Coated glass-ceramics containing a main crystalline phase and a secondary crystalline phase, and method for making and use thereof

Abstract

The present application relates to a coated glass-ceramic comprising a main crystalline phase and a secondary crystalline phase, and a method for manufacturing and using the same, the coated glass-ceramic being a glass-ceramic or glass-ceramic containing a hydrophobic and oleophobic composite coating on its surface, characterized in that, starting from the surface of the glass, it comprises: a hydrophobic and oleophobic layer, an intermediate layer, a primer layer and a glass-ceramic or glass-ceramic, wherein the intermediate layer is an intermediate layer formed by an ionic crystal containing a lattice energy of 700-3000 kJ / mol, and the primer layer comprises a compound containing Si-O bond or a mixed silicon oxide layer. Through the present application, even if the coated interface of the glass-ceramic has little Si-O structure, a firm, durable and excellent performance hydrophobic and oleophobic coating can be formed, and excellent hydrophobic and oleophobic properties can be achieved regardless of whether the high crystallinity glass has been ion exchanged.

Description

[0001] This application is a divisional application of Chinese patent application No. 202110128889.1, entitled "A Coated Microcrystalline Glass with Improved Hydrophobicity and Oleophobicity, its Preparation and Application", filed on January 29, 2021. Technical Field

[0002] This invention relates to a coated glass with hydrophobic and oleophobic properties, its preparation method and application, and particularly to a microcrystalline glass with a hydrophobic and oleophobic composite coating on its surface, especially to a coated microcrystalline glass containing a primary crystalline phase and a secondary crystalline phase, its preparation method and application. Background Technology

[0003] Glass generally has high surface activity, resulting in poor hydrophobicity and oleophobicity. This means it easily attracts dirt, which is difficult to clean once it's on the surface. In many applications, such as glass cooktops, range hoods, and touchscreen interfaces for mobile phones, tablets, and other human-computer interaction devices, a hydrophobic film is coated onto the glass surface to reduce surface activity and enhance its hydrophobic and oleophobic properties. Increased hydrophobicity results in a noticeable increase in the smoothness of contact when fingers touch the glass surface. This is because the increased hydrophobicity lowers the coefficient of 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 usually adopted. The coating material is generally PFPE (perfluoropolyether, a type of fluorinated polyether silicon oxide), and the structure of this fluorinated polyether silicon oxide (e.g., alkoxysilane) is shown in the following formula (1):

[0005]

[0006] Wherein, 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 epoxy alkyl group, an acyloxy hydrocarbon group, a hydrocarbon group, a sulfur group, etc.

[0007] The bonding process between PFPE and glass is a chemical reaction, involving the hydrolysis of PFPE (PFPE-Si-OR+H2O->PFPE-Si-OH+ROH), followed by a dehydration condensation reaction (e.g., Figure 1 As shown, PFPE-Si-OH+HO-Si→H2O+PFPE-Si-O-Si-), ultimately the PFPE film forms valence bonds with the Si-O structure on the glass interface, rather than relying on the physical phenomenon of intermolecular van der Waals forces as in most vacuum coatings.

[0008] The existing film coating method is generally as follows. Since there are a large number of Si-O structures in the glass, PFPE has the condition to react directly with the glass to form a film, but the mass fraction of SiO2 in the glass is generally not more than 70% at most, in order to improve the film coating effect and durability, the following two film coating methods are generally used:

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

[0010] b) Wet method: also called spray coating method, the surface of the glass is first bombarded by plasma in the atmosphere, on the one hand to clean the surface of the glass, and on the other hand to roughen the surface of the glass, to increase the surface area of the glass indirectly and increase the Si-O ratio, and then spray a layer of PFPE solution.

[0011] The existing patent CN208747932U discloses the structure of a transparent microcrystalline glass surface anti-fouling coating, characterized in that the outer surface of the microcrystalline glass body (1) is attached with a colorless transparent anti-fouling layer (11) with a thickness of 4-30 nm, and the anti-fouling layer (11) is a fluorosilicon hydrolysis compound. In this patent, it is recorded that the microcrystalline glass device is characterized in that the anti-fouling layer (11) has a thickness of 3-20 nm.

[0012] But the microcrystalline glass feature protected by this patent is "the mass ratio of crystal phase to glass phase in the microcrystalline glass body is 0.25-1.2", which belongs to a microcrystalline glass with medium-low crystallinity. The glass phase in the microcrystalline glass body uniformly wraps around the crystal phase, and the glass phase contains alkali metal ions such as sodium, lithium and potassium, and the mass of alkali metal oxides divided by the mass of aluminum oxide plus the mass of silicon dioxide in the glass phase is 6%-30%. The crystallinity of this microcrystalline glass is 20-54.54%, and the Si-O structure in the glass phase of this microcrystalline glass is still sufficient to support the formation of a good valence bond between PFPE and the microcrystalline glass. However, the invention does not mention the related issues for high-crystallinity microcrystalline glass.

[0013] The existing patent CN106715352A aims to solve the problem of poor binding force and durability of the ion exchange generated pre-stressed glass surface double-repellent or anti-fingerprint coating: "It has been found that chemical pre-stressing significantly reduces the durability of the double-repellent or anti-fingerprint coating. This is shown, for example, in a corresponding test, for example in a neutral salt spray test, for example specifically in WO 2012 / 163946 and WO 2012 / 163947, with shorter durability." The patent discloses its solution: "The present invention is therefore based on the object of overcoming the disadvantages of the prior art and providing a glass substrate which is chemically pre-stressed and has a double-repellent coating which has sufficient long-term durability. A method for producing a coated and chemically pre-stressed glass substrate should also be provided. The above object is achieved in a surprising manner in that the glass substrate is chemically pre-stressed by ion exchange through all layers on the glass, the functional coating present on the glass substrate is then activated, and only then is the double-repellent coating applied which acts as an anti-fingerprint coating." That is, first "functional coating" on the glass without ion exchange, then "ion exchange", then "activate the functional coating", and then "double-repellent coating plating". The patent mentions that it is found that it is particularly advantageous that the functional layer, in particular the uppermost functional layer, preferably comprises one or more Si compounds, particularly preferably one or more silicon oxide compounds, which can be selected from silicon oxides, for example. Preferably: silicon oxide SiOx, where x is less than or equal to 2; SiOC; SiON; SiOCN and Si3N4; and hydrogen which can be combined with SiOx (x less than or equal to 2), SiOC, SiON and SiOCN in any amount. In a preferred embodiment, the functional layer, in particular 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 double-repellent coating is generally reduced by chemical pre-stressing. This disadvantage is eliminated according to the invention. According to the invention, the surface of at least one functional layer is activated after chemical pre-stressing, so that the surface of the functional layer interacts with the double-repellent coating to be applied"; and the patent believes that the accumulation of potassium ions in the surface of the uppermost functional layer reduces the number of effective connection sites, such as Si-OH in Si-containing functional layers, and thus hinders covalent bonding on the double-repellent coating, so that the double-repellent coating is poorly adhered and has low long-term stability. In addition, the surface of the uppermost functional layer is usually subjected to the load of organic and inorganic contamination, which can 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 ability of the double-repellent coating, that is, the patent is a complete technical optimization for glass rich in Si-O structure and functional primer layer rich in Si-O structure. SUMMARY

[0014] The present application is directed to the prior art glass coating principle is based on inorganic glass as the substrate of the hydrophobic and oleophobic coating, generally speaking, the hydrophobic and oleophobic effect can reach: initial water drop angle test 110 ° or more, 115 ° or so, water drop angle can still reach 100 ° or more after rubbing 5000 times; but for the high crystallinity of more than 60% of the crystalline glass, also according to the principle and method of the prior art (using surface activation to activate Si-O to increase the double-sparse coating ability) to do, the effect is very poor, the initial water drop angle can only reach about 100 °, the water drop angle is only about 60 ° after rubbing 2500 times. The crystalline glass is also a kind of glass, the content of Si-O in its composition will not be less than that of ordinary inorganic glass, but why is there such a big difference? It can be understood that the traditional method is to develop a hydrophobic and oleophobic coating solution for the interface rich in Si-O structure, which cannot work effectively in the case of high crystallinity or lack of glass phase or Si-O structure on the interface.

[0015] In order to solve the prior art problems as described above, the present application provides the following technical solutions:

[0016] A crystalline glass containing a hydrophobic and oleophobic composite coating on the surface, characterized in that, from the outermost surface of the crystalline glass, it comprises in order: a hydrophobic and oleophobic layer, an intermediate layer and a primer layer, wherein the intermediate layer is an ionic crystal intermediate layer containing a lattice energy of 700-3000 kJ / mol, and the primer layer comprises a compound containing Si-O bond or a mixed silicon oxide layer.

[0017] Preferably, for any of the preceding crystalline glasses, the crystallinity can be greater than 60%; or can be greater than 70%; or can be greater than 80%.

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

[0019] Or a compound with a lattice energy of 9400-11400 KJ / mol, preferably a fluorosilicate, as the original coating material to form a fluoride intermediate layer.

[0020] Preferably, for any of the preceding crystalline glasses, the intermediate layer contains a fluorinated alkali metal or a fluorinated alkaline earth metal compound; or an intermediate layer formed by an ionic crystal selected from a fluorosilicate alkali metal and a fluorosilicate alkaline earth metal as the original coating material.

[0021] Preferably, for any one of the foregoing microcrystalline glass, the intermediate layer is an ionic crystal intermediate layer with a lattice energy less than 1050 KJ / mol, preferably less than 940 KJ / mol.

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

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

[0024] Preferably, for any one of the foregoing microcrystalline glass, the intermediate layer has a thickness of 1-5 nm, preferably 1-2 nm.

[0025] Preferably, for any one of the foregoing microcrystalline glass, the primer layer has a thickness of 3-15 nm, preferably 5-10 nm, more preferably 5-8 nm.

[0026] Preferably, for any one of the foregoing microcrystalline glass, the hydrophobic and oleophobic layer has a thickness of no less than 10 nm, preferably no less than 15 nm, and can be 10-25 nm.

[0027] Preferably, for any one of the foregoing microcrystalline glass, wherein, in the case where the primer layer is a plurality of layers, the compound containing Si-O bonds or the mixed silicon oxide layer is the outermost primer layer, and the mixed silicon oxide is a silicon oxide SiO x a mixture of an oxide of at least one element other than silicon and / or magnesium fluoride, wherein x is less than or equal to 2;

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

[0029] Preferably, for any one of the foregoing microcrystalline glasses, 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 in any proportion with any one of SiOx, SiOC, SiON and / or SiOCN, where x is less than or equal to 2.

[0030] Preferably, for any one of the foregoing microcrystalline glasses, the hydrophobic and oleophobic layer is a fluorine-based polymer layer, preferably a fluorine-containing polyether siloxane layer having a molecular weight of not less than 2000; preferably the coating layer has a thickness of not less than 10 nm.

[0031] Preferably, for any one of the foregoing microcrystalline glasses, the microcrystalline glass composition contains oxides in the following proportions in mol%:

[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 oxide: 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 one of the foregoing microcrystalline glasses, the rare earth oxide is selected from one or more, or two or more, of CeO2, Y2O3, La2O3, Ta2O3, Tm2O5 and Nd2O5.

[0045] Preferably, for any one of the preceding microcrystalline glasses, the microcrystalline glass can further comprise 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 one of the preceding microcrystalline glasses, the coloring additive is preferably present in a molar content of no more than 5% relative to the overall composition of the glass; preferably the coloring additive comprises 0.5 mol% or more of CoO and / or Cr2O3, and further preferably comprises 1 mol% or more of any one or more of Fe2O3, NiO or MnO2, relative to the molar content of the overall composition of the glass.

[0047] Preferably, for any one of the preceding microcrystalline glasses, the microcrystalline glass comprises a fining agent; preferably the fining agent is selected from one or more of As2O3, Sb2O3, SnO2, chlorides, fluorides, compounds containing SO3 - , and compounds containing NO3 - ; preferably the fining agent is selected from one or more of SnO2, compounds containing SO3 - , chlorides, and compounds containing NO3 - ; preferably the fining agent is present in a content of 0-2 mol%.

[0048] Preferably, for any one of the preceding microcrystalline glasses, the main crystalline 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 disilicate, lithium metasilicate, quartz, zirconia, magnetite; preferably the average grain size is 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 one of the preceding microcrystalline glasses, the microcrystalline glass is ion-exchanged or not ion-exchanged.

[0050] Further preferably, for any one of the preceding microcrystalline glasses, the microcrystalline glass is a glass-ceramic having a crystallinity of less than 60%.

[0051] The present application also provides a method for producing any one of the above-described microcrystalline glasses, comprising the following steps:

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

[0053] 2) coating the primer layer obtained in step 1) with an intermediate layer;

[0054] 3) coating the surface of the obtained intermediate layer of step 2) with a hydrophobic and oleophobic layer.

[0055] Preferably, for the above-mentioned preparation method, the coating is performed by vacuum evaporation.

[0056] Preferably, for any one of the above-mentioned preparation methods, the glass-ceramic is an ion-exchanged glass-ceramic.

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

[0058] (I) homogenizing the glass raw materials by high-temperature melting at 1600±50℃, and then annealing at 400-650℃ to obtain a homogenized glass sheet;

[0059] (II) forming the homogenized glass sheet into a shaped glass sheet by overflow down-draw method, float method or calendering method; and

[0060] (III) microcrystallizing the shaped glass sheet by secondary heat treatment to obtain a glass-ceramic preform, and then ion-exchanging or not ion-exchanging directly as the raw material of the glass-ceramic, which is used for coating the required primer layer, the intermediate layer and the hydrophobic and oleophobic layer on its surface in sequence, wherein the first heat treatment temperature is 500-1000℃, and the second heat treatment temperature is 550-1100℃.

[0061] Preferably, the glass-ceramic of any one of the above-mentioned or the glass-ceramic obtained by the above-mentioned preparation method is used in a display screen of a mobile phone, a tablet computer, a notebook computer, a palm game machine, a portable digital device, a vehicle display screen, a windshield or a camera.

[0062] In another preferred embodiment, the present application further provides the following technical solutions.

[0063] A glass-ceramic with a hydrophobic and oleophobic composite coating on its surface, characterized in that, from the outermost surface of the glass-ceramic, it comprises in sequence: a hydrophobic and oleophobic layer, an intermediate layer and a primer layer, wherein the intermediate layer is an ionic crystal intermediate layer with a lattice energy of 700-3000 kJ / mol, and the intermediate layer is a polar or non-polar compound; the primer layer comprises a compound containing Si-O bond or a mixed silicon oxide layer.

[0064] The glass-ceramic contains a main crystal phase and a secondary crystal phase, wherein the crystallinity content of the main crystal phase is 60-90 wt%, and the content of the secondary crystal phase is 60% or less.

[0065] It is also preferred that the crystallinity of the glass-ceramic according to the above is greater than 60%; or greater than 70%; or greater than 80%.

[0066] It is also preferred that the glass-ceramic according to any of the above, the intermediate layer is an intermediate layer formed using an ionic crystal having a lattice energy of 725-3000 kJ / mol, more preferably 770-3000 kJ / mol, as the original plating material.

[0067] or a fluoride intermediate layer formed using a compound having a lattice energy of 9400-11400 kJ / mol, preferably a fluorosilicate, as the original plating material.

[0068] It is also preferred that the glass-ceramic according to any of the above, the intermediate layer contains a fluorinated alkali or a fluorinated alkaline earth compound; or an intermediate layer formed using an ionic crystal selected from a fluorosilicate alkali and a fluorosilicate alkaline earth as the original plating material.

[0069] It is also preferred that the glass-ceramic according to any of the above, 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.

[0070] It is also preferred that the glass-ceramic according to any of the above, the intermediate layer is a crystal formed using at least one ionic crystal selected from LiF, NaF and / or KF as the original plating material; or an intermediate layer formed using at least one of MgF2, CaF2, SrF2 or BaF2 as the original plating material; or a fluoride intermediate layer formed using at least one of Li2SiF6, Na2SiF6, K2SiF6, Rb2SiF6, Cs2SiF6, BeSiF6, MgSiF6, CaSiF6, SrSiF6, or BaSiF6 as the original plating material.

[0071] It is preferred that the intermediate layer is formed using NaF or KF ionic crystals as the original plating material.

[0072] In addition, it is also preferred that the glass-ceramic according to any of the above, the intermediate layer is polar.

[0073] In addition, it is also preferred that the glass-ceramic according to any of the above, the thickness of the intermediate layer is 1-5 nm, preferably 1-2 nm.

[0074] In addition, it is also preferred that the glass-ceramic, the thickness of the primer layer is 3-15 nm, preferably 5-10 nm, more preferably 5-8 nm.

[0075] Further, it is also preferred that the microcrystalline glass according to any one of the aspects has a hydrophobic and oleophobic layer having a thickness of not less than 10 nm, preferably not less than 15 nm, and can be 10 nm to 25 nm.

[0076] Further, it is also preferred that the microcrystalline glass according to any one of the aspects, wherein, in the case where the primer layer is a multi-layer, the compound containing Si-O bond or the mixed silicon oxide layer as the outermost primer layer, the mixed silicon oxide is silicon oxide SiO x a mixture with an oxide of at least one element other than silicon and / or magnesium fluoride, wherein x is less than or equal to 2;

[0077] Preferably, the other element is an element of 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 with an oxide of aluminum.

[0078] Further, it is also preferred that the microcrystalline glass according to 11, the compound containing Si-O bond is SiOx, wherein 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 ratio, wherein x is less than or equal to 2.

[0079] Further, it is also preferred that the microcrystalline glass according to any one of the aspects, the hydrophobic and oleophobic layer is a fluorine-based polymer layer, preferably a fluorine-containing polyether siloxane layer having a molecular weight of not less than 2000; preferably, the plating layer has a thickness of not less than 10 nm.

[0080] Further, it is also preferred that the microcrystalline glass according to any one of the aspects, the microcrystalline glass composition contains

[0081] oxides in the following mol% ratio:

[0082] SiO2: 40-75%, preferably 45-72%;

[0083] Al2O3: 2-20%, preferably 4-15%;

[0084] B2O3: 0-20%, preferably 0.4-1.6%;

[0085] P2O5: 0-10%, preferably 0.8-1.5%;

[0086] ZrO2+TiO2: 0-15%, preferably 0.9-4%;

[0087] MgO: 0-5%, preferably 0.1-2%;

[0088] ZnO: 0-4%, preferably 0.9-3.0%;

[0089] Rare earth oxide: 0-5%, preferably 0.01-1%;

[0090] Na2O: 0-5.5%;

[0091] K2O: 0-4%;

[0092] Li2O: 2-34%, preferably 10-34%; and

[0093] Na2O + K2O + Li2O: 4-40%, preferably 15-40%

[0094] Further, it is also preferred that the glass-ceramics according to any one of the preceding items, the rare earth oxide is selected from one or more than one of CeO2, Y2O3, La2O3, T a2 O3, Tm2O5and Nd2O5.

[0095] Further, it is also preferred that the glass-ceramics according to any one of the preceding items, the main crystalline phase of the glass-ceramics is selected from one or more than one of β-quartz solid solution, β-spodumene solid solution, β-eucryptite, spinel, rutile, mullite, olivine, enstatite, cordierite, petalite, lithium disilicate, lithium metasilicate, quartz, zirconia, magnetite; preferably the average grain size is less than 100 nm, more preferably less than or equal to 50 nm, particularly preferably less than or equal to 30 nm.

[0096] Further, it is also preferred that the glass-ceramics according to any one of the preceding items, the glass-ceramics is ion-exchanged or non-ion-exchanged.

[0097] Further, it is also preferred that the glass-ceramics according to any one of the preceding items, the glass-ceramics is a glass-ceramic with a crystallinity less than 60%.

[0098] Further, it is also preferred that the method for preparing the glass-ceramics according to any one of the preceding items, comprising the following steps:

[0099] 2) coating the glass-ceramics with a Si-O containing oxide or mixed silicon oxide layer to form a primer layer on the surface of the glass-ceramics;

[0100] 2) coating the surface of the primer layer obtained in step 1) with an intermediate layer;

[0101] 3) coating the surface of the intermediate layer obtained in step 2) with a hydrophobic and oleophobic layer.

[0102] Further, it is also preferred that the method according to any one of the preceding items, wherein the coating is performed by vacuum evaporation.

[0103] In addition, it is also preferred that the microcrystalline glass or the microcrystalline glass prepared by the preparation method described above is applied to a display screen of a mobile phone, a display screen of a tablet computer, a display screen of a notebook computer, a palm game machine, a portable digital device, a vehicle display screen, a windshield or a camera display screen.

[0104] By the present application, even if the Si-O structure is very small at the interface of the microcrystalline glass or glass ceramic coating, a firm, durable and excellent performance hydrophobic and oleophobic coating can be formed, and excellent hydrophobic and oleophobicity can be achieved regardless of whether the high crystallinity glass is ion exchanged or not. BRIEF DESCRIPTION OF DRAWINGS

[0105] Figure 1 is a reaction process diagram of the hydrolysis product of PFPE connecting with glass. DETAILED DESCRIPTION

[0106] The composition of the microcrystalline glass is very similar to that of ordinary inorganic glass, and is generally SiO2

[0107] <70wt%, which should be able to prepare a good hydrophobic and oleophobic film according to the traditional coating method; but the microcrystalline glass has a large number of crystals in the body, and SiO2 usually enters the crystal during the formation of the microcrystalline glass, thereby changing the structure and causing the Si-O to be not well released to combine with the hydrophobic and oleophobic layer. The proportion of these small crystals is usually 20-100%, that is, when the proportion of the crystal is high, the glass phase in the microcrystalline glass is reduced, and the Si-O on the interface is greatly reduced, which is the main reason for the low quality of the hydrophobic and oleophobic coating. The present application provides a solution to this "rootless" problem.

[0108] Specifically, the present application provides the following technical solutions:

[0109] A composite coating design for a hydrophobic and oleophobic film on the surface of a high crystallinity microcrystalline glass or glass ceramic, which is formed in order from the outermost surface: a hydrophobic and oleophobic layer → an intermediate layer → a primer layer on the glass, that is, the primer layer is inside the microcrystalline glass or glass ceramic, and the hydrophobic and oleophobic layer is on the outside.

[0110] That is, the method of the present application realizes the formation of a hydrophobic and oleophobic film on a microcrystalline glass or glass ceramic with a crystallinity of more than 60%, and 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 application solves the problem of forming a hydrophobic and oleophobic film on a microcrystalline glass or glass ceramic with a crystallinity of more than 60%, a superior hydrophobic and oleophobic film composite coating can also be formed on a microcrystalline glass or glass ceramic with a crystallinity of less than 60% by the method of the present application.

[0111] Preferably, the intermediate layer is an ionic crystal having a lattice energy of 700-3000 kJ / mol (in terms of the magnitude of the lattice energy, the ionic crystal layer as the intermediate layer is preferably limited in composition 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).

[0112] The lattice energy of some common ionic crystals (kJ-mol -1 ) is shown in Table A below.

[0113] Table A Lattice energy of ionic crystals (kJ-mol -1 )

[0114] F - ]]> Cl - ]]> Br - ]] I - ]] Li + ]]> 1036 853 807 757 Na + ]]> 923 786 747 704 K + ]]> 821 715 682 649 Rb + ]] 785 689 660 630 Cs + ]] 740 659 631 604

[0115] Preferably, the lattice energy of the ionic crystal is preferably less than 1050 kJ / mol (the ionic crystal layer is preferably limited to alkali metal fluorides, LiF, NaF, and KF), and more preferably less than 940 kJ / mol (the ionic crystal layer is preferably limited to NaF and KF).

[0116] Li2SiF6, Na2SiF6, K2SiF6, and other alkali metal fluorosilicates and alkaline earth metal fluorosilicates can also be used as the intermediate layer.

[0117] Preferably, the intermediate layer is a polar or non-polar compound (preferably, alkali metal fluorides are non-polar, and alkaline earth metal fluorides are polar).

[0118] Further preferably, the compound is a non-polar compound (preferably, limited to alkali metal fluorides which are non-polar).

[0119] Preferably, the thickness of the intermediate layer is 1-5 nm, and more preferably 1-2 nm.

[0120] Preferably, the primer layer contains or consists of a Si compound, which is preferably selected from:

[0121] -SiOx, where x is less than or equal to 2, and in the case of multiple layers, at least the outermost or uppermost layer includes or consists of silicon oxide.

[0122] - SiOC, SiON, SiOCN and Si3N4, and hydrogen bonds in any proportion with SiOx, SiOC, SiON and SiOCN, wherein x is less than or equal to 2 (here "hydrogen bonds" means hydrogen bonds formed by any air component, such as moisture, with the silicate of the glass), wherein x is less than or equal to 2; or

[0123] - mixed silicates consisting of a silicate SiOxwith at least one oxide of an element other than silicon and / or magnesium fluoride, wherein the other element is preferably selected from at least one of aluminum, tin, magnesium, phosphorus, cerium, zirconium, titanium, cesium, barium, strontium, niobium, zinc, boron; particularly preferred is a mixture of the silicate SiOxwith at least one oxide of the element aluminum, wherein x is less than or equal to 2;

[0124] wherein preferably the total thickness of the primer layer is 3-15 nm, preferably 5-10 nm, more preferably 5-8 nm.

[0125] wherein the hydrophobic and oleophobic layer is also referred to as AF layer (anti-fingerprint layer), which is a layer formed by a fluorine-based polymer, which can be selected from the group consisting of perfluoropolyether

[0126] (perfluoropolyether), vinylidene fluoride polymer, tetrafluoroethylene polymer, hexafluoropropylene polymer, chlorotrifluoroethylene polymer and combinations thereof, preferably it can be a perfluoropolyether (PFPE). Further preferably, the hydrophobic and oleophobic layer is a PFPE having a molecular weight of not less than 2000, a coating thickness of not less than 10 nm, preferably not less than 15 nm, which can be in the range of 10-25 nm.

[0127] Further, preferably, the above-mentioned microcrystalline glass is transparent or opaque, before ion exchange or after ion exchange, i.e. with or without pre-stress.

[0128] Further, preferably, the method according to at least one of the above technical solutions is characterized in that the microcrystalline glass has the following glass composition or consists of a glass (in mol %):

[0129] SiO2: 40-75%, preferably 45-72%;

[0130] Al2O3: 2-20%, preferably 4-15%;

[0131] B2O3: 0-20%, preferably 0.4-1.6%;

[0132] P2O5: 0-10%, preferably 0.8-1.5%;

[0133] ZrO2+TiO2: 0-15%, preferably 0.9-4%;

[0134] MgO: 0-5%, preferably 0.1-2%;

[0135] ZnO: 0-4%, preferably 0.9-3.0%;

[0136] Rare earth oxide: 0-5%, preferably 0.01-1%;

[0137] Na2O: 0-5.5%;

[0138] K2O: 0-4%;

[0139] Li2O: 2-34%, preferably 10-34%; and

[0140] Na2O+K2O+Li2O: 4-40%, preferably 15-40%.

[0141] wherein the rare earth oxide is selected from one or more of CeO2, Y2O3, La2O3, Ta2O3, Tm2O5, and Nb2O5.

[0142] In addition, in some preferred embodiments, the above glass composition can contain: an additive of coloring oxide, such as Nd2O3, Fe2O3, CoO, NiO, V2O5, MnO2, TiO2, CuO, and Cr2O3; a rare earth oxide in an amount of 0-5 mol% or 0-5 mol% for "black glass"; and a fining agent in an amount of 0-2 mol%, such as one or more of As2O3, Sb2O3, SnO2, a compound containing CI - , a compound containing F - , a compound containing SO3 - , and a compound containing NO3 - .

[0143] In addition, in some preferred embodiments, the method according to at least one of the above technical solutions is characterized in that the main crystalline phase of the glass-ceramic is preferably selected from one or more of a beta-quartz solid solution, a beta-spodumene solid solution, a beta-eucryptite, a spinel, a rutile, a mullite, an olivine, an enstatite, a cordierite, a petalite, a lithium disilicate, a lithium metasilicate, a quartz, a zirconia, a magnetite; wherein the average grain size is preferably less than 100 nm, particularly preferably less than or equal to 50 nm, very particularly preferably less than or equal to 30 nm.

[0144] The present application adopts a combination of a primer layer, such as a SiO2 layer or a SiOx layer or a mixture layer containing silicon oxide (collectively referred to as "silicon oxide layer", here taking SiO2 as an example, which is not limited to SiO2 in practice) + an intermediate layer (referred to as "RF layer" for short, taking NaF as an example) + a hydrophobic and oleophobic layer such as PFPE: wherein the SiO2 layer cannot be too thick, about 5 nm, not more than 15 nm, the SiO2 layer has a network or chain structure under a microscope, the 5 nm SiO2 coating layer is very thin, and the SiO2 coating layer can also retain the network holes in its structure (coating too thick, which will cause the network holes to disappear due to the mutual overlapping of the SiO2 coating layers); a thinner intermediate layer RF is further coated, RF is a compound with a relatively low lattice energy, especially a non-polar compound, RF is selected from a compound with a relatively low lattice energy, and RF reacts with water to form R + 、F - 、H + 、OH - :

[0145]

[0146] Because of the presence of voids in the primer layer, R + 、F - 、H + 、OH - can very easily penetrate into the Si-O-Si structure in the interface of the glass-ceramic and the crystal, open the Si-O in the crystal structure, and form a basis that can better react with the hydrophobic and oleophobic layer and form a film:

[0147] ≡Si-O-Si≡+R + +OH - →≡Si-OH+RO-Si≡

[0148] ≡Si-O-Si≡+H + +F - →SiF4+H2O→H2SiO3+H2SiF6

[0149] When enough Si-O in the interface of the glass-ceramic and the primer layer is closely connected to the glass-ceramic base, enough valence bond connection will be generated when reacting with the uppermost layer of the hydrophobic and oleophobic layer PFPE, thereby greatly increasing the performance and wear resistance of the hydrophobic and oleophobic layer.

[0150] The intermediate layer with a more suitable lattice energy is the key to the working principle of the present application. If the lattice energy is slightly low, the intermediate layer is active and prone to reaction; if the lattice energy is moderate, the substance can be stable. The intermediate layer of the present application needs a certain range of lattice energy. The hydrolysis and activity of the intermediate layer material in the range of the lattice energy are still relatively high. After hydrolysis, it has a certain corrosive property. Therefore, it cannot be plated too thick. Otherwise, it is excessive. Generally, it cannot exceed 5 nm. If it is too thick, the reaction product cannot be consumed during the entire reaction process and will erode into the glass, causing serious corrosion points on the surface of the glass and also causing the weather resistance of the plated film layer to decrease.

[0151] Regarding the term "glass-ceramic or glass ceramic":

[0152] In the present application, the terms "glass-ceramic" and "glass ceramic" have the same meaning, referring to glass with crystalline phase, different from amorphous glass. Therefore, the terms "glass-ceramic or glass ceramic", "glass-ceramic" or "glass ceramic" appearing in the present specification all have the same meaning.

[0153] Regarding lattice energy:

[0154] Lattice energy refers to the energy absorbed when an ionic crystal becomes a gaseous positive ion and a gaseous negative ion under standard conditions. It is a parameter for measuring the stability of the lattice. Factors affecting the size of the lattice energy include ion radius, ion charge, and electron layer configuration of the ion. Referring to the method for calculating lattice energy in the literature "Topological Study of Lattice Energy and Magnetic Susceptibility of Alkaline Earth Metal Halides" by Qin Zhenglong and Liu Changjun, the formula obtained by fitting is as follows:

[0155] U = 1129.1 - 441.8 0 F + 3600.5 1 F

[0156] n F = ∑(E i × E j × E k ×...) -0.5 . n F is the topological index, and E is the valence electron energy level value.

[0157] The lattice energy of fluorides (KJ / mol) calculated by this method is shown in Table B below.

[0158] Table B Lattice energy of fluorides (KJ / mol)

[0159]

[0160] The regression equation obtained by applying the method has good correlation, and is also applicable to calculating the lattice energy of fluorosilicate. The results are shown in Table C below.

[0161] Table C Lattice energy (KJ / mol) of fluorosilicon compounds

[0162]

[0163] It should be particularly pointed out that the original substance of the coating and the substance finally formed on the primer layer at the glass interface are not necessarily the same concept. Taking the fluorosilicate alkali metal R2SiF6 calculated above as an example, R2SiF6 is a relatively stable solid at room temperature, and will decompose when heated to about 300°C during coating: R2SiF6-->RSi+SiF4(gas), that is, the substance with relatively high lattice energy seems to play a key role after film formation, but in fact the substance has undergone qualitative change, and its lattice energy is within the optimal working range claimed in the present application. For example, sodium silicate Na2SiF6 is a white granular or crystalline powder, odorless, tasteless; after heating (300°C or more), it decomposes into sodium fluoride NaF and silicon tetrafluoride SiF4.

[0164] Based on the above description of the principles of the present application, whether the interface of the coated microcrystalline glass is ion exchanged has no effect on the implementation and effect of the present application. Small ions in the glass must be in a state where ion movement can occur in order to exchange with large ions in the external salt bath. To achieve ion movement, temperature is a key factor. In general, the glass phase is relatively easy to achieve ion movement at a relatively low temperature (for example, starting at about 200 degrees Celsius at the strain point temperature, for example, 360°C), while the alkali metal elements in the microcrystalline phase are part of the crystal structure before they become movable ions, and require higher energy to break the crystal structure to become free exchangeable ions. This temperature is usually closer to the softening point of the glass (for example, 600 degrees Celsius or more). Therefore, ion exchange usually occurs mostly in the glass phase, and when the salt bath temperature is extremely high, it also occurs first in the glass phase and then in the crystal.

[0165] The glass phase of the high crystallinity glass-ceramics targeted by the present application is particularly small, even if there is a small glass phase, and ion exchange occurs, and the ions entering the glass phase are very small, and the ability to change the Si-O structure and coordination in the glass phase is very small, very local, and therefore has little influence on the formation of the coating valence bond described in the present application. That is, whether the high crystallinity glass has been ion exchanged or not, the interface is lack of Si-O structure, and the present application is targeted for such application scenarios. If high temperature is used, the ions in the crystal participate in ion exchange, that is, the crystal is damaged, and therefore the Si-O in the crystal will be opened, which will only help the formation of the coating valence bond described in the present application. The present application is exactly to solve the problem of how to form a firm, durable, and excellent performance hydrophobic and oleophobic coating under the condition of having very little Si-O structure at the coating interface. Whether the high crystallinity glass has been ion exchanged or not, it will not be rigidly implemented in the present application.

[0166] The preparation method of the glass-ceramics or glass ceramics with a surface containing a hydrophobic and oleophobic composite coating according to the present application is described in detail as follows.

[0167] The glass with the following composition is fired according to the following method to obtain a glass-ceramics or glass ceramics.

[0168] SiO2: 40-75%, preferably 45-72%;

[0169] Al2O3: 2-20%, preferably 4-15%;

[0170] B2O3: 0-20%, preferably 0.4-1.6%;

[0171] P2O5: 0-10%, preferably 0.8-1.5%;

[0172] ZrO2+TiO2: 0-15%, preferably 0.9-4.0%;

[0173] MgO: 0-5%, preferably 0.1-2%;

[0174] ZnO: 0-4%, preferably 0.9-3.0%;

[0175] Rare earth oxides: 0-5%, preferably 0.01-1%;

[0176] Na2O: 0-5.5%;

[0177] K2O: 0-4%

[0178] Li2O: 2-34%, preferably 10-34%; and

[0179] Na2O+K2O+Li2O: 4-40%; preferably 15-40%.​

[0180] wherein the glass-ceramic or glass-ceramics is prepared by a method comprising the following steps:

[0181] (I) melting each of the glass raw materials at a high temperature of 1600±50°C, and then annealing at 400-650°C to obtain a homogenized glass sheet;

[0182] (II) forming the homogenized glass sheet into a shaped glass sheet by an overflow downdraw method, a float method or a calendering method; and (III) crystallizing the shaped glass sheet by a secondary heat treatment to obtain a glass-ceramic preform, wherein the first heat treatment is performed at a temperature of 500-1000°C for 0.5-5h, and the second heat treatment is performed at a temperature of 550-1100°C for 0.5-6h; and then

[0183] (IV) ion-exchanging the glass-ceramic preform or directly using the glass-ceramic preform without ion-exchanging to sequentially coat a required primer layer, an intermediate layer and a water- and oil-repellent layer on the surface thereof.

[0184] wherein the ion-exchange can be performed by a conventional method, for example, by using a mixed molten salt containing 10-75wt% of NaNO3and 25-90wt% of KNO3by weight, and performing the ion-exchange at a temperature of 380-500°C for 5-10h.

[0185] Specifically, the sintering method comprises the following steps: weighing the glass raw materials, melting at a high temperature of 1600±50°C, and then annealing at about 400-650°C to homogenize the glass, and forming a glass-ceramic substrate, which can also be referred to as a glass sheet, is a glass sheet that has not been subjected to crystallization treatment and does not contain crystals. The glass sheet can be formed by an overflow downdraw method, a float method or a calendering method, and has a thickness of 0.1-5mm. The glass sheet can also be formed into a block shape, annealed and then cut into a sheet shape.

[0186] After the glass-ceramic substrate is formed, the glass-ceramic substrate is subjected to a secondary heat treatment to crystallize the glass-ceramic substrate, thereby obtaining a glass-ceramic preform, wherein the first heat treatment is performed at a temperature of 500-1000°C for 0.5-5h, and the second heat treatment is performed at a temperature of 550-1100°C for 0.5-6h. After crystallization, the required glass-ceramic or glass-ceramics is formed. Then, the glass-ceramic preform is ion-exchanged or directly used in a vacuum coating machine PVD without ion-exchanging, and the parameters for coating are set, and a primer layer, an intermediate layer and a water- and oil-repellent layer are sequentially coated. The process in the vacuum coating machine is as follows: glass loading- vacuumizing- plasma cleaning- evaporation- opening (vacuum to atmospheric pressure)- unloading.

[0187] The following examples are provided to illustrate how to prepare the chemically strengthened glass of the present application and the stress performance characteristics of the chemically strengthened glass of the present application.

[0188] First Part Example: Glass Preparation Example

[0189] The following example 1 is used to illustrate how to prepare the glass substrate:

[0190] (1) The materials of example 1 shown in Table 1 below were mixed, and the mixed materials were placed in a platinum crucible, melted in a high temperature furnace at 1600°C for 5h, then poured into a preheated stainless steel mold, and then placed in an annealing furnace at 580°C for 24h for annealing to eliminate the internal stress of the glass. After the annealing was completed, the glass brick was cut on six sides to obtain a glass brick, and then a wire cutting machine, a CNC engraving machine, a flat grinding machine, and a polishing machine were used for size precision cutting, flat grinding, and edge sweeping to obtain a raw glass plate with a size of 155mm x 78mm x 0.65mm.

[0191] The instrument model used in the above procedure is described as follows:

[0192] Multi-wire cutting machine: ch5625, Taizhou Chenhong CNC Equipment Manufacturing Co., Ltd.,

[0193] CNC machine tool engraving machine: CN-650, Shandong Chino CNC Equipment Co., Ltd.,

[0194] Flat grinding machine: YJ-13B6LD, Hunan Ningjing Machinery Co., Ltd., and

[0195] Polishing machine: YJ-13B6PD, Hunan Ningjing Machinery Co., Ltd.

[0196] (2) First, the raw glass plate was subjected to a first heat treatment at 650°C for 3h in a high temperature furnace to form crystal nuclei; and then subjected to a second heat treatment at 730°C for 3h to precipitate crystals, thereby preparing a glass ceramic. The glass ceramic was subjected to crystal analysis, including crystallinity, crystal type (i.e., main crystal phase and secondary crystal phase type), main crystal phase and secondary crystal phase ratio, and average grain size. The Vickers hardness, fracture toughness, average visible light transmittance, and haze of the glass ceramic (hereinafter also referred to as "glass ceramic without ion exchange") were also tested.

[0197] (3) The glass ceramic was subjected to ion exchange using a mixed salt bath of 40wt% NaNO3 and 60wt% KNO3, the strengthening temperature (i.e., ion exchange temperature) was 380°C, the strengthening time was 9h, and after the strengthening was completed, the glass ceramic was washed to obtain a strengthened glass ceramic (hereinafter also referred to as "glass ceramic subjected to ion exchange").

[0198] (4) The obtained strengthened glass ceramic is subjected to corresponding characterization tests, including haze, average transmittance of visible light, surface compressive stress, compressive stress depth and Young's modulus tests, and the specific test results are shown in Table 3.

[0199] Wherein, the definitions and test methods of crystallinity, main crystal phase, secondary crystal phase, average grain size, Vickers hardness, fracture toughness, average transmittance of visible light, haze, surface compressive stress, compressive stress depth and Young's modulus are as follows:

[0200] The surface compressive stress here refers to that after chemical strengthening of the glass, the alkali metal ions with small radius on the surface are replaced by alkali metal ions with large radius. Due to the crowding effect of the alkali metal ions with large radius, the surface of the glass thus produces a compressive stress, which is called surface compressive stress.

[0201] Crystallinity: The diffraction peak curve is obtained by XRD diffractometer analysis, wherein the incident angle range is 2Theta = 10-50 degrees, and the scanning speed is 6 degrees / min. The equipment used in this embodiment is Shimadzu

[0202] XRD-6000. The crystallinity is calculated according to formula (1-1):

[0203]

[0204] In the formula, I c is the diffraction integral intensity of the crystalline part of the glass-ceramic sample at 2Theta = 10-50 degrees;

[0205] I a is the diffraction integral intensity of the amorphous part of the glass-ceramic sample at 2Theta = 10-50 degrees;

[0206] K is the relative scattering factor per unit mass of the crystalline part and the amorphous part of the glass-ceramic sample at 2Theta = 10-50 degrees.

[0207] Main crystal phase proportion: In the glass ceramic, the crystal phase with the highest percentage by weight exists relative to other crystal phases.

[0208] Secondary crystal phase proportion: In addition to the main crystal phase, one or more other crystal phases can exist in the ceramic part of the glass ceramic, and the weight % of the secondary crystal phase is less than that of the main crystal phase.

[0209] Average grain size: average value of grain length in the glass-ceramics observed at a magnification of 100,000-1,000,000 times. Observation and measurement are performed by using a transmission electron microscope (model: ThermoFisher Scientific (former FEI) Talos F200S). When measuring, a magnified photo of a grain in a certain part is taken, there are limited grains in the area of the magnified photo, the size of the limited grains is marked according to the scale, and then the average value is obtained. In the embodiments of the present application, the magnification is 500,000 times when measuring.

[0210] Vickers hardness: the Vickers hardness is tested by using a Vickers hardness tester, and the test is performed according to the standard test method of GB / T 37900-2019 “Hardness and Fracture Toughness Test Methods for Ultra-thin Glass - Small Load Vickers Indentation Method”. In the embodiments, the equipment used is a digital small load Vickers hardness tester VTD405 (Beijing Wawoo Technology Co., Ltd.).

[0211] Fracture toughness: represents the concave measurement result. After polishing the test sample, a conical diamond indenter on the Vickers hardness tester is pressed on the sample at a load of 300 N for 10 seconds to form an indentation, so that the vertex of the indentation will generate a corresponding crack. The fracture toughness value K IC is calculated according to the indentation load P and the crack propagation length C. The specific fracture toughness is calculated according to the standard test method of GB / T 37900-2019 “Hardness and Fracture Toughness Test Methods for Ultra-thin Glass - Small Load Vickers Indentation Method”.

[0212] Surface compressive stress (MPa): the surface compressive stress of the glass to be tested is tested by using a waveguide light stress meter FSM-6000LE manufactured by ORIHARA Co., Ltd. of Japan.

[0213] Compressive stress depth (μm): the distance from the surface of the glass to be tested to the position where the compressive stress is zero.

[0214] Haze: the percentage of the intensity of the transmitted light deviating from the incident light by more than 2.5° to the total intensity of the transmitted light. The measurement is performed by using a colorimeter (model: CM-3600A).

[0215] Visible light transmittance: the ratio of the radiant energy projected and transmitted through the object to the total radiant energy projected onto the object in the process of the incident light flux from the illuminated surface or the medium incident surface to the other surface.

[0216] Average transmittance of visible light: the transmittance at each wavelength is measured at intervals of 10 nm wavelength within a certain wavelength range, and the sum of the measured transmittance at each wavelength is divided by the number of the measured transmittance at each wavelength to obtain the value. For example, the average transmittance of 360-400 nm wavelength is calculated as follows: the transmittance at wavelength of 360 nm, 370 nm, 380 nm, 390 nm and 400 nm is measured respectively, the number of the measured transmittance of 360-400 nm is 5, and the sum of the above transmittance is divided by 5 to obtain the average transmittance of 360-400 nm wavelength.

[0217] Young's modulus (Gpa): the Young's modulus of the sample obtained by using the acoustic wave method, and the instrument is IET-1600P high temperature elastic modulus tester.

[0218] Examples 2-15

[0219] The preparation method steps are the same as Example 1, and the differences are shown in Table 1, Table 2 and Table 3, that is, the specific glass frit raw material composition, the heat treatment process conditions of step (2), and the performance test of the obtained glass-ceramics, and the ion exchange process conditions of step (3) and the performance test results of the obtained strengthened glass-ceramics are shown in Table 1, Table 2 and Table 3.

[0220] Table 1: Each raw material for preparing glass (mol%)

[0221]

[0222] Table 2: Treatment conditions of the elementary glass (unstrengthened glass-ceramics) and performance parameters of the glass-ceramics after heat treatment

[0223]

[0224]

[0225] As can be seen from the above Table 2, the crystallinity of the glass-ceramics obtained by the present application after heat treatment is as low as 61.2% and as high as 90.35%, the visible light transmittance is between 89-92%, the average grain size is between 15.7 nm-25.5 nm, the haze is between 0.09-0.20%, the Vickers hardness is 718-796 HV, and the fracture toughness is 1.4-1.9 MPa·m 1 / 2 .

[0226] Table 3: Ion exchange conditions of the elementary glass and performance parameters of the strengthened glass obtained by ion exchange

[0227]

[0228] As can be seen from the above glass composition, rare earth oxides can be contained in the glass formula, specifically, in the present application, any one or more than two of CeO2, Y2O3, La2O3, Ta2O3, Tm2O5, and Nb2O5 can be added, and the content of these rare earth oxides is generally not more than 5 mol%; in addition, colorants and fining agents can be added as needed, specifically, in the above glass composition, Nb2O3 acts as a colorant, and in the present application, any one or more of the following substances can be added as a colorant in addition to Nb2O3: Nd2O3, Fe2O3, CoO, NiO, V2O5, MnO2, TiO2, CuO, CeO2, and Cr2O3; after the colorant is added, the visible light transmittance of the glass decreases; the more colorant added, the lower the transmittance; generally, the proportion added is not more than 5 mol%, and more than 1 mol% is added, and the overall color and transmittance of the glass change significantly; after too much colorant is added (for example, about 5 mol%), the crystallinity and crystal size of the glass-ceramic are affected; in the present application, the addition of 1 mol% of any combination of Fe2O3, NiO, MnO2, and other colorants in any proportion to the overall composition of the above examples will make the glass black, and the addition of 0.5 mol% or more of any combination of CoO, Cr2O3, and other colorants in any proportion will make the glass black with a blue phase. The use of no more than 5 mol% of colorant does not affect other properties of the glass.

[0229] In the glass of the present application, the fining agent can be used singly or in combination according to the actual melting conditions, and the fining agent is selected from one or more of As2O3, Sb2O3, SnO2, SO3 - containing compounds, fluorides or salts, chlorides or salts, and nitrate salts. Among them, As2O3 and Sb2O3 have good fining effect as fining agents, but are not preferred due to their toxicity; fluorides can also be used as fining agents, but are not preferred due to their corrosiveness; generally, single substances or combinations of SnO2, SO3 (such as Na2SO4), Cl compounds (such as NaCl), and NO3 - containing compounds (such as NaNO3) are commonly used fining agents, and the amount is generally not more than 1 mol%.

[0230] Second part of the embodiment: preparation of hydrophobic and oleophobic composite coating

[0231] 1. The glass-ceramics in Example 4 that have not been ion exchanged and have been ion exchanged are respectively formed into composite coatings as glass substrates

[0232] The glass ceramics prepared by the first part of Example 4, i.e. the glass ceramics without ion exchange, were used as the glass substrate (i.e. without ion exchange treatment of step (3)) (Nos. #4-A1 to 4-A15) and the glass ceramics with ion exchange as the glass substrate (i.e. with ion exchange treatment of step (3)) (Nos. #4-B1 to 4-B15) to form the composite coating layer comprising the SiO2, NaF and AF films, and the glass ceramics without ion exchange (Nos. #4-A16 to 4-A18) and the glass ceramics with ion exchange as the glass substrate (Nos. #4-B16 to 4-B18) were used to form the composite coating layer comprising the SiO2 and AF films, respectively. Specifically, the vacuum coating instrument described in Table 4-1 and the coating conditions described in Table 4-2 were used (Note: in each example, the coating time was controlled according to the thickness of the target coating layer, and the coating was stopped when the target thickness was reached), and the composite coating layer was formed by the following method: the surfaces of the glass substrates were cleaned by ultrasonic cleaning (or flat brush cleaning) respectively; after the surfaces of the glass substrates were cleaned, the surfaces of the substrates were sequentially coated with substantially uniform film layers by vacuum coating; the process of vacuum coating was as follows: the glass samples to be coated were placed on an umbrella-shaped coating rack, the umbrella-shaped coating rack was placed in the workpiece rack of the vacuum coating machine, SiO2 and NaF coating materials were separately placed in the two electron gun crucibles of the vacuum coating machine (using the Korean Vacuum 2050 type electron gun vacuum coating machine), and the materials were not mixed, the materials filled the crucibles and were flush with the surface of the crucible mouth, the AF film material (the crucible with steel wool after 600 ml of AF liquid was dropped into the crucible was called the AF film material) for forming the AF film (Anti-Fingerprint Glass, anti-fingerprint film) was placed in the molybdenum boat, the vacuum chamber was closed, and vacuum pumping was started; when the base vacuum degree reached the vacuum degree specified in Table 4-2 of the set process, the device automatically introduced Ar gas, the amount of Ar gas was 28 sccm; the IonBeam Source Hall ion source was operated, ion bombardment and cleaning of the sensitized glass surface were carried out; then the specific conditions such as the process vacuum degree, ion source voltage, ion source current, neutralization current, Ar and O2 gas ratio, electron gun working current, film forming rate, coating thickness (wherein the coating time parameter was controlled and adjusted when plasma cleaning was carried out before coating) were controlled and adjusted according to Table 4-2, and SiO2 and NaF (the raw materials used were both in the form of particles) were sequentially coated according to these conditions; then the specific conditions such as the process vacuum degree, molybdenum boat working current, film forming rate and coating thickness were controlled and adjusted according to Table 4-2, and AF was coated according to these conditions, wherein the L5 type SiO2 from the German Merck Company was used as the coating material for the SiO2 film.

[0233] 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 type fluorinated polyether manufactured by Shin-Etsu Chemical Industry Co., Ltd. of Japan as the AF main agent (manufactured by Shin-Etsu Chemical Industry Co., Ltd.) coating material (abbreviated as "PFPE" film).

[0234] After the coating is completed, the contact angle of the outer surface of the glass ceramic without ion exchange and the glass ceramic with ion exchange is tested. The test results of the thickness and contact angle of each layer of the SiO2, NaF and AF films are shown in Tables 5-1 and 5-2.

[0235] After coating, the water contact angle, oleic acid contact angle, and water droplet angle on the coated surface are measured to examine the coating quality and durability.

[0236] The water contact angle (°) of the AF membrane surface was measured using the method according to JIS R 3257 (1999).

[0237] The method for determining the oleic acid contact angle on the AF film surface is as follows: a 7 μL droplet is placed on a horizontally coated sample, and its tangential angle is measured.

[0238] The contact angle of oleic acid was tested by replacing water with hexadecane on glass-ceramics that had not undergone ion exchange. The test results for glass-ceramics numbered #4-A10, #4-A11, and #4-A12 are as follows:

[0239]

[0240] Abrasion resistance test: at 1cm 2 The indenter uses a Korean Minoan solid eraser (6mm diameter, Type A) (manufactured by MIRAESCIENCE Co., Ltd., Minoan) as a wear-resistant indenter. Under a load of 1kgf, the surface of the AF film formed on the glass substrate is rubbed back and forth 2500 times (or more) at a stroke radius of 40mm and a speed of 40mm / second. Then, the surface of the AF film is cleaned by dry wiping with a cloth [manufactured by Ozu Sangyo Co., Ltd., DUSPER (registered trademark)]. After the AF film wear resistance test, the water contact angle (°) is measured at three positions on the surface. Each position is measured and repeated three times, and the average water contact angle (°) at a total of 9 positions is measured.

[0241] Table 4-1 Instrument models used in vacuum coating of the embodiments of the present invention

[0242] Vacuum coater model Hanil Vacuum 2050 model electron gun vacuum coater Mechanical pump model Leybold SV630B Roots pump model Leybold WAU2001 Diffusion pump model HDP-700 (28'') PolyCold model PFC-1102HC Ion source model Hanil self-made Ion Beam Source Electron gun model HEG-103 Film thickness controller Inficon XTC / 3S

[0243] Note: In order to form a desired vacuum condition for plating, a person skilled in the art can select and use some or all of the pumps listed in Table 4-1 according to conventional means. Among them, the mechanical pump, also called the backing pump, uses oil to maintain the sealing effect and relies on mechanical methods to constantly change the volume of the suction cavity in the pump, so that the volume of the gas in the container to be pumped is constantly expanded to obtain a vacuum; the Roots pump is a booster pump, which functions to increase the pressure difference between the gas inlet and outlet, and is used with a mechanical pump as a backing pump; the diffusion pump is a pump used to obtain high vacuum, and when using a diffusion pump, a mechanical pump and a Roots pump are used as a backing pump; Polycold is a cryogenic water vapor pump, which is used to capture residual gas present in the high vacuum environment using a diffusion pump, and its working principle is to place a refrigeration coil capable of reaching -120°C or below at the pump port of the diffusion pump, and through the low-temperature condensation effect on its surface, the residual gas in the vacuum system is rapidly captured.

[0244] Table 4-2 Conditions for forming a composite coating in each embodiment of the present application

[0245]

[0246] Table 5-1 Formation of a composite coating using a glass-ceramic (crystallinity 80.1%) that has not been ion exchanged in Example 4 as a glass substrate

[0247]

[0248] Table 5-2 Formation of a composite coating using a glass-ceramic (crystallinity 80.1%) that has been ion exchanged in Example 4 as a glass substrate

[0249]

[0250] 2. Formation of a composite coating using a glass-ceramic that has not been ion exchanged and a glass-ceramic that has been ion exchanged in Example 8 as a glass substrate

[0251] Similar to the operation described above in Section 1 for forming a composite coating using a glass-ceramic formed in Example 4 as a glass substrate, the difference is that in this section, a glass-ceramic that has not been ion exchanged (Nos. #8-A1 to #8-A15) and a glass-ceramic that has been ion exchanged (Nos. #8-B1 to #8-B15) in Example 8 are used as a glass substrate to form a composite coating containing SiO2, NaF and AF films and a composite coating containing only SiO2 and AF films (glass-ceramic that has not been ion exchanged: Nos. #8-A16 to #8-A18; glass-ceramic that has been ion exchanged: Nos. #8-B16 to #8-B18), and the test results of the water contact angle of the outer surface of the coating are shown in Tables 6-1 and 6-2.

[0252] Table 6-1 Composite coatings formed on glass substrates of the glass-ceramics (crystallinity 90.35%) of Example 8 that were not ion exchanged

[0253]

[0254] Table 6-2 Composite coatings formed on glass substrates of the glass-ceramics (crystallinity 90.35%) of Example 8 that were ion exchanged

[0255]

[0256] 3. Composite coatings formed on glass substrates of the glass-ceramics of Example 12 that were not ion exchanged and were ion exchanged

[0257] Similar to the procedure described in Section 1 above for forming composite coatings on the glass-ceramics formed in Example 4 as glass substrates, except that in this section, glass-ceramics of Example 12 that were not ion exchanged (labeled #12-A1 through #12-A15, respectively) and were ion exchanged (labeled #12-B1 through #12-B15, respectively) were used as glass substrates to form composite coatings comprising SiO2, NaF and AF films, and composite coatings comprising only SiO2and AF films (glass-ceramics that were not ion exchanged: labeled #12-A16 through #12-A18, respectively; glass-ceramics that were ion exchanged: labeled #12-B16 through #12-B18, respectively), and the results of the water contact angle test on the outer surface of the coatings are shown in Tables 7-1 and 7-2.

[0258] Table 7-1 Composite coatings formed on glass substrates of the glass-ceramics (crystallinity 71.60%) of Example 12 that were not ion exchanged

[0259]

[0260] Table 7-2 Composite coatings formed on glass substrates of the glass-ceramics (crystallinity 71.60%) of Example 12 that were ion exchanged

[0261]

[0262] 4. Composite coatings formed on glass substrates of the glass-ceramics of Example 13 that were not ion exchanged and were ion exchanged

[0263] Similar to the operation of forming a composite coating layer on the glass ceramic formed in Example 4 as a glass substrate in Section 1 above, the difference is that in this section, the glass ceramics not ion exchanged (Nos. #13-A1 to #13-A15) and the glass ceramics ion exchanged (Nos. #13-B1 to #13-B15) in Example 13 are used as the glass substrate to form a composite coating layer containing SiO2, NaF and AF film, and a composite coating layer containing only SiO2 and AF film (glass ceramics not ion exchanged: Nos. #13-A16 to #13-A18; glass ceramics ion exchanged: Nos. #13-B16 to #13-B18), and the test results of the water contact angle of the outer surface of the coating layer are shown in Table 8-1 and Table 8-2.

[0264] Table 8-1 Formation of a composite coating layer on the glass ceramic not ion exchanged (crystallinity 61.20%) in Example 13 as a glass substrate

[0265]

[0266] Table 8-2 Formation of a composite coating layer on the glass ceramic ion exchanged (crystallinity 61.20%) in Example 13 as a glass substrate

[0267]

[0268] From the experimental results in Table 5-1, Table 5-2, Table 6-1, Table 6-2, Table 7-1, Table 7-2, Table 8-1 and Table 8-2 above, four different glass ceramics with different crystal proportions are selected from the 13 glass ceramic formulations, and the glass ceramics not ion exchanged and ion exchanged are used as the glass substrate to form a three-layer coating, and the following conclusions can be drawn from these data:

[0269] 1) When the primer layer is too thick, more than 20 nm, the wear resistance of AF is not good, so it is best not to exceed 15 nm in thickness;

[0270] 2) When the intermediate layer is too thick, more than 5 nm, the initial performance and wear resistance of AF are poor, but if there is no intermediate layer, it can be seen from the contact angle data in the last three rows of each table that the initial contact angle is mostly less than 100 degrees, and the contact angle after rubbing 2500 times is up to about 60 degrees;

[0271] 3) The effect of the primer layer being moderate, the intermediate layer being thin, and the AF layer being thick to thin is good;

[0272] 4) The surface layer is not less than 10 nm, and the composite coating obtained has good hydrophobic and oleophobic properties and excellent wear resistance, and it is preferred to be not less than 15 nm, the thicker the better, and from the cost point of view, the coating obtained by not more than 25 nm has ideal hydrophobic and oleophobic properties and wear resistance.

[0273] 5) even if ion exchange, i.e. prestressing, is not performed, the three-layer composite coating formed directly on the glass ceramic is excellent in water and oil repellency; when the strengthened glass subjected to ion exchange is further subjected to formation of the three-layer composite coating, the abrasion resistance test shows that the contact angle is greater, i.e. the water and oil repellency is more excellent.

[0274] In summary, it can be seen that the thickness of the primer layer is preferably 3-15 nm, the thickness of the intermediate layer is 1-5 nm, the thickness of the AF film layer is not less than 10 nm, preferably not less than 15 nm, and can be 10-25 nm; in addition, the thickness of the intermediate layer is preferably 1-2 nm; and the thickness of the primer layer is preferably 5-10 nm, and most preferably 5-8 nm.

[0275] 5. The glass ceramic not subjected to ion exchange in the first part of Example 4 (prepared according to the steps (1) and (2) based on the 4# formula, without the ion exchange treatment of step (3)) was subjected to formation of a surface composite coating according to the operation method and conditions described in Section 1 above (denoted as #4-a1, #4-a2, #4-a3, respectively), which differed only in the thickness of each coating, as shown in Table 9 below, and the quality and durability of the composite coating formed on the surface were tested, and the results are also summarized in Table 9 below.

[0276] The glass ceramic subjected to ion exchange in the first part of Example 4 was subjected to formation of a surface composite coating according to the operation method and conditions described in Section 1 above (also referred to as strengthened glass, denoted as #4-b1, #4-b2, #4-b3, respectively), which differed only in the thickness of each coating, as shown in Table 9 below, and the 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 the first part of Example 4, and all the test results are also summarized in Table 9 below.

[0277] The glass-ceramics not ion-exchanged in the first part of Example 4 were respectively doped with black colorant, i.e. based on the original raw glass formula, 0.5 mol% NiO, 1 mol% Fe203, 0.3 mol% CoO were additionally added to the total amount of each substance in the original raw glass formula of the 4# formula, and the glass-ceramics were prepared according to steps (1) and (2) in the first part "Glass preparation examples", and the surface forming composite coating was formed according to the operation method and operation condition described in the above section 1 (also referred to as black glass not ion-exchanged or black glass not pre-stressed, numbered #4-c1, #4-c2, #4-c3 respectively), the only difference being that the thickness of each coating is different, as shown in Table 9 below, and the plating film quality and durability of the surface formed composite coating were tested, and the results are also summarized in Table 9 below. The appearance of the obtained black glass is opaque black, and under strong white light irradiation it appears dark blue black.

[0278] Table 9 Plating film performance of composite coatings not ion-exchanged, ion-exchanged and added with black colorant

[0279]

[0280] As can be seen from Table 9 above, when the intermediate layer is thin in the range of 1-3 nm, whether or not it is ion-exchanged, i.e. glass pre-stressed, the AF film adhesion and wear resistance of the outer surface of the composite coating obtained are excellent, and even after adding black colorant, the AF film adhesion and wear resistance are not affected.

Claims

1. A microcrystalline glass having a surface containing a hydrophobic and oleophobic composite coating, characterized in that, From the outermost surface of the glass-ceramics, in order, comprises: a hydrophobic and oleophobic layer, an intermediate layer and a primer layer, wherein the intermediate layer is an ionic crystal intermediate layer containing a lattice energy of 700-3000kJ / mol, the intermediate layer is a polar or non-polar compound, the intermediate layer contains a fluorinated alkali or a fluorinated alkaline earth compound, or an ionic crystal selected from a fluorosilicon alkali and a fluorosilicon alkaline earth is used as the original coating material to form the intermediate layer; the primer layer comprises a compound containing Si-O bond or a mixed silicon oxide layer; The glass-ceramics contains a main crystal phase and a secondary crystal phase, wherein the main crystal phase has a crystallinity content of 60-90wt%, and the secondary crystal phase has a content of 60% or less; The thickness of the primer layer is 3-15nm, and the thickness of the intermediate layer is 1-5nm.

2. The glass-ceramics according to claim 1, having a crystallinity of greater than 60%.

3. The glass-ceramics according to claim 2, having a crystallinity of greater than 70%.

4. The glass-ceramics according to claim 3, having a crystallinity of greater than 80%.

5. The glass-ceramics according to claim 1, wherein the intermediate layer is an ionic crystal intermediate layer formed by using an ionic crystal with a lattice energy of 725-3000kJ / mol as the original coating material.

6. The glass-ceramics according to claim 5, wherein the intermediate layer is an ionic crystal intermediate layer formed by using an ionic crystal with a lattice energy of 770-3000kJ / mol as the original coating material.

7. The glass-ceramics according to claim 1, wherein the intermediate layer is an ionic crystal intermediate layer with a lattice energy of less than 1050KJ / mol.

8. The glass-ceramics according to claim 7, wherein the intermediate layer is an ionic crystal intermediate layer with a lattice energy of less than 940kJ / mol.

9. The glass-ceramics according to claim 1, wherein the intermediate layer is a crystal formed by using at least one of LiF, NaF and / or KF as the original coating material; or is an intermediate layer formed by using at least one of MgF2, CaF2, SrF2 or BaF2 as the original coating material; or is a fluoride intermediate layer formed by using at least one of Li2SiF6, Na2SiF6, K2SiF6, Rb2SiF6, Cs2SiF6, BeSiF6, MgSiF6, CaSiF6, SrSiF6, or BaSiF6 as the original coating material.

10. The glass-ceramics according to claim 1, wherein the intermediate layer is formed by using an ionic crystal of NaF or KF as the original coating material.

10. The glass-ceramic according to claim 9, wherein, 11. The glass-ceramics according to any one of claims 1-10, wherein the intermediate layer is polar.

12. The glass-ceramics according to any one of claims 1-10, wherein the thickness of the intermediate layer is 1-2nm.

13. The glass-ceramics according to any one of claims 1-10, wherein the thickness of the primer layer is 5-10nm.

14. The glass-ceramics according to claim 13, wherein the thickness of the primer layer is 5-8nm. ​ 15. The glass-ceramic according to any one of claims 1 to 10, wherein the water- and oil-repellent layer has a thickness of not less than 10 nm.

16. The glass-ceramic according to claim 15, wherein the water- and oil-repellent layer has a thickness of not less than 15 nm.

17. The glass-ceramic according to claim 16, wherein the water- and oil-repellent layer has a thickness of 10 nm to 25 nm.

18. The glass-ceramic according to any one of claims 1 to 10, wherein, In the case where the primer layer is a multi-layer, the compound containing Si-O bond or the mixed silicon oxide layer is the outermost primer layer, and the mixed silicon oxide is a mixture of silicon oxide SiOx and oxide of at least one element other than silicon, and / or magnesium fluoride, wherein x is less than or equal to 2.

19. The glass-ceramic according to claim 18, wherein the compound containing Si-O bond is SiOx, wherein 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 ratio, wherein x is less than or equal to 2. The other element is an element selected from the group consisting of aluminum, tin, magnesium, phosphorus, cerium, zirconium, titanium, cesium, barium, strontium, niobium, zinc and boron.

20. The microcrystalline glass of claim 18, wherein, The mixed silicon oxide is a mixture of silicon oxide SiOx and oxide of aluminum.

21. The glass-ceramic according to any one of claims 1 to 10, wherein the water- and oil-repellent layer is a fluorine-based polymer layer.

22. The glass-ceramic according to claim 21, wherein the water- and oil-repellent layer is a fluorine-containing polyether siloxane layer having a molecular weight of not less than 2000.

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

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

25. The glass-ceramic according to claim 18, wherein the glass-ceramic composition contains oxides in the following mol% ratio: SiO2: 40 to 75%; Al2O3: 2 to 20%; B2O3: 0 to 20%; P2O5: 0 to 10%; ZrO2 + TiO2: 0 to 15%; MgO: 0 to 5%; ZnO: 0-4%; rare earth oxide: 0-5%; Na2O: 0-5.5%; K2O: 0-4%; Li2O: 2-34%; and Na2O + K2O + Li2O: 4-40%.

26. The glass-ceramic according to claim 23, the glass-ceramic composition comprising oxides in the following mol% proportions: 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 oxide: 0.01-1%; Na2O: 0-5.5%; K2O: 0-4%; Li2O: 10-34%; and Na2O + K2O + Li2O: 15-40%.

27. The glass-ceramic according to claim 23, the rare earth oxide being selected from one or more of CeO2, Y2O3, La2O3, Ta2O3, Tm2O5, and Nd2O5.

28. The glass-ceramic according to any one of claims 1-10, the main crystalline phase of the glass-ceramic being selected from one or more of β-quartz solid solution, β-spodumene solid solution, β-eucryptite, spinel, rutile, mullite, olivine, enstatite, cordierite, petalite, lithium silicates, lithium disilicates, quartz, zirconia, and magnetite.

29. The glass-ceramic according to claim 23, the main crystalline phase of the glass-ceramic being selected from one or more of β-quartz solid solution, β-spodumene solid solution, β-eucryptite, spinel, rutile, mullite, olivine, enstatite, cordierite, petalite, lithium silicates, lithium disilicates, quartz, zirconia, and magnetite.

30. The glass-ceramic according to claim 24, the main crystalline phase of the glass-ceramic being selected from one or more of β-quartz solid solution, β-spodumene solid solution, β-eucryptite, spinel, rutile, mullite, olivine, enstatite, cordierite, petalite, lithium silicates, lithium disilicates, quartz, zirconia, and magnetite.

31. The glass-ceramic according to claim 25, the main crystalline phase of the glass-ceramic being selected from one or more of β-quartz solid solution, β-spodumene solid solution, β-eucryptite, spinel, rutile, mullite, olivine, enstatite, cordierite, petalite, lithium silicates, lithium disilicates, quartz, zirconia, and magnetite.

32. The glass-ceramic according to claim 28, having an average crystalline grain size of 100 nm or less.

33. The glass-ceramic according to claim 28, having an average crystalline grain size of 50 nm or less.

34. The glass-ceramic according to claim 28, having an average crystalline grain size of 30 nm or less.

35. The glass-ceramic according to any one of claims 1-10, the glass-ceramic being ion exchanged or not ion exchanged.

36. The glass-ceramic according to claim 1, the glass-ceramic being a glass-ceramic having a crystallinity of less than 60%.

37. The method for preparing the glass-ceramics according to any one of claims 1-36, comprising the following steps: 1) coating the glass-ceramics with a Si-O containing oxide or mixed silicon oxide layer to form a primer layer on the surface of the glass-ceramics; 2) coating the surface of the primer layer obtained in step 1) with an intermediate layer; 3) coating the surface of the intermediate layer obtained in step 2) with a water and oil repellent layer.

38. The method of manufacturing according to claim 37, wherein, The coating is performed by vacuum evaporation.

39. The use of the glass-ceramics according to any one of claims 1-36 or the glass- ceramics prepared by the method according to claim 37 in mobile phone display screens, tablet computer display screens, notebook computer display screens, palm game consoles, vehicle display screens, windshields or camera display screens.

40. The use of the glass-ceramics according to any one of claims 1-36 or the glass- ceramics prepared by the method according to claim 37 in portable digital devices.

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