Fluorine-containing polymer hydrophobic and oleophobic layer-coated microcrystalline glass, method for manufacturing the same, and use thereof

Abstract

This invention relates to coated microcrystalline glass with a fluorinated polymer hydrophobic and oleophobic layer, its preparation method, and applications. The coated glass is a microcrystalline glass or glass-ceramic with a hydrophobic and oleophobic composite coating on its surface. The invention is characterized by comprising, starting from the outermost surface of the glass: a hydrophobic and oleophobic layer, an intermediate layer, a base layer, and the microcrystalline glass or glass-ceramic. The intermediate layer is formed by ionic crystals containing lattice energy of 700-3000 kJ / mol, and the base layer comprises a compound containing Si-O bonds or a mixed silicon oxide layer. This invention enables the formation of a robust, durable, and high-performance hydrophobic and oleophobic coating at the coating interface of the microcrystalline glass, even with minimal Si-O structure. Excellent hydrophobic and oleophobic properties can be achieved regardless of whether the highly crystalline glass has undergone ion exchange.

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, particularly to a microcrystalline glass with a hydrophobic and oleophobic composite coating on its surface, and especially to a coated microcrystalline glass with a fluorinated polymer hydrophobic and oleophobic coating, 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 (per-fluorinated polyether, 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] (1);

[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 deposition processes.

[0008] The coating methods in the prior art are generally as follows. Given the large amount of Si-O structures within glass, PFPE has the potential to react directly with glass to form a film. However, the mass proportion of SiO2 in glass is usually no more than 70%. To improve the coating effect 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 first deposited on the glass surface in a vacuum to increase the Si-O ratio, and then a layer of PFPE is deposited in the vacuum environment.

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

[0011] Existing patent CN208747932U discloses the structure of an anti-fouling coating on the surface of a transparent microcrystalline glass. Its characteristic is that a colorless and transparent anti-fouling layer (11) with a thickness of 4-30 nm is attached to the outer surface layer of the microcrystalline glass body (1), and the anti-fouling layer (11) is a fluorosilicone hydrolysis compound. Furthermore, this patent describes that the microcrystalline glass device is characterized by having a silicon dioxide layer with a thickness of 3-20 nm beneath the anti-fouling layer (11).

[0012] However, the key feature of the microcrystalline glass protected by this patent is that "the mass ratio of the crystalline phase to the glass phase in the microcrystalline glass body is 0.25-1.2," which belongs to the category of microcrystalline glass with low to medium crystallinity. In this microcrystalline glass body, the glass phase is uniformly wrapped around the crystalline phase, and the glass phase contains alkali metal ions such as sodium, lithium, and potassium. Furthermore, the mass of the alkali metal oxides in the glass phase divided by (the mass of aluminum oxide plus the mass of silicon dioxide) is 6%-30%, and the crystallinity of this microcrystalline glass is 20-54.54%. The Si-O structure in the glass phase of this microcrystalline glass is still sufficiently abundant to support the formation of good valence bonds between PFPE and the microcrystalline glass. However, this invention does not mention the relevant issues for high-crystallinity microcrystalline glass.

[0013] Existing patent CN106715352A addresses the problem of poor adhesion and durability of ion-exchange-generated prestressed glass surfaces with double-repellent or anti-fingerprint coatings: "It has been found that chemical prestressing significantly reduces the durability of double-repellent or anti-fingerprint coatings. This is demonstrated, for example, in corresponding tests, such as the neutral salt spray test, which is specifically described in WO2012 / 163946 and WO 2012 / 163947." This patent discloses its solution as follows: The present invention is therefore based on the objective of overcoming the deficiencies of the prior art and providing a glass substrate that is chemically prestressed and has a double-repellent coating, which possesses sufficient long-term durability. A method for manufacturing a coated and chemically prestressed glass substrate should also be provided. The above objective is thus achieved in a surprising way: the glass substrate is chemically prestressed by ion exchange through all layers of the glass, followed by activation of the functional coating present on the glass substrate, and then the double-repellent coating acting as an anti-fingerprint coating is applied. In other words, the process involves first applying a "functional coating" to glass that has not undergone ion exchange, then performing "ion exchange," followed by "activating the functional coating," and finally "applying a dual-hydrophobic coating." The patent mentions that it is particularly advantageous that the functional layer, especially the uppermost functional layer, preferably comprises one or more Si compounds, particularly one or more silicon oxide compounds. The Si compounds can be selected from silicon oxides, for example: silicon oxide SiOx, where x is less than or equal to 2; SiOC; SiON; SiOCN and Si3N4; and hydrogen capable of combining 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 primarily composed of inorganic components containing a Si-O structure. The patent states that "chemical prestressing typically weakens the long-term stability of dual-hydrophobic coatings. This defect is eliminated according to the present invention." According to the present invention, the surface of at least one functional layer is activated after chemical prestressing, thereby allowing the surface of the functional layer to interact with the bihydrophobic coating to be applied. Furthermore, the patent argues that the accumulation of potassium ions on the surface of the uppermost functional layer reduces the number of effective bonding sites, such as Si-OH in Si-containing functional layers, thereby hindering covalent bonding on the bihydrophobic coating, resulting in poor adhesion and low long-term stability. Additionally, the surface of the uppermost functional layer is typically loaded with organic and inorganic contaminants that oppose the desired interaction. Therefore, the patent adjusts the ion exchange sequence and employs surface activation to activate Si-O to increase the adhesion of the bihydrophobic coating. In other words, the patent is a technical optimization specifically for Si-O-rich glass and Si-O-rich functional underlayers. Summary of the Invention

[0014] This invention addresses the issue that existing glass coating principles are based on hydrophobic and oleophobic coatings using inorganic glass as a substrate. Generally, these coatings achieve an initial water droplet angle of over 110° to around 115°, and maintain over 100° even after 5000 rubs. However, for highly crystalline microcrystalline glass (over 60% crystallinity), following existing principles and methods (using surface activation to activate Si-O to enhance the double-hydrophobic coating's effectiveness) yields very poor results. The initial water droplet angle typically only reaches around 100°, and after 2500 rubs, it drops to only around 60°. Microcrystalline glass is also a type of glass, and its Si-O content is not less than that of ordinary inorganic glass. Why then such a large difference? This can be understood as follows: traditional methods are designed for interfaces rich in Si-O structures, and these solutions are ineffective in high-crystallinity environments or where the interface lacks a glass phase or Si-O structure.

[0015] To address the problems of the prior art as described above, the present invention provides the following technical solution:

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

[0017] Preferably, for any of the aforementioned microcrystalline glasses, the crystallinity may be greater than 60%; or greater than 70%; or greater than 80%.

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

[0019] Alternatively, it can be a compound with a lattice energy of 9400-11400 KJ / mol, preferably a fluoride intermediate layer, formed using a fluoride as the primary coating material.

[0020] Preferably, for any of the aforementioned microcrystalline glasses, the intermediate layer contains alkali metal fluoride or alkaline earth metal fluoride compounds; or the intermediate layer is formed using an ionic crystal selected from alkali metal fluoride and alkaline earth metal fluoride as the original coating material.

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

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

[0023] Preferably, for any of the aforementioned microcrystalline glasses, the intermediate layer is a polar or non-polar compound; more preferably, it is a polar compound.

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

[0025] Preferably, for any of the microcrystalline glass described above, the thickness of the underlayer is 3-15 nm, more preferably 5-10 nm, and even more preferably 5-8 nm.

[0026] Preferably, for any of the aforementioned microcrystalline glasses, 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 to 25 nm.

[0027] Preferably, for any of the aforementioned microcrystalline glass layers, wherein, in the case of a multi-layered underlayer, the compound containing Si-O bonds or the mixed silicon oxide layer serves as the outermost underlayer, and the mixed silicon oxide is silicon oxide (SiO₂). x A mixture of oxides 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 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 (SiO₂). x A mixture with aluminum oxide.

[0029] Preferably, for any of the aforementioned microcrystalline glasses, 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 formed 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 of the aforementioned microcrystalline glass, the hydrophobic and oleophobic layer is a fluorinated polymer layer, preferably a fluorinated polyether silicon oxide layer with a molecular weight of not less than 2000; preferably, the coating thickness is not less than 10 nm.

[0031] Preferably, for any of the aforementioned glass-ceramics, the glass-ceramic composition contains the following mol% proportion 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 oxide is selected from one or more of CeO2, Y2O3, La2O3, Ta2O3, Tm2O5 and Nd2O5.

[0045] Preferably, for any of the aforementioned microcrystalline glass, 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.

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

[0047] Preferably, for any of the aforementioned microcrystalline glasses, the microcrystalline glass contains a clarifying agent; preferably, the clarifying agent is selected from As2O3, Sb2O3, SnO2, chlorides, fluorides, and SO3-containing compounds. - Compounds and those containing NO3 - One or more of the compounds, preferably selected from SnO2 and SO3-containing compounds. - Compounds, chlorides, and NO3-containing compounds - One or more of the compounds; preferably, the content of the clarifying agent is 0-2 mol.

[0048] Preferably, for any of the aforementioned 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-nepheline, spinel, rutile, mullite, olivine, enstatite, cordierite, petalite, lithium silicate, lithium disilicate, quartz, zirconium oxide, and 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 of the aforementioned microcrystalline glasses, the microcrystalline glass is glass that has undergone ion exchange or has not undergone ion exchange.

[0050] Preferably, for any of the aforementioned microcrystalline glasses, the microcrystalline glass is a glass-ceramic with a crystallinity of less than 60%.

[0051] The present invention also provides a method for preparing any of the microcrystalline glasses described above, which includes the following steps:

[0052] 1) A layer of Si-O-containing oxide or mixed silicon oxide is deposited on the surface of the glass-ceramic to form a base layer;

[0053] 2) The intermediate layer is plated onto the surface of the base layer obtained in step 1);

[0054] 3) Coat the surface of the intermediate layer obtained in step 2) with a water-repellent and oil-repellent layer.

[0055] Preferably, in the preparation method described above, the coating is performed using a vacuum evaporation method.

[0056] Preferably, in any of the preparation methods described above, the glass-ceramic is an ion-exchanged glass-ceramic.

[0057] Preferably, for any of the preceding preparation methods, the microcrystalline glass is obtained by firing a process comprising the following steps before coating the underlayer, intermediate layer, and hydrophobic and oleophobic layer:

[0058] (I) The glass raw materials are melted at 1600±50℃ and then annealed at 400-650℃ to obtain homogenized plain glass plates.

[0059] (II) The raw glass sheet is shaped into a finished raw glass sheet by overflow drawing, float glass, or rolling; and

[0060] (III) The molded glass plate is microcrystallized by secondary heat treatment to obtain a microcrystalline glass preform. Then, ion exchange is performed or no ion exchange is performed and it is used directly as the raw material for microcrystalline glass. The required base layer, intermediate layer and hydrophobic and oleophobic layer are sequentially coated on its surface. The first heat treatment temperature is 500-1000℃ and the second heat treatment temperature is 550-1100℃.

[0061] Preferably, the microcrystalline glass described above or the microcrystalline glass obtained by any of the preparation methods described above is used in displays for mobile phones, tablet computers, laptops, handheld game consoles, portable digital devices, automotive displays, windshields, or cameras.

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

[0063] A microcrystalline glass with a hydrophobic and oleophobic composite coating on its surface, characterized in that, starting from the outermost surface of the microcrystalline glass, it comprises, in sequence: a hydrophobic and oleophobic layer, an intermediate layer, and a base layer, wherein the intermediate layer is formed by using an ionic crystal with a lattice energy of 725-3000 kJ / mol or a compound with a lattice energy of 9400-11400 kJ / mol as the original coating material, and the base layer comprises a compound containing Si-O bonds or a mixed silicon oxide layer;

[0064] The hydrophobic and oleophobic layer is a fluorinated polymer layer with a thickness of 10nm-25nm.

[0065] Preferably, the microcrystalline glass may also contain coloring additives.

[0066] More preferably, according to the microcrystalline glass described above, the intermediate layer is formed by using an ionic crystal with a lattice energy of 770-3000 kJ / mol as the original coating material.

[0067] Alternatively, a fluoride intermediate layer can be formed using fluorine-silicon compounds with a lattice energy of 9400-11400 KJ / mol as the initial coating material.

[0068] Preferably, according to the aforementioned microcrystalline glass, the intermediate layer contains alkali metal fluoride or alkaline earth metal fluoride compounds; or the intermediate layer is formed using an ionic crystal selected from alkali metal fluoride and alkaline earth metal fluoride as the original coating material.

[0069] More preferably, according to the aforementioned microcrystalline glass, the intermediate layer is an ionic crystal intermediate layer with a lattice energy of less than 1050 kJ / mol, preferably less than 940 kJ / mol.

[0070] Preferably, according to the aforementioned microcrystalline glass, the intermediate layer is a crystal formed by using at least one ionic crystal selected from LiF, NaF, and / or KF as the original coating material; or an intermediate layer formed by using at least one selected from MgF2, CaF2, SrF2, or BaF2 as the original coating material; or a fluoride intermediate layer formed by using at least one selected from Li2SiF6, Na2SiF6, K2SiF6, Rb2SiF6, Cs2SiF6, BeSiF6, MgSiF6, CaSiF6, SrSiF6, or BaSiF6 as the original coating material for coating.

[0071] The intermediate layer is preferably formed using NaF or KF ionic crystals as the original coating material.

[0072] More preferably, in the microcrystalline glass according to any of the preceding claims, the intermediate layer is a polar or non-polar compound; preferably a polar compound.

[0073] More preferably, in the microcrystalline glass according to any of the preceding claims, the thickness of the intermediate layer is 1-5 nm, more preferably 1-2 nm.

[0074] More preferably, in the microcrystalline glass according to any of the preceding claims, the thickness of the underlayer is 3-15 nm, more preferably 5-10 nm, and even more preferably 5-8 nm.

[0075] More preferably, in the case of a multi-layered underlayer, the compound containing Si-O bonds or the mixed silicon oxide layer serves as the outermost underlayer, wherein the mixed silicon oxide is silicon oxide (SiO₂). x A mixture of oxides of at least one element other than silicon and / or magnesium fluoride, wherein x is less than or equal to 2;

[0076] 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 (SiO₂). x A mixture with aluminum oxide.

[0077] More preferably, in the microcrystalline glass according to any of the preceding claims, the compound containing Si-O bonds 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 formed in any proportion with any one of SiOx, SiOC, SiON and / or SiOCN, wherein x is less than or equal to 2.

[0078] More preferably, the microcrystalline glass according to any of the preceding claims comprises an oxide in the following mol% proportion:

[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] More preferably, in the microcrystalline glass according to any of the preceding claims, the rare earth oxide is selected from one or more of CeO2, Y2O3, La2O3, Ta2O3, Tm2O5 and Nd2O5.

[0092] More preferably, in the microcrystalline glass according to any of the preceding claims, the coloring additive is selected from one or more of Nd2O3, Fe2O3, CoO, NiO, V2O5, MnO2, TiO2, CuO and Cr2O3.

[0093] More preferably, in the microcrystalline glass according to any of the preceding claims, the coloring additive has a molar content of no more than 5% relative to the overall glass composition; preferably, the coloring additive contains more than 0.5 mol% of CoO and / or Cr2O3 relative to the overall glass composition, and even more preferably, it contains more than 1 mol% of any one or more selected from Fe2O3, NiO or MnO2.

[0094] More preferably, in the microcrystalline glass according to any of the preceding claims, the main crystalline phase of the microcrystalline glass is selected from one or more of β-quartz solid solution, β-spodumene solid solution, β-nepheline, spinel, rutile, mullite, olivine, enstatite, cordierite, petalite, lithium silicate, lithium disilicate, quartz, zirconium oxide, and 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.

[0095] More preferably, the microcrystalline glass according to any of the preceding claims is a glass that has undergone ion exchange or has not undergone ion exchange.

[0096] More preferably, the microcrystalline glass according to any of the preceding claims may be a glass-ceramic with a crystallinity greater than 60%; or greater than 60%, greater than 70%, or greater than 80%.

[0097] In addition, the present invention also provides a method for preparing the microcrystalline glass described in any of the preceding claims, which includes the following steps:

[0098] 1) A layer of Si-O-containing oxide or mixed silicon oxide is deposited on the surface of the glass-ceramic to form a base layer;

[0099] 2) The intermediate layer is plated onto the surface of the base layer obtained in step 1);

[0100] 3) Coat the surface of the intermediate layer obtained in step 2) with a water-repellent and oil-repellent layer.

[0101] More preferably, according to the preparation method described above, the microcrystalline glass is obtained by firing a process comprising the following steps before coating the underlayer, intermediate layer, and hydrophobic and oleophobic layer:

[0102] (I) The glass raw materials are melted at 1600±50℃ and then annealed at 400-650℃ to obtain homogenized plain glass plates.

[0103] (II) The raw glass sheet is shaped into a finished raw glass sheet by overflow drawing, float glass, or rolling; and

[0104] (III) The molded glass plate is microcrystallized by secondary heat treatment to obtain a microcrystalline glass preform. Then, ion exchange is performed or no ion exchange is performed and it is used directly as the raw material for microcrystalline glass. The required base layer, intermediate layer and hydrophobic and oleophobic layer are sequentially coated on its surface. The first heat treatment temperature is 500-1000℃ and the second heat treatment temperature is 550-1100℃.

[0105] More preferably, the microcrystalline glass obtained according to any of the preceding claims or the preparation method described herein is used in displays for mobile phones, tablet computers, laptop computers, handheld game consoles, portable digital devices, automotive displays, windshields, or cameras.

[0106] This invention enables the formation of a robust, durable, and high-performance hydrophobic and oleophobic coating at the coating interface of microcrystalline glass or glass-ceramic, even when the Si-O structure is minimal. It achieves excellent hydrophobic and oleophobic properties regardless of whether the highly crystalline glass has undergone ion exchange. Attached Figure Description

[0107] Figure 1 This is a diagram illustrating the reaction process of PFPE hydrolysis products bonding with glass. Detailed Implementation

[0108] The composition of glass-ceramics appears very similar to that of ordinary inorganic glass, generally with SiO2 < 70wt%, seemingly allowing for the preparation of excellent hydrophobic and oleophobic films using traditional coating methods. However, due to the presence of numerous crystals within the glass-ceramic structure, SiO2 typically infiltrates these crystals during formation, altering the structure and preventing Si-O from being effectively released and combining with the hydrophobic and oleophobic layer. These tiny crystals typically comprise 20-100% of the structure; in other words, a higher crystal ratio reduces the glass phase within the glass-ceramic, significantly decreasing the Si-O at the interface, which is the primary cause of poor quality hydrophobic and oleophobic coatings. This invention precisely addresses this fundamental problem, providing a solution.

[0109] Specifically, the present invention provides the following technical solution:

[0110] A composite coating design for a hydrophobic and oleophobic film on the surface of highly crystalline microcrystalline glass or glass ceramic is formed sequentially from the outermost surface: hydrophobic and oleophobic layer → intermediate layer → underlayer on the glass. That is, the underlayer is inside the microcrystalline glass or glass ceramic, while the hydrophobic and oleophobic layer is on the outermost surface.

[0111] In other words, the method of the present invention enables 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 problem of hydrophobic and oleophobic properties of microcrystalline glass or glass-ceramic with a crystallinity of 60% or more that are difficult to form hydrophobic and oleophobic films, the method of the present invention can also form an excellent hydrophobic and oleophobic composite coating on microcrystalline glass or glass-ceramic with a crystallinity of less than 60%.

[0112] Preferably, the intermediate layer is an ionic crystal with a lattice energy of 700-3000 kJ / mol (based on the lattice energy, the composition of the ionic crystal layer used 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 even more preferably greater than or equal to 770 kJ / mol (excluding radioactive substances).

[0113] Lattice energy of some common ionic crystals / (kJ·mol) -1 As shown in Table A below.

[0114]

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

[0116] Alternatively, fluorosilicified alkali metals such as Li2SiF6, Na2SiF6, and K2SiF6, as well as fluorosilicified alkaline earth metals, can be used as the intermediate layer.

[0117] Preferably, the intermediate layer is a polar or nonpolar compound (preferably a nonpolar alkali metal fluoride or a polar alkaline earth metal fluoride).

[0118] More preferably, the compound is a nonpolar compound (preferably narrowed down to alkali metal fluorides - nonpolar).

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

[0120] Preferably, the substrate contains or is composed of a Si compound, and the Si compound is preferably selected from:

[0121] -SiOx, where x is less than or equal to 2, wherein in the case of multiple layers, at least the outermost or uppermost layer comprises or is composed of silicon oxide;

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

[0123] - A mixed silicon oxide, consisting of silicon oxide SiOx and an oxide of at least one 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, and boron; particularly preferred is a mixture of silicon oxide SiOx and an oxide of at least one element aluminum, wherein x is less than or equal to 2;

[0124] Preferably, the total thickness of the underlayer is 3-15nm, more preferably 5-10nm, and even more preferably 5-8nm.

[0125] The hydrophobic and oleophobic layer, also known as the AF layer (anti-fingerprint layer), is a layer formed by a fluorinated polymer. This fluorinated polymer can be selected from perfluoropolyether, vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, chlorotrifluoroethylene, 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 be between 10 nm and 25 nm.

[0126] In addition, preferably, the microcrystalline glass described above is transparent or opaque, is before or after ion exchange, that is, it is pre-stressed or not pre-stressed.

[0127] Furthermore, 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 a glass composed thereof (in mol%):

[0128] SiO2: 40-75%, preferably 45-72%;

[0129] Al2O3: 2-20%, preferably 4-15%;

[0130] B2O3: 0-20%, preferably 0.4-1.6%;

[0131] P2O5: 0-10%, preferably 0.8-1.5%;

[0132] ZrO2+TiO2: 0-15%, preferably 0.9-4%;

[0133] MgO: 0-5%, preferably 0.1-2%;

[0134] ZnO: 0-4%, preferably 0.9-3.0%;

[0135] Rare earth oxides: 0-5%, preferably 0.01-1%;

[0136] Na2O: 0-5.5%;

[0137] K2O: 0-4%;

[0138] Li2O: 2-34%, preferably 10-34%; and

[0139] Na2O+K2O+Li2O: 4-40%, preferably 15-40%.

[0140] The rare earth oxides are selected from one or more of CeO2, Y2O3, La2O3, Ta2O3, Tm2O5 and Nb2O5.

[0141] In addition, in some preferred embodiments, the glass composition may contain: coloring oxide additives, such as Nd₂O₃, Fe₂O₃, CoO, NiO, V₂O₅, MnO₂, TiO₂, CuO, and Cr₂O₃; rare earth oxides in a content of 0-5 mol%, or 0-5 mol% for "black glass"; and clarifying agents in a content of 0-2 mol%, such as As₂O₃, Sb₂O₃, SnO₂, and Cl₂. - Compounds containing F - Compounds containing SO3 - Compounds and those containing NO3 - One or more of the compounds.

[0142] 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 microcrystalline glass is preferably selected from one or more of β-quartz solid solution, β-spodumene solid solution, β-nepheline, 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.

[0143] This invention employs a combination of a base layer, such as a SiO2 layer, a SiOx layer, or a mixture of silicon oxides (collectively referred to as a "silicon oxide layer," with SiO2 as an example, but not limited to SiO2) + an intermediate layer (referred to as an "RF layer," with NaF as an example) + a hydrophobic and oleophobic layer such as PFPE. The SiO2 layer should not be too thick, approximately 5 nm, not exceeding 15 nm. SiO2 exhibits a network or chain structure at the microscopic level. A 5 nm SiO2 coating is very thin, allowing it to retain the network structure (too thick a coating would cause the network to disappear due to overlapping of the SiO2 layers). An even thinner intermediate layer, RF, is then deposited. RF is a compound with a relatively low lattice energy, especially a nonpolar compound. RF is selected from compounds with relatively low lattice energy, and in the atmosphere, RF readily reacts with water to form R. + F - H + OH - :

[0144]

[0145] Because there are voids in the bottom layer, R + F - H + OH - It can very easily penetrate the interface of glass-ceramics 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 and film formation with hydrophobic and oleophobic layers:

[0146] ≡Si-O-Si≡ + R + +OH - → ≡Si-OH +RO-Si≡

[0147] ≡Si-O-Si≡ + H + +F - →SiF4 + H2O → H2SiO3 + H2SiF6

[0148] When sufficient Si-O is generated at the glass-ceramic interface and in the substrate, which is tightly bonded to the glass-ceramic matrix, it will generate sufficient valence bonds when reacting with the top hydrophobic and oleophobic PFPE layer, thereby significantly increasing the performance and wear resistance of the hydrophobic and oleophobic layer.

[0149] The key to the working principle of this invention lies in the intermediate layer with a suitable lattice energy. A slightly lower lattice energy makes the intermediate layer more active and facilitates the reaction. A moderate lattice energy is necessary to maintain the stability of the material. The intermediate layer of this invention requires a certain range of lattice energy. Within this range, the intermediate layer material has relatively high hydrolytic activity and is corrosive after hydrolysis. Therefore, it cannot be coated too thickly, otherwise it will be counterproductive. Generally, it should not exceed 5 nm. If it is too thick, the reaction products cannot be consumed in the entire reaction process and will erode into the glass, causing severe corrosion spots on the glass surface and reducing the weather resistance of the coating layer.

[0150] Regarding the term "microcrystalline glass or glass-ceramic":

[0151] In this invention, the terms "microcrystalline glass" and "glass ceramic" have equivalent meanings, referring to glass with a crystalline phase, unlike glass without a crystalline phase or amorphous shape. Therefore, the terms "microcrystalline glass" or "glass ceramic" appearing in this specification have equivalent meanings.

[0152] Regarding lattice energy:

[0153] Lattice energy refers to the energy absorbed when an ionic crystal transforms into gaseous positive and negative ions under standard conditions; it is a parameter measuring lattice stability. Factors affecting the magnitude of lattice energy include ionic radius, ionic charge, and the electronic configuration of the ions. Following the method used to calculate lattice energy in the paper "Topological Study of Lattice Energy and Magnetic Susceptibility of Alkaline Earth Metal Halides" by Qin Zhenglong and Liu Changjun, the following formula is obtained through fitting:

[0154]

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

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

[0157]

[0158] The regression equation obtained by fitting the data using this method shows good correlation and is also applicable to calculating the lattice energy of fluorinated silicides. The results are shown in Table C below.

[0159]

[0160] It is important to note that the original material used for coating and the material ultimately formed on the underlayer at the glass interface are not necessarily the same. Taking the alkali metal fluorosilicide R2SiF6 calculated above as an example, R2SiF6 is typically a relatively stable solid at room temperature. However, when heated to around 300°C during coating, it decomposes: R2SiF6 --> 2RF + SiF4 (gas). This means that while the material appears to have a high lattice energy, the key components undergo a qualitative change after film formation, and their lattice energy remains within the optimal operating range claimed in this invention. For example, sodium fluorosilicide Na2SiF6 is a white granular or crystalline powder, odorless and tasteless; upon heating (above 300°C), it decomposes into sodium fluoride NaF and silicon tetrafluoride SiF4.

[0161] Based on the above description of the principles of this invention, whether or not the interface of the coated microcrystalline glass undergoes ion exchange has no impact on the implementation and effect of this invention. Small ions in the glass must be in a state where ion movement is possible in order to exchange with large ions in the external salt bath. Temperature is a key factor for ion movement. Generally, the glass phase is more likely to achieve ion movement at relatively low temperatures (e.g., starting at around 200 degrees Celsius at the strain point, such as 360°C). However, alkali metal elements in the microcrystalline phase are part of the crystal structure before becoming mobile ions. Higher energy is required to break the constraints of the crystal structure and become freely exchangeable ions. This temperature is usually closer to the softening point of the glass (e.g., above 600 degrees Celsius). Therefore, ion exchange usually occurs mostly in the glass phase. Even when the salt bath temperature is extremely high, it also occurs first in the glass phase and only secondarily in the crystal phase.

[0162] This invention targets highly crystalline microcrystalline glasses with a very small amount of glass phase. Even if a small amount of glass phase exists and ion exchange has occurred, the number of ions entering the glass phase is very small, and their ability to change the Si-O structure and coordination within the glass phase is negligible and localized. Therefore, their influence on the formation of valence bonds in the coating described in this invention is minimal. In other words, regardless of whether ion exchange has been performed, the interface of highly crystalline glass lacks Si-O structure. This invention is specifically designed for this application scenario. If high temperatures are used, causing ions in the crystal to participate in ion exchange, meaning the crystal is damaged, the Si-O in the crystal will open, which will only help with the formation of valence bonds in the coating described in this invention. The problem this invention aims to solve is how to form a robust, durable, and high-performance hydrophobic and oleophobic coating when the coating interface has very little Si-O structure, regardless of whether the highly crystalline glass has undergone ion exchange, which does not necessarily preclude the implementation of this invention.

[0163] The preparation method of the microcrystalline glass or glass ceramic with a hydrophobic and oleophobic composite coating on the surface of the present invention is described in detail below.

[0164] Microcrystalline glass or glass-ceramic is obtained by firing glass with the following composition according to the following method.

[0165] SiO2: 40-75%, preferably 45-72%;

[0166] Al2O3: 2-20%, preferably 4-15%;

[0167] B2O3: 0-20%, preferably 0.4-1.6%;

[0168] P2O5: 0-10%, preferably 0.8-1.5%;

[0169] ZrO2+TiO2: 0-15%, preferably 0.9-4.0%;

[0170] MgO: 0-5%, preferably 0.1-2%;

[0171] ZnO: 0-4%, preferably 0.9-3.0%;

[0172] Rare earth oxides: 0-5%, preferably 0.01-1%;

[0173] Na2O: 0-5.5%;

[0174] K2O: 0-4%

[0175] Li2O: 2-34%, preferably 10-34%; and

[0176] Na2O+K2O+Li2O: 4-40%; preferably 15-40%.

[0177] The microcrystalline glass or glass-ceramic is obtained by firing a material comprising the following steps:

[0178] (I) The glass raw materials are melted at 1600±50℃ and then annealed at 400℃ to 650℃ to obtain homogenized plain glass plates.

[0179] (II) The raw glass plate is shaped into a molded raw glass plate by overflow pull-down method, float method or rolling method; and (III) The molded raw glass plate is microcrystallized by secondary heat treatment to obtain a microcrystalline glass preform, wherein the first heat treatment is carried out at a temperature of 500-1000℃ for 0.5-5h, and the second heat treatment is carried out at a temperature of 550-1100℃ for 0.5-6h; then (IV) the microcrystalline glass preform is subjected to ion exchange or is used directly without ion exchange to sequentially coat the required underlayer, intermediate layer and hydrophobic and oleophobic layer on its surface.

[0180] The ion exchange can be carried out using conventional methods, such as using a mixed molten salt containing 10-75 wt% NaNO3 and 25-90 wt% KNO3 by weight, and performing ion exchange for 5-10 hours at a temperature of 380-500℃.

[0181] Specifically, the firing method includes the following steps: First, the glass raw material is weighed and melted at a high temperature such as 1600±50℃, then annealed at approximately 400℃ to 650℃ to homogenize the glass, forming a microcrystalline glass matrix. The microcrystalline glass matrix, also known as a raw glass sheet, is a glass sheet that has not undergone crystallization treatment and does not contain crystals. Depending on its high-temperature viscosity and material properties, it can be formed using methods such as overflow drawing, float glass, or rolling, resulting in raw glass sheets with a thickness between 0.1 and 5 mm. Alternatively, it can be formed into a block shape, annealed, and then cut into a sheet shape.

[0182] After the microcrystalline glass substrate is formed, it undergoes a second heat treatment to achieve microcrystallization, thus producing a microcrystalline glass preform. The first heat treatment is carried out at approximately 500-1000℃ for 0.5-5 hours, and the second heat treatment is carried out at approximately 550-1100℃ for 0.5-6 hours. After crystallization, the desired microcrystalline glass or glass-ceramic is formed. Then, after ion exchange or without ion exchange, it is directly fed into a vacuum coating machine (PVD). The coating parameters are set, and the underlayer, intermediate layer, and hydrophobic and oleophobic layer are deposited sequentially. The process in the vacuum coating machine is as follows: glass loading - vacuuming - plasma cleaning - vapor deposition - vacuuming (releasing the vacuum to atmospheric pressure) - unloading.

[0183] 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.

[0184] Part 1: Examples of Glass Preparation

[0185] Example 1 will be used as an example to illustrate how to prepare a glass substrate:

[0186] (1) Mix the materials of Example 1 shown in Table 1 below, and put the mixture into a platinum crucible. Melt it in a high-temperature lifting furnace at 1600℃ for 5 hours. Then pour it into a preheated stainless steel mold and place it in an annealing furnace. Anneal it at 580℃ for 24 hours to eliminate the internal stress of the glass. After annealing, cut the glass bricks on all six sides to obtain glass bricks. Then use a wire cutting machine, CNC engraving machine, flat grinder, and polishing machine to perform dimensional precision cutting, flat grinding, and edge sweeping to obtain a plain glass plate with dimensions of 155mm×78mm×0.65mm.

[0187] The instrument models used in the above processes are described below:

[0188] Multi-wire cutting machine: CH5625, Taizhou Chenhong CNC Equipment Manufacturing Co., Ltd.

[0189] CNC engraving machine: CN-650, Shandong China CNC Equipment Co., Ltd.

[0190] Surface mill: YJ-13B6LD, Hunan Ningjing Machinery Co., Ltd., and

[0191] Polishing machine: YJ-13B6PD, Hunan Ningjing Machinery Co., Ltd.

[0192] (2) First, the plain glass plate is subjected to a first heat treatment at 650°C for 3 hours in a high-temperature heating furnace to form crystal nuclei; then, a second heat treatment is performed at 730°C for 3 hours to precipitate crystals, thereby obtaining glass ceramics. The glass ceramics are subjected to crystal analysis, including crystallinity, crystal type, i.e., the type of main crystal phase and secondary crystal phase, as well as the ratio of main crystal phase and secondary crystal 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") are tested.

[0193] (3) The glass ceramic is subjected to ion exchange. The molten salt is a mixed salt bath of 40wt% NaNO3 and 60wt% KNO3. The strengthening temperature (i.e. ion exchange temperature) is 380℃ and the strengthening time is 9h. After strengthening, it is taken out and washed to obtain the strengthened glass ceramic (hereinafter also referred to as "glass ceramic that has undergone ion exchange").

[0194] (4) The obtained reinforced glass ceramics were subjected to corresponding characterization tests, including tests of haze, average visible light transmittance, surface compressive stress, compressive stress depth and Young's modulus. The specific test results are shown in Table 3.

[0195] The 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 defined and tested as follows:

[0196] The surface compressive stress here refers to the compressive stress generated on the glass surface after the glass has been chemically strengthened, in which smaller alkali metal ions on the surface are replaced with larger alkali metal ions. Due to the crowding effect of the larger alkali metal ions, compressive stress is generated on the glass surface.

[0197] Crystallinity: The diffraction peak curve was obtained by XRD analysis, where the incident angle range was 2Theta = 10~50 degrees, and the scanning speed was 6 degrees / min. In this embodiment, the equipment used was a Shimadzu XRD-6000. Crystallinity was calculated according to formula (1-1):

[0198]

[0199] In the formula I c The integral diffraction intensity of the crystalline portion of the microcrystalline glass sample with a theta value of 10~50 degrees.

[0200] I a The integral diffraction intensity of the amorphous portion of the microcrystalline glass sample with a Theta value of 10~50;

[0201] K is the relative scattering factor per unit mass of the crystalline and amorphous parts of the microcrystalline glass sample, where 2Theta = 10~50.

[0202] Main crystalline phase percentage: In glass and ceramics, the crystalline phase that has the highest percentage of presence relative to other crystalline phases by weight.

[0203] Secondary crystalline phase proportion: In addition to the main crystalline phase, one or more other crystalline phases may exist in the ceramic part of glass ceramics, and the secondary crystalline phase is less than the weight of the main crystalline phase.

[0204] Average grain size: Based on the average grain length observed in the glass-ceramic at magnifications of 100,000 to 1,000,000 times. It was measured using a transmission electron microscope (TEM: Thermo Fisher Scientific (formerly FEI) Talos F200S). The measurement is equivalent to taking a magnified photograph of a specific area of ​​grains; the size of these grains is marked to scale, and then the average is calculated. In this embodiment of the invention, the magnification is 500,000 times.

[0205] Vickers hardness: The Vickers hardness was tested using a Vickers hardness tester according to the standard GB / T 37900-2019 Test Method for Hardness and Fracture Toughness of Ultra-thin Glass - Small Load Vickers Hardness Indentation Method. In this example, the equipment used was a digital display small load Vickers hardness tester VTD405 (Beijing Woway Technology Co., Ltd.).

[0206] Fracture toughness: This represents the result of indentation measurement. After polishing, the test sample is pressed with a conical diamond indenter on a Vickers hardness tester for 10 seconds under a load of 300 N, creating an indentation. A crack will then appear at the apex of the indentation. The fracture toughness value K is calculated based on the indentation load P and the crack propagation length C. IC The specific fracture toughness calculation was obtained according to the standard test calculation of "GB / T37900-2019 Test Method for Hardness and Fracture Toughness of Ultra-thin Glass - Small Load Vickers Hardness Indentation Method".

[0207] Surface compressive stress (MPa): The surface compressive stress of the glass under test was measured using a waveguide optical stress meter FSM-6000LE manufactured by ORIHARA Corporation of Japan.

[0208] Compressive stress depth (μm): The distance from the surface of the glass to be tested to the location where the compressive stress is zero;

[0209] Haze: The percentage of transmitted light intensity that deviates from the incident light angle by more than 2.5° out of the total transmitted light intensity. Measured using a colorimeter (model CM-3600A).

[0210] Visible light transmittance: In the visible light band, the ratio of the radiant energy projected and transmitted through an object to the total radiant energy projected onto the object as the incident light flux travels from the incident surface of the illuminated surface to the other side.

[0211] Average transmittance of visible light: 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 the 360-400nm wavelength range is calculated as follows: The transmittance at wavelengths of 360nm, 370nm, 380nm, 390nm, and 400nm is measured respectively. The number of transmittances measured in the 360-400nm range is 5. The sum of the above transmittances is divided by 5 to obtain the average transmittance for the 360-400nm wavelength range.

[0212] Young's modulus (GPa): The Young's modulus of the sample obtained by acoustic wave testing, using an IET-1600P high-temperature elastic modulus tester.

[0213] Examples 2-15

[0214] The preparation method and steps are the same as in Example 1, except that the differences are detailed in Tables 1, 2 and 3. That is, the specific composition of each raw material in the glass formula, the heat treatment process conditions in step (2) and the performance test results of the obtained glass ceramics, and the ion exchange process conditions in step (3) and the performance test results of the obtained reinforced glass ceramics are detailed in Tables 1, 2 and 3.

[0215]

[0216]

[0217]

[0218] As shown in Table 2 above, the glass-ceramic obtained after heat treatment of the raw glass of this invention has 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 of 718-796 HV, and a fracture toughness of 1.4-1.9 MPa·m. 1 / 2 .

[0219]

[0220] As can be seen from the glass composition above, rare earth oxides can be included in the glass formulation. Specifically, in this invention, one or more of the following rare earth oxides can be added: CeO2, Y2O3, La2O3, Ta2O3, Tm2O5, and Nb2O5. The content of these rare earth oxides is usually no more than 5 mol%. In addition, colorants and clarifying agents can be added as needed. Specifically, in the above glass composition, Nb2O3 acts as a colorant. In this invention, in addition to Nb2O3, one or more of the following substances can be added as colorants: Nd2O3, Fe2O3, CoO, NiO, V2O5, MnO2, TiO2, CuO, CeO2, and Cr2O3. O3; After adding colorant, the visible light transmittance of glass will decrease; the more colorant added, the lower the transmittance; generally, the addition ratio should not exceed 5 mol%, and adding more than 1 mol% will cause significant changes in 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 glass-ceramic. In this invention, adding 1 mol% of any combination of Fe2O3, NiO, MnO2 and other colorants in any proportion to the overall composition of the above embodiments 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 hue. The use of colorant not exceeding 5 mol% will not affect other properties of the glass.

[0221] In the glass of this invention, a clarifying agent can be used alone or in combination, depending on the actual melting conditions. The clarifying agent is selected from As2O3, Sb2O3, SnO2, and SO3-containing agents. -One or more of the following: compounds, fluorides or salts, chlorides or salts, and nitrates. Among these, As₂O₃ and Sb₂O₃ have excellent clarifying effects as clarifying agents, but are not preferred due to their toxicity; fluorides can also be used as clarifying agents, but are not preferred due to their corrosiveness; typically, SnO₂, SO₃ (e.g., Na₂SO₄), chlorides (e.g., NaCl), and compounds containing NO₃⁻ are preferred. - A single substance or combination of compounds (such as NaNO3) is commonly used as a clarifying agent, generally not exceeding 1 mol.

[0222] Part Two: Examples of Preparation of Hydrophobic and Olephobic Composite Coatings

[0223] 1. Composite coatings were formed using the glass-ceramics from Example 4 that had not undergone ion exchange and those that had undergone ion exchange, respectively, as glass substrates.

[0224] A composite coating comprising SiO2, NaF and AF films was formed on a batch of unexchanged glass ceramics (i.e., those not subjected to the ion exchange treatment in step (3)) prepared using the first part of Example 4 as glass substrates (numbered #4-A1 to 4-A15) and glass ceramics subjected to ion exchange (i.e., those subjected to the ion exchange treatment in step (3)) as glass substrates (numbered #4-B1 to 4-B15). Furthermore, a composite coating comprising only SiO2 and AF films was formed on the glass ceramics (numbered #4-A16 to 4-A18) and the glass ceramics (numbered #4-B16 to 4-B18) that were not subjected to ion exchange as glass substrates. Specifically, the vacuum coating instrument described in Table 4-1 and the coating conditions in Table 4-2 are used (Note: In each embodiment, the coating time is controlled according to the thickness of the target coating layer, and coating is stopped when the target thickness is reached), and a composite coating layer is formed according to the following method: the surfaces of these glass substrates are cleaned separately using ultrasonic cleaning (or a flat brush cleaning); after the glass substrate surfaces are cleaned, a basically uniform film layer is formed sequentially on the substrate surface using a vacuum coating method; the vacuum coating process is as follows: the glass sample to be coated is placed on an umbrella-shaped coating rack, and then the umbrella-shaped coating rack is placed in the workpiece rack of the machine. SiO2 and NaF coating materials are placed separately in the two electron gun crucibles of the vacuum coating machine (using the Hanyi Vacuum 2050 electron gun vacuum coating machine), without mixing, so that the materials fill the crucibles and are level with the surface of the crucible opening. The material used to form the AF film (Anti-Fingerprint) is placed in the molybdenum boat. The AF film material (600ml of AF liquid is dropped into a crucible containing steel wool; the crucible after the AF liquid has dried is called the AF film material) is used for glass (anti-fingerprint film). The vacuum chamber is closed, and vacuuming begins. When the background vacuum reaches the vacuum level specified in Table 4-2 of the set process, the equipment automatically introduces Ar gas at a rate of 28 sccm. The self-made Ion Beam is then run. The source Hall ion source is used to bombard and clean the sensitized glass surface. Specific conditions such as process vacuum, ion source voltage, ion source current, neutralization current, Ar and O2 gas ratio, electron gun operating current, film formation rate, and film thickness (with the film formation time parameter adjusted during plasma cleaning before coating) are shown in Table 4-2. SiO2 and NaF (both SiO2 and NaF are granular raw materials) are deposited sequentially according to these conditions. AF is then deposited according to these conditions, with Merck L5 SiO2 used as the coating material.

[0225] 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).

[0226] 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.

[0227] 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.

[0228] The water contact angle (°) of the AF membrane surface was measured using the method according to JIS R 3257 (1999).

[0229] 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.

[0230] 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:

[0231]

[0232] 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 the wear-resistant indenter. Under a load of 1kgf, the AF film surface formed on the glass substrate is rubbed back and forth 2500 times (or more) at a stroke amplitude of 40mm and a speed of 40mm / second. Then, the AF film surface is cleaned by dry rubbing 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.

[0233]

[0234] Note: To create the required vacuum conditions for coating, those skilled in the art can select some or all of the pumps listed in Table 4-1 above and use them as needed, according to conventional methods. Among them, mechanical pumps, also known as backing pumps, use oil to maintain a seal and rely on mechanical methods to continuously change the volume of the suction cavity inside the pump, causing the volume of gas in the evacuated container to continuously expand, thus achieving a vacuum; Roots pumps are booster pumps, whose function is to increase the pressure difference between the inlet and outlet, and they are used with mechanical pumps as backing pumps; diffusion pumps are used to obtain high vacuum, and when using diffusion pumps, mechanical pumps and Roots pumps are used as backing pumps; Polycold is a cryogenic water vapor pump, used to capture residual gas present in the high vacuum environment of diffusion pumps. Its working principle is to place a cooling coil capable of reaching below -120°C at the pump inlet of the diffusion pump, and through the low-temperature condensation effect on its surface, rapidly capture residual gas in the vacuum system.

[0235]

[0236]

[0237]

[0238] 2. A composite coating is formed using the glass-ceramics from Example 8, both those that have undergone ion exchange and those that have, as glass substrates.

[0239] Similar to the operation of forming a composite coating using the glass ceramic formed in Example 4 as a glass substrate in Section 1 above, the difference is 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) as glass substrates in Example 8 to form a composite coating containing SiO2, NaF and AF films, as well as a composite coating containing only SiO2 and AF films (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 water contact angle test results of the outer surface of the coating are shown in Tables 6-1 and 6-2.

[0240]

[0241]

[0242] 3. A composite coating is formed using the glass-ceramics from Example 12 that have not undergone ion exchange and those that have undergone ion exchange as glass substrates.

[0243] Similar to the operation of forming a composite coating using the glass ceramic formed in Example 4 as a glass substrate in Section 1 above, the difference is 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) as glass substrates in Example 12 to form a composite coating containing SiO2, NaF and AF films, as well as a composite coating containing only SiO2 and AF films (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 water contact angle test results of the outer surface of the coating are shown in Tables 7-1 and 7-2.

[0244]

[0245]

[0246] 4. A composite coating is formed using the glass-ceramics from Example 13 that have not undergone ion exchange and those that have undergone ion exchange as glass substrates.

[0247] Similar to the operation of forming a composite coating using the glass ceramic formed in Example 4 as a glass substrate in Section 1 above, the difference is 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) as glass substrates to form a composite coating containing SiO2, NaF and AF films, as well as a composite coating containing only SiO2 and AF films (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 water contact angle test results of the outer surface of the coating are shown in Tables 8-1 and 8-2.

[0248]

[0249]

[0250] The experimental results in Tables 5-1, 5-2, 6-1, 6-2, 7-1, 7-2, 8-1, and 8-2 show that, among the 13 glass-ceramic formulations, four glass-ceramics with different crystal ratios were selected. Using both un-ion-exchanged and ion-exchanged glass substrates as the base material, three-layer coatings were formed. Based on these data, the following conclusions can be drawn:

[0251] 1) When the thickness of the base layer is too thick, exceeding 20nm, the wear resistance of AF is not good, so it is best not to exceed 15nm in thickness;

[0252] 2) When the intermediate layer is too thick, exceeding 5nm, the initial performance and wear resistance of AF are very poor. However, without the intermediate layer, as can be seen from the contact angle data in the last three rows of each table, the initial contact angle is mostly less than 100 degrees, while after 2500 friction cycles, the contact angle reaches a maximum of about 60 degrees.

[0253] 3) A moderate base coat, a thinner middle coat, and an AF coat of varying thickness are all acceptable;

[0254] 4) A surface layer of not less than 10nm will result in a composite coating with good hydrophobicity and oleophobicity, and excellent wear resistance. It is preferable to have a surface layer of not less than 15nm. The thicker the coating, the better the wear resistance. From a cost perspective, a coating with a surface layer of not more than 25nm will have ideal hydrophobicity, oleophobicity, and wear resistance.

[0255] 5) Even without ion exchange or prestressing treatment, the three-layer composite coating is formed directly on the glass ceramic, and its hydrophobic and oleophobic properties are excellent. When the three-layer composite coating is formed on the strengthened glass after ion exchange, the wear resistance test shows that the contact angle is larger, which means that the hydrophobic and oleophobic effect is even better.

[0256] In summary, it can be seen that the preferred thickness of the underlayer is 3-15nm, the thickness of the intermediate layer is 1-5nm, and the thickness of the AF film layer is not less than 10nm, preferably not less than 15nm, and can be between 10-25nm; in addition, the intermediate layer is preferably 1-2nm; and the effect of forming the underlayer is good at 5-10nm, and preferably 5-8nm.

[0257] 5. For the glass ceramics in Example 4 that have not undergone ion exchange (the glass ceramics are prepared according to steps (1) and (2) based on the 4# formula, without the ion exchange treatment in step (3)) in the first part of Example 4, a composite coating (numbered #4-a1, #4-a2, #4-a3) is formed on the surface according to the operation method 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.

[0258] The glass-ceramics that underwent ion exchange in Example 4 of Part 1 were subjected to a composite coating (also known as tempered glass, numbered #4-b1, #4-b2, and #4-b3) on their surface according to the operating methods and conditions described in Section 1 above. The only difference between the two coatings was their thickness, 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 methods of Example 4 of Part 1. All test results are summarized in Table 9 below.

[0259] Black coloring agents were added to the glass ceramics that had not undergone ion exchange in Example 4 of Part 1. Specifically, based on the No. 4 formulation, 0.5 mol% NiO, 1 mol% Fe2O3, and 0.3 mol% CoO were added as a base, and the glass ceramics were prepared according to steps (1) and (2) in the "Glass Preparation Examples" of Part 1. Composite coatings (also known as black glass without ion exchange or black glass without prestressing treatment, numbered #4-c1, #4-c2, and #4-c3) were formed on the surface according to the operation methods and conditions described in Section 1 above. The only difference between them 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 results are also summarized in Table 9 below. The obtained black glass was opaque black in appearance and appeared deep blue-black when irradiated with strong white light.

[0260]

[0261] As can be seen from Table 9 above, the intermediate layer is relatively thin, ranging from 1 to 3 nm. Regardless of whether it has undergone ion exchange or glass prestressing treatment, the AF film adhesion and wear resistance of the composite coating are excellent. Furthermore, even after adding a black colorant, it does not affect the AF film adhesion and wear resistance.

Claims

1. A microcrystalline glass with a hydrophobic and oleophobic composite coating on its surface, characterized in that, Starting from the outermost surface of the microcrystalline glass, the coating comprises, in sequence: a hydrophobic and oleophobic layer, an intermediate layer, and a base layer. The intermediate layer is a fluoride intermediate layer formed using an ionic crystal with a lattice energy of 725-3000 kJ / mol or a compound with a lattice energy of 9400-11400 kJ / mol as the initial coating material. Furthermore, the intermediate layer contains alkali metal fluorides or alkaline earth metal fluorides, or is a fluoride intermediate layer formed using an ionic crystal selected from alkali metal fluorides and alkaline earth metal fluorides as the initial coating material. The base layer comprises a compound containing Si-O bonds or a mixed silicon oxide layer. The thickness of the intermediate layer is 1-5 nm, and the thickness of the base layer is 3-15 nm. The hydrophobic and oleophobic layer is a fluorinated polymer layer with a thickness of 10nm-25nm.

2. The microcrystalline glass according to claim 1, wherein the microcrystalline glass contains coloring additives.

3. The microcrystalline glass according to claim 1, wherein the intermediate layer is formed by using an ionic crystal with a lattice energy of 770-3000 kJ / mol as the original coating material.

4. The microcrystalline glass according to claim 2, wherein the intermediate layer is formed by using an ionic crystal with a lattice energy of 770-3000 kJ / mol as the original coating material.

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

6. The microcrystalline glass according to claim 1, wherein the intermediate layer is an ionic crystal intermediate layer with a lattice energy of less than 940 kJ / mol.

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

8. The microcrystalline glass according to claim 1, wherein the intermediate layer is formed by using NaF or KF ionic crystals as the original coating material.

9. The microcrystalline glass according to any one of claims 1-8, wherein the thickness of the intermediate layer is 1-2 nm.

10. The microcrystalline glass according to any one of claims 1-8, wherein the thickness of the underlayer is 5-10 nm.

11. The microcrystalline glass according to any one of claims 1-8, wherein the thickness of the underlayer is 5-8 nm.

12. The glass-ceramic according to any one of claims 1-8, wherein, In the case where the substrate layer is multi-layered, the compound layer containing Si-O bonds or the mixed silicon oxide layer serves as the outermost substrate layer, and the mixed silicon oxide is silicon oxide (SiO₂). x A mixture of oxides of at least one element other than silicon and / or magnesium fluoride, wherein x is less than or equal to 2.

13. The microcrystalline glass according to claim 12, wherein, The other elements are elements selected from aluminum, tin, magnesium, phosphorus, cerium, zirconium, titanium, cesium, barium, strontium, niobium, zinc, or boron.

14. The microcrystalline glass according to claim 12, wherein, The mixed silicon oxide is silicon oxide (SiO₂). x A mixture with aluminum oxide.

15. The glass-ceramic according to claim 12, wherein the compound containing Si-O bonds is SiOx, wherein x is less than or equal to 2; or is any one of SiOC, SiON and / or SiOCN.

16. The glass-ceramic according to any one of claims 1-8, wherein the glass-ceramic composition contains the following mol% proportion of oxides: 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%.

17. The glass-ceramic according to claim 12, wherein the glass-ceramic composition contains the following mol% proportion of oxides: 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%.

18. The glass-ceramic according to claim 13, wherein the glass-ceramic composition contains the following mol% proportion of oxides: 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%.

19. The glass-ceramic according to claim 14, wherein the glass-ceramic composition contains the following mol% proportion of oxides: 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%.

20. The glass-ceramic of claim 15, wherein the glass-ceramic composition contains the following mol% proportion of oxides: 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%.

21. The glass-ceramic according to claim 16, wherein the glass-ceramic composition contains the following mol% proportion of oxides: 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%.

22. The microcrystalline glass according to claim 16, wherein the rare earth oxide is selected from one or more of CeO2, Y2O3, La2O3, Tm2O5 and Nd2O5.

23. The microcrystalline glass according to claim 2, wherein the coloring additive is selected from one or more of Nd2O3, Fe2O3, CoO, NiO, V2O5, MnO2, TiO2, CuO and Cr2O3.

24. The microcrystalline glass according to claim 23, wherein, The coloring additive has a molar content of no more than 5% relative to the overall glass composition.

25. The microcrystalline glass according to claim 24, wherein the coloring additive contains more than 0.5 mol% CoO and / or Cr2O3 relative to the molar content of the overall glass composition.

26. The microcrystalline glass according to claim 25, wherein the coloring additive contains 1 mol% or more of any one of Fe2O3, NiO or MnO2 relative to the molar content of the overall glass composition.

27. The glass-ceramic according to any one of claims 1-8, 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-nepheline, spinel, rutile, mullite, olivine, enstatite, cordierite, petalite, lithium silicate, lithium disilicate, quartz, zirconium oxide, and magnetite.

28. The microcrystalline glass according to claim 12, wherein the main crystalline phase of the microcrystalline glass is selected from one or more of β-quartz solid solution, β-spodumene solid solution, β-nepheline, spinel, rutile, mullite, olivine, enstatite, cordierite, petalite, lithium silicate, lithium disilicate, quartz, zirconium oxide, and magnetite.

29. The microcrystalline glass according to claim 13, wherein the main crystalline phase of the microcrystalline glass is selected from one or more of β-quartz solid solution, β-spodumene solid solution, β-nepheline, spinel, rutile, mullite, olivine, enstatite, cordierite, petalite, lithium silicate, lithium disilicate, quartz, zirconium oxide, and magnetite.

30. The microcrystalline glass according to claim 15, wherein the main crystalline phase of the microcrystalline glass is selected from one or more of β-quartz solid solution, β-spodumene solid solution, β-nepheline, spinel, rutile, mullite, olivine, enstatite, cordierite, petalite, lithium silicate, lithium disilicate, quartz, zirconium oxide, and magnetite.

31. The microcrystalline glass according to claim 16, wherein the main crystalline phase of the microcrystalline glass is selected from one or more of β-quartz solid solution, β-spodumene solid solution, β-nepheline, spinel, rutile, mullite, olivine, enstatite, cordierite, petalite, lithium silicate, lithium disilicate, quartz, zirconium oxide, and magnetite.

32. The microcrystalline glass according to claim 22, wherein the main crystalline phase of the microcrystalline glass is selected from one or more of β-quartz solid solution, β-spodumene solid solution, β-nepheline, spinel, rutile, mullite, olivine, enstatite, cordierite, petalite, lithium silicate, lithium disilicate, quartz, zirconium oxide, and magnetite.

33. The microcrystalline glass according to claim 23, wherein the main crystalline phase of the microcrystalline glass is selected from one or more of β-quartz solid solution, β-spodumene solid solution, β-nepheline, spinel, rutile, mullite, olivine, enstatite, cordierite, petalite, lithium silicate, lithium disilicate, quartz, zirconium oxide, and magnetite.

34. The microcrystalline glass according to claim 24, wherein the main crystalline phase of the microcrystalline glass is selected from one or more of β-quartz solid solution, β-spodumene solid solution, β-nepheline, spinel, rutile, mullite, olivine, enstatite, cordierite, petalite, lithium silicate, lithium disilicate, quartz, zirconium oxide, and magnetite.

35. The microcrystalline glass according to claim 25, wherein the main crystalline phase of the microcrystalline glass is selected from one or more of β-quartz solid solution, β-spodumene solid solution, β-nepheline, spinel, rutile, mullite, olivine, enstatite, cordierite, petalite, lithium silicate, lithium disilicate, quartz, zirconium oxide, and magnetite.

36. The microcrystalline glass according to claim 26, wherein the main crystalline phase of the microcrystalline glass is selected from one or more of β-quartz solid solution, β-spodumene solid solution, β-nepheline, spinel, rutile, mullite, olivine, enstatite, cordierite, petalite, lithium silicate, lithium disilicate, quartz, zirconium oxide, and magnetite.

37. The microcrystalline glass according to claim 27, wherein the average grain size is less than 100 nm.

38. The microcrystalline glass according to claim 27, wherein the average grain size is less than or equal to 50 nm.

39. The microcrystalline glass according to claim 27, wherein the average grain size is less than or equal to 30 nm.

40. The glass-ceramic according to any one of claims 1-8, wherein the glass-ceramic is an ion-exchanged or non-ion-exchanged glass.

41. The glass-ceramic according to any one of claims 1-8, wherein the glass-ceramic is a glass-ceramic with a crystallinity of less than 60%.

42. The glass-ceramic according to any one of claims 1-8, wherein the glass-ceramic has a crystallinity of greater than 60%.

43. The glass-ceramic according to any one of claims 1-8, wherein the glass-ceramic has a crystallinity of greater than 70%.

44. The glass-ceramic according to any one of claims 1-8, wherein the glass-ceramic has a crystallinity of greater than 80%.

45. A method for preparing microcrystalline glass according to any one of claims 1-44, comprising the following steps: 1) A layer of Si-O-containing oxide or mixed silicon oxide is deposited on the surface of the glass-ceramic to form a base layer; 2) The intermediate layer is plated onto the surface of the base layer obtained in step 1); 3) Coat the surface of the intermediate layer obtained in step 2) with a water-repellent and oil-repellent layer.

46. ​​The preparation method according to claim 45, wherein, The microcrystalline glass is obtained by firing a process comprising the following steps before coating the underlayer, intermediate layer and hydrophobic and oleophobic layer: (I) The glass raw materials are melted at 1600±50℃ and then annealed at 400-650℃ to obtain homogenized plain glass plates. (II) The raw glass plate is shaped by overflow pull-down method, float glass method or rolling method; and (III) The molded glass plate is microcrystallized by secondary heat treatment to obtain a microcrystalline glass preform. Then, ion exchange is performed or no ion exchange is performed and it is used directly as the raw material for microcrystalline glass. The required base layer, intermediate layer and hydrophobic and oleophobic layer are sequentially coated on its surface. The first heat treatment temperature is 500-1000℃ and the second heat treatment temperature is 550-1100℃.

47. The microcrystalline glass according to any one of claims 1-44 or the microcrystalline glass obtained by the preparation method according to claim 45 or 46 is used for mobile phone displays, tablet computer displays, laptop computer displays, handheld game consoles, vehicle displays, windshields or camera displays.

48. The microcrystalline glass according to any one of claims 1-44 or the microcrystalline glass obtained by the preparation method according to claim 45 or 46 is used in portable digital devices.

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