating of the embodiments of the present invention

[0240] Vacuum coating machine model Hanyi Vacuum 2050 Electron Gun Vacuum Coating Machine Mechanical pump model Leybold SV630B Roots pump model Leybold WAU2001 Diffusion pump model HDP-700(28'') PolyCold Models PFC-1102HC Ion source model Hanyi's homemade IonBeamSource Electron gun model HEG-103 Film thickness controller InficonXTC / 3S

[0241] Note: In order to form the required vacuum conditions for plating, those skilled in the art can select some or all of the pumps listed in Table 4-1 above according to conventional means and use them as needed. Among them, the mechanical pump is also called the fore-stage pump, which uses oil to maintain the sealing effect and relies on mechanical methods to continuously change the volume of the suction cavity in the pump, so that the volume of the gas in the pumped container continues to expand to obtain a vacuum; the Roots pump is a booster pump, whose function is to increase the pressure difference between the inlet and the exhaust port, and it uses a mechanical pump as a fore-stage pump; the diffusion pump is a pump used to obtain a high vacuum, and when using the diffusion pump, a mechanical pump and a Roots pump are used as fore-stage pumps; Polycold is a low-temperature water vapor pump, which is used to capture residual gas in the high vacuum environment using the diffusion pump. Its working principle is to place a refrigeration coil that can reach below -120°C at the pump port of the diffusion pump, and quickly capture the residual gas in the vacuum system through the low-temperature condensation effect on its surface.

[0242] Table 4-2 Conditions for forming composite coatings in various embodiments of the present invention

[0243]

[0244] Table 5-1 Composite coating formed by using glass ceramic (crystallinity 80.1%) without ion exchange in Example 4 as glass substrate

[0245]

[0246] Table 5-2 Composite coating formed by using the glass ceramic (crystallinity 80.1%) that has undergone ion exchange in Example 4 as a glass substrate

[0247]

[0248] 2. Forming a composite coating using the glass ceramics that have not undergone ion exchange and those that have undergone ion exchange in Example 8 as glass substrates

[0249] The operation of forming a composite coating using the glass ceramics formed in Example 4 as the glass substrate is similar to that described in Section 1 above, except that this section uses the glass ceramics that have not undergone ion exchange (numbered #8-A1 to #8-A15) and the glass ceramics that have undergone ion exchange (numbered #8-B1 to #8-B15) in Example 8 as glass substrates to form a composite coating containing SiO2, NaF and AF film, as well as a composite coating containing only SiO2 and AF film (glass ceramics that have not undergone ion exchange: numbered #8-A16 to #8-A18; glass ceramics that have undergone ion exchange: numbered #8-B16 to #8-B18). The test results of the water contact angle of the outer surface of the coating are shown in Tables 6-1 and 6-2.

[0250] Table 6-1 Composite coating formed by using glass ceramic (crystallinity 90.35%) without ion exchange in Example 8 as glass substrate

[0251]

[0252] Table 6-2 Composite coating formed by using the glass ceramic (crystallinity 90.35%) that has undergone ion exchange in Example 8 as a glass substrate

[0253]

[0254] 3. Forming a composite coating using the glass ceramics that have not undergone ion exchange and those that have undergone ion exchange in Example 12 as glass substrates

[0255] The operation of forming a composite coating using the glass ceramics formed in Example 4 as the glass substrate is similar to that described in Section 1 above, except that this section uses the glass ceramics that have not undergone ion exchange (numbered #12-A1 to #12-A15) and the glass ceramics that have undergone ion exchange (numbered #12-B1 to #12-B15) in Example 12 as glass substrates to form a composite coating containing SiO2, NaF and AF film, as well as a composite coating containing only SiO2 and AF film (glass ceramics that have not undergone ion exchange: numbered #12-A16 to #12-A18; glass ceramics that have undergone ion exchange: numbered #12-B16 to #12-B18). The test results of the water contact angle of the outer surface of the coating are shown in Tables 7-1 and 7-2.

[0256] Table 7-1 Composite coating formed by using glass ceramic (crystallinity 71.60%) without ion exchange in Example 12 as glass substrate

[0257]

[0258] Table 7-2 Composite coating formed by using the glass ceramic (crystallinity 71.60%) that has undergone ion exchange in Example 12 as a glass substrate

[0259]

[0260] 4. Forming a composite coating using the glass ceramics that have not undergone ion exchange and those that have undergone ion exchange in Example 13 as glass substrates

[0261] The operation of forming a composite coating using the glass ceramics formed in Example 4 as the glass substrate is similar to that described in Section 1 above, except that this section uses the glass ceramics that have not undergone ion exchange (numbered #13-A1 to #13-A15) and the glass ceramics that have undergone ion exchange (numbered #13-B1 to #13-B15) in Example 13 as glass substrates to form a composite coating containing SiO2, NaF and AF film, as well as a composite coating containing only SiO2 and AF film (glass ceramics that have not undergone ion exchange: numbered #13-A16 to #13-A18; glass ceramics that have undergone ion exchange: numbered #13-B16 to #13-B18). The test results of the water contact angle of the outer surface of the coating are shown in Tables 8-1 and 8-2.

[0262] Table 8-1 Composite coating formed by using glass ceramic (crystallinity 61.20%) without ion exchange in Example 13 as glass substrate

[0263]

[0264] Table 8-2 Composite coating formed by using the glass ceramic (crystallinity 61.20%) subjected to ion exchange in Example 13 as a glass substrate

[0265]

[0266] From the experimental results in Tables 5-1, 5-2, 6-1, 6-2, 7-1, 7-2, 8-1, and 8-2 above, it can be seen that among the 13 glass-ceramic formulas, 4 glass-ceramics with different crystal ratios were selected, and three-layer coatings were formed using glass substrates without ion exchange and after ion exchange. The following conclusions can be drawn from these data:

[0267] 1) When the thickness of the base layer is too thick, exceeding 20nm, the wear resistance of AF is poor, so it is best not to exceed 15nm;

[0268] 2) When the intermediate layer is too thick, exceeding 5 nm, the initial performance and wear resistance of AF are very poor. However, if there is no intermediate layer, the contact angle data in the last three rows of each table show that the initial contact angle is mostly less than 100 degrees, and the contact angle reaches a maximum of about 60 degrees after 2500 frictions;

[0269] 3) The effect can be achieved with a moderate base layer, a thin middle layer, and a thick or thin AF layer;

[0270] 4) The surface layer is not less than 10nm, and the obtained composite coating has good hydrophobicity and oleophobicity and excellent wear resistance. It is preferably not less than 15nm. The thicker the better the wear resistance. From a cost perspective, the hydrophobicity and wear resistance of the coating obtained by not exceeding 25nm are ideal.

[0271] 5) Even if the three-layer composite coating is directly formed on the glass ceramic without ion exchange, i.e., prestressing treatment, its hydrophobicity and oleophobicity are also excellent; when the ion-exchanged strengthened glass is then used to form the three-layer composite coating, the wear resistance test shows that the contact angle is larger, that is, the hydrophobicity and oleophobicity effect is even better.

[0272] In summary, it can be seen that the preferred thickness of the base layer is 3-15nm, the thickness of the middle layer is 1-5nm, the thickness of the AF film layer is not less than 10nm, preferably not less than 15nm, and can be 10-25nm; in addition, the middle layer is preferably 1-2nm; and the effect of forming a base layer of 5-10nm is good, and the best is 5-8nm.

[0273] 5. For the glass ceramics in the first part of Example 4 that have not undergone ion exchange (the glass ceramics are prepared according to the steps (1) and (2) on the basis of the 4# formula, and the ion exchange treatment of step (3) is not performed), the composite coatings (numbered #4-a1, #4-a2, and #4-a3) on the surface are formed according to the operating methods and conditions described in Section 1 above. The only difference is the thickness of each coating, as shown in Table 9 below. The coating quality and durability of the composite coating formed on the surface are tested, and the results are also summarized in Table 9 below.

[0274] The glass ceramics subjected to ion exchange in Example 4 of the first part were subjected to the operation method and conditions described in Section 1 above to form a composite coating on the surface (also called strengthened glass, numbered #4-b1, #4-b2, #4-b3). The only difference was the thickness of each coating, as shown in Table 9 below. The coating quality and durability of the composite coating formed on the surface were tested, and the surface compressive stress and compressive stress depth were tested according to the test method of Example 4 of the first part. All test results are also summarized in Table 9 below.

[0275] Black colorants were added to the glass ceramics that were not ion-exchanged in Example 4 of the first part. That is, based on the 4# formula, 0.5 mol% NiO, 1 mol% Fe2O3, and 0.3 mol% CoO were added to the original plain glass formula in accordance with steps (1) and (2) of the first part "Glass Preparation Example" to prepare glass ceramics. The surface composite coatings (also referred to as black glass that was not ion-exchanged or black glass that was not prestressed, numbered #4-c1, #4-c2, and #4-c3) were formed according to the operation method and operation conditions described in Section 1 above. The only difference was the thickness of each coating layer, as shown in Table 9 below. The coating quality and durability of the composite coatings formed on the surface were tested, and the results are also summarized in Table 9 below. The obtained black glass has an opaque black appearance and appears dark blue-black under strong white light.

[0276] Table 9 Coating properties of composite coatings without ion exchange, with ion exchange and with black colorant added

[0277]

[0278] It can be seen from Table 9 above that the intermediate layer is relatively thin in the range of 1-3 nm. Regardless of whether it has undergone ion exchange or glass prestressing treatment, the AF film bonding strength and wear resistance of the outer surface of the composite coating are excellent, and even after the addition of black colorant, the AF film bonding strength and wear resistance are not affected.

Claims

1. A glass-ceramic display screen, which is made of glass-ceramic with a hydrophobic and oleophobic composite coating on its surface, characterized in that: Starting from the outermost surface of the microcrystalline glass, it includes in sequence: a hydrophobic and oleophobic layer, an intermediate layer and a base layer, wherein the intermediate layer is an intermediate layer formed by an ionic crystal with a lattice energy of 725-3000kJ / mol as the original coating material, or is a fluoride intermediate layer formed by a fluoride silicide with a lattice energy of 9400-11400KJ / mol as the original coating material, and the intermediate layer contains alkali metal fluorides or alkaline earth metal fluorides compounds or an intermediate layer formed by ionic crystals selected from alkali metal fluorides and alkaline earth metal fluorides as the original coating material; the base layer includes a compound containing Si-O bonds or a mixed silicon oxide layer, the intermediate layer has a thickness of 1-5nm, and the base layer has a thickness of 3-15nm; the hydrophobic and oleophobic layer is a fluorine-based polymer layer, and the thickness of the hydrophobic and oleophobic layer is not less than 10nm.

2. The glass-ceramic display screen according to claim 1, wherein the crystallinity thereof is greater than 60%. The glass-ceramic display screen according to claim 2 , wherein the crystallinity thereof is greater than 70%. The glass-ceramic display screen according to claim 3 , wherein the crystallinity thereof is greater than 80%.

5. The glass-ceramic display according to claim 1, wherein the intermediate layer is an intermediate layer formed by an ionic crystal having a lattice energy of 770-3000 kJ / mol as an original coating material. The glass-ceramic display according to claim 1 , wherein the intermediate layer is an ionic crystal intermediate layer having a lattice energy less than 1050 kJ / mol. 7 . The glass-ceramic display screen according to claim 6 , wherein the intermediate layer is an ionic crystal intermediate layer having a lattice energy less than 940 kJ / mol.

8. The glass-ceramic display according to claim 1 , wherein the intermediate layer is a crystal formed by using at least one ionic crystal of LiF, NaF, and / or KF as a primary coating material; or an intermediate layer formed by using at least one ionic crystal of MgF2, CaF2, SrF2, or BaF2 as a primary coating material; or a fluoride intermediate layer formed by coating using at least one ionic crystal of Li2SiF6, Na2SiF6, K2SiF6, Rb2SiF6, Cs2SiF6, BeSiF6, MgSiF6, CaSiF6, SrSiF6, or BaSiF6 as a primary coating material. 9 . The glass-ceramic display according to claim 8 , wherein the intermediate layer is an intermediate layer formed by using NaF or KF ionic crystals as the original coating material. 10 . The glass-ceramic display according to claim 1 , wherein the intermediate layer is a polar or non-polar compound. The glass-ceramic display according to claim 10 , wherein the intermediate layer is a polar compound. 12 . The glass-ceramic display according to claim 1 , wherein the thickness of the intermediate layer is 1-2 nm. The glass-ceramic display screen according to claim 1 , wherein the thickness of the base layer is 5-10 nm. The glass-ceramic display screen according to claim 13 , wherein the bottom layer has a thickness of 5-8 nm. The glass-ceramic display according to claim 1 , wherein the hydrophobic and oleophobic layer has a thickness of not less than 15 nm. The glass-ceramic display according to claim 15 , wherein the hydrophobic and oleophobic layer has a thickness of 10 nm to 25 nm.

17. The glass-ceramic display according to any one of claims 1 to 16, wherein: In the case where the base layer is multi-layer, the compound containing Si-O bonds or the mixed silicon oxide layer serves as the outermost base layer, and the mixed silicon oxide is a mixture of silicon oxide SiOx and at least one oxide of an element other than silicon and / or magnesium fluoride, where x is less than or equal to 2.

18. The glass-ceramic display screen according to claim 17, wherein: The other elements are elements selected from aluminum, tin, magnesium, phosphorus, cerium, zirconium, titanium, cesium, barium, strontium, niobium, zinc or boron.

19. The glass-ceramic display screen according to claim 18, wherein: The mixed silicon oxide is a mixture of silicon oxide SiOx and aluminum oxide.

20. The glass-ceramic display according to claim 17, wherein the compound containing Si-O bonds is SiOx, where x is less than or equal to 2; or is any one of SiOC, SiON, SiOCN and / or Si3N4, or a hydrogen bond with any one of SiOx, SiOC, SiON and / or SiOCN in any proportion, where x is less than or equal to 2.

21. The glass-ceramic display according to any one of claims 1 to 16, wherein the hydrophobic and oleophobic layer is a fluorine-containing polyether silicon oxide layer having a molecular weight of not less than 2000.

22. The glass-ceramic display according to any one of claims 1 to 16, wherein the glass-ceramic composition comprises the following oxides in a molar ratio: SiO2: 40-75%; Al2O3: 2-20%; B2O3: 0-20%; P2O5: 0-10%; ZrO2+TiO2:0-15%; MgO: 0-5%; ZnO: 0-4%; Rare earth oxides: 0-5%; Na2O: 0-5.5%; K2O: 0-4%; Li2O: 2-34%; and Na2O+K2O+Li2O:4-40%.

23. The glass-ceramic display according to claim 17, wherein the glass-ceramic composition comprises the following oxides in a molar ratio: SiO2: 40-75%; Al2O3: 2-20%; B2O3: 0-20%; P2O5: 0-10%; ZrO2+TiO2:0-15%; MgO: 0-5%; ZnO: 0-4%; Rare earth oxides: 0-5%; Na2O: 0-5.5%; K2O: 0-4%; Li2O: 2-34%; and Na2O+K2O+Li2O:4-40%.

24. The glass-ceramic display according to claim 20, wherein the glass-ceramic composition comprises the following oxides in a molar ratio: SiO2: 40-75%; Al2O3: 2-20%; B2O3: 0-20%; P2O5: 0-10%; ZrO2+TiO2:0-15%; MgO: 0-5%; ZnO: 0-4%; Rare earth oxides: 0-5%; Na2O: 0-5.5%; K2O: 0-4%; Li2O: 2-34%; and Na2O+K2O+Li2O:4-40%.

25. The glass-ceramic display according to claim 22, wherein the glass-ceramic composition contains the following oxides in a mol ratio: SiO2: 45-72%; Al2O3: 4-15%; B2O3: 0.4-1.6%; P2O5: 0.8-1.5%; ZrO2+TiO2:0.9-4%; MgO: 0.1-2%; ZnO: 0.9-3.0%; Rare earth oxides: 0.01-1%; Na2O: 0-5.5%; K2O: 0-4%; Li2O: 10-34%; and Na2O+K2O+Li2O:15-40%.

26. The microcrystalline glass display according to claim 22, wherein the rare earth oxide is selected from one or more of CeO2, Y2O3, La2O3, Ta2O3, Tm2O5 and Nd2O5.

27. The microcrystalline glass display according to claim 23, wherein the rare earth oxide is selected from one or more of CeO2, Y2O3, La2O3, Ta2O3, Tm2O5 and Nd2O5.

28. The microcrystalline glass display according to claim 24, wherein the rare earth oxide is selected from one or more of CeO2, Y2O3, La2O3, Ta2O3, Tm2O5 and Nd2O5.

29. The glass-ceramic display according to any one of claims 1 to 16, wherein the glass-ceramic display further contains a coloring additive.

30. The glass-ceramic display according to claim 29, wherein the coloring additive is selected from one or more of Nd2O3, Fe2O3, CoO, NiO, V2O5, MnO2, TiO2, CuO and Cr2O3.

31. The glass-ceramic display screen according to claim 29, wherein: The molar content of the coloring additive relative to the overall composition of the glass does not exceed 5%.

32. The glass-ceramic display screen according to claim 31, wherein: The coloring additive contains 0.5 mol% or more of CoO and / or Cr2O3 based on the molar content of the entire glass components.

33. The glass-ceramic display screen according to claim 32, wherein: The coloring additive further contains 1 mol % or more of any one selected from Fe2O3, NiO or MnO2.

34. The glass-ceramic display screen according to any one of claims 1 to 16, wherein the main crystalline phase of the glass-ceramic is selected from one or more of β-quartz solid solution, β-spodumene solid solution, β-eucryptite, spinel, rutile, mullite, olivine, enstatite, cordierite, petalite, lithium silicate, lithium disilicate, quartz, zirconium oxide, and magnetite. The glass-ceramic display screen according to claim 34 , wherein the average grain size is less than 100 nm.

36. The microcrystalline glass display screen according to claim 35, wherein the average grain size of the main crystalline phase of the microcrystalline glass is less than or equal to 50 nm.

37. The microcrystalline glass display screen according to claim 36, wherein the average grain size of the main crystal phase of the microcrystalline glass is less than or equal to 30 nm.

38. The glass-ceramic display according to any one of claims 1 to 16, wherein the glass-ceramic is ion-exchanged or non-ion-exchanged glass. The glass-ceramic display according to claim 1 , wherein the glass-ceramic is a glass ceramic having a crystallinity of less than 60%.

40. The method for preparing a glass-ceramic display screen according to any one of claims 1 to 39, wherein the glass-ceramic display screen is prepared by a method comprising the following steps: 1) coating the glass-ceramic with an oxide containing Si—O or a mixed silicon oxide layer, Forming a base layer on the surface of the glass-ceramic; 2) plating an intermediate layer on the surface of the base layer obtained in step 1); 3) A hydrophobic and oleophobic layer is plated on the surface of the intermediate layer obtained in step 2).

41. The preparation method according to claim 40, wherein The plating adopts a vacuum evaporation method.

42. The microcrystalline glass display screen described in any one of claims 1 to 39 or the microcrystalline glass display screen obtained by the preparation method described in claim 40 or 41 is used as a mobile phone microcrystalline glass display screen, a tablet computer microcrystalline glass display screen, a laptop computer microcrystalline glass display screen, a handheld game console, a car microcrystalline glass display screen, a windshield or a camera microcrystalline glass display screen.

43. The glass-ceramic display screen described in any one of claims 1 to 39 or the glass-ceramic display screen obtained by the preparation method described in claim 40 or 41 is used as a glass-ceramic display screen for portable digital devices.

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