Method for manufacturing microcrystalline glass containing a coating layer with excellent water-repellent and oil-repellent properties

Abstract

To provide a microcrystalized glass coated to have water repellency and oil repellency, a method for manufacturing the same, and application of the same.SOLUTION: The microcrystalized glass or glass ceramics containing a water-repellent and oil-repellent composite coating layer comprises a water-repellent and oil-repellent layer, an intermediate layer, and an undercoating layer in order from the outermost surface of the glass. The intermediate layer is formed by an ion crystal containing crystal lattice energy of 700-3000 kJ / mol, and the undercoating layer includes a compound containing Si-O coupling or a mixed silicon oxide layer. Even when Si-O structures are limited in a coating interface of the microcrystalized glass, a water-repellent and oil-repellent coating layer strong, durable, and excellent in performance can be formed, and excellent water repellency and oil repellency can be achieved irrespective of ion exchanging of the highly crystalized glass.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a water-repellent and oil-repellent coated glass, a method for manufacturing the same, and its applications, and more particularly to a microcrystalline glass having a water-repellent and oil-repellent composite coating layer on the surface of a microcrystalline glass with a high degree of crystallinity. [Background technology]

[0002] Glass generally has high surface activity, resulting in low water and oil repellency. This means that dirt easily adheres to the surface, and cleaning is very difficult once the surface is soiled. For example, in many applications such as cookware, range hood glass products, mobile phones, tablets, and touchscreen human-machine interaction windows, coating the glass surface with a single layer of "water-repellent" film reduces the surface activity of the glass, improving its "water and oil repellency" and hydrophobicity. After the hydrophobicity is improved, when you touch the glass surface with your finger, you can clearly feel the improvement in "slipperiness." This is because the hydrophobicity has improved and the coefficient of friction has decreased, which is a function that improves the user experience for touch interfaces.

[0003] Conventional techniques typically employ a method of directly coating the glass surface to improve its water- and oil-repellent properties. Common coating film materials are PFPE (perfluoropolyether, a type of fluorine-containing polyether silicon oxide), and the structure of such fluorine-containing polyether silicon oxide (e.g., alkoxysilicides) is as shown in formula (1) below. [ka] Here, R can be carbon, hydrogen, or silicon, and Y can be an ether bond, a sulfur-containing hydrocarbon group, a sulfur-containing alkoxy, a nitrogen-containing hydrocarbon group, a nitrogen-containing alkoxy, an epoxyalkyl group, an acyloxy hydrocarbon group, a hydrocarbon group, a thio group, etc.

[0004] The process of bonding 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 (as shown in Figure 1, PFPE-Si-OH + HO-Si → H2O + PFPE-Si-O-Si-). Ultimately, unlike most vacuum coatings which rely on intermolecular van der Waals forces, the Si-O structure at the interface between the PFPE film and the glass forms a valence bond.

[0005] In conventional technology, the coating method is usually as follows. Because glass contains a large amount of Si-O structure, PFPE has the conditions to react directly with glass and form a film. However, the mass ratio of SiO2 in glass is usually no more than 70%, and in order to improve the coating effect and durability, the following two coating methods are generally employed.

[0006] a) Dry method: Also known as the vacuum coating method, this method involves applying a single layer of SiO2 coating to the surface of the current glass under vacuum to increase the Si-O ratio, and then applying a single layer of PFPE under vacuum conditions.

[0007] b) Wet method: Also known as the spray coating method, this method involves using plasma to impact the glass surface in the air, cleaning the glass surface while simultaneously roughening it. This increases the surface area at a microscopic level, indirectly increasing the Si-O ratio, before spraying a single layer of PFPE solution.

[0008] Existing Patent Document 1 discloses the structure of an antifouling coating layer on the surface of transparent microcrystalline glass, characterized in that a colorless, transparent antifouling layer (11) with a thickness of 4 to 30 nm is attached to the outer surface layer of the microcrystalline glass body (1), and the antifouling layer (11) is a fluorosilicone hydrolysis compound. Hereinafter, the patent describes the microcrystalline glass device characterized in that there is a silicon dioxide layer with a thickness of 3 to 20 nm below the antifouling layer (11).

[0009] However, the characteristic of the microcrystalline glass primarily protected by the patent is that "the mass ratio of the crystalline phase to the glass phase of the microcrystalline glass body is 0.25 to 1.2," meaning it is a microcrystalline glass with intermediate to low crystallinity levels, where the glass phase of the microcrystalline glass body uniformly surrounds the outer periphery of the crystalline phase, and the glass phase contains alkali metal ions such as sodium, lithium, and potassium. The value obtained by dividing the mass of the alkali metal oxide in the glass phase by (the mass of alumina plus the mass of silica) is 6% to 30%, resulting in a crystallinity of 20% to 54.54%. Since the glass phase in the microcrystalline glass still contains a sufficient amount of Si-O structures, it can support the formation of better valence bonds between PFPE and the microcrystalline glass. However, the invention does not address related issues concerning microcrystalline glass with a high degree of crystallinity.

[0010] Existing Patent Document 2 addresses the problem of poor bonding strength and durability of hydrophobic or oleophobic coating layers or anti-fingerprint coating layers on glass surfaces due to prestressing by ion exchange: "Currently, it has been found that chemical prestressing significantly reduces the durability of hydrophobic or oleophobic coating layers or anti-fingerprint coating layers. This is evident in, for example, corresponding tests and neutral salt spray tests, which are specifically described in, for example, Patent Documents 3 and 4." The present invention discloses the following solution to this problem. Based on this objective, the present invention not only solves the shortcomings of the prior art but also provides a glass substrate having a hydrophobic or oleophobic coating layer that is chemically prestressed and has sufficient long-term durability. Furthermore, it should provide a method for manufacturing a glass substrate that is coated and chemically prestressed. The above objectives are achieved in the following surprising way: The glass substrate is chemically prestressed by passing through all layers of glass using an ion exchange method, and then the functional coating layer on the glass substrate is activated before applying the hydrophobic or oleophobic coating layer that functions as an anti-fingerprint coating layer. In other words, first, a "functional coating layer" is created on glass that has not undergone ion exchange, then "ion exchange" is performed, followed by "activation of the functional coating layer," and then "coating of the hydrophobic and oleophobic coating layer." Here, the patent mentions that it is preferable for the functional layer, especially the top functional layer, to contain one or more Si compounds, and particularly preferable for it to contain one or more silicon oxide compounds, and that it is particularly advantageous for the Si compound to be selected from, for example, silicon oxide. Preferably, it is silicon oxide SiOx (x is 2 or less), SiOC, SiON, SiOCN and Si3N4, and hydrogen that can bond with SiOx (x is 2 or less), SiOC, SiON and SiOCN in any amount. In one preferred embodiment, the functional layer, especially the top functional layer, is a silicon mixed oxide layer. Accordingly, the patent discloses that the "functional coating layer" is mainly composed of inorganic components containing a Si-O structure. The patent states that "chemical prestressing usually weakens the long-term stability of the hydrophobic and oleophobic coating layer. This defect is eliminated by the present invention."According to the present invention, after chemically prestressing, by activating the surface of at least one functional layer, an interaction is generated between the surface of the functional layer and a hydrophobic and oleophobic coating layer symmetric to the coating. And in this patent, it is pointed out that by accumulating potassium ions on the surface of the topmost functional layer, the number of effective bonding positions such as Si-OH in the functional layer containing Si, for example, decreases, and this hinders the covalent bond of the hydrophobic and oleophobic coating layer, thereby considering that the adhesion of the hydrophobic and oleophobic coating layer is poor and the long-term stability is low. Also, the surface of the topmost functional layer usually has the burden of being contaminated by organic or inorganic contaminants, and these contaminations prevent the desired interaction. Therefore, this patent adjusts the order of ion exchange and uses surface activation to activate Si-O to enhance the bonding ability of the hydrophobic and oleophobic coating layer. That is, this patent is completely engaged in the technical optimization of glass rich in Si-O structure and a functional undercoat layer rich in Si-O structure.

Prior Art Documents

Patent Documents

[0011]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Summary of the Invention

Problems to be Solved by the Invention

[0012] The glass coating principles in the prior art of this invention are all based on water-repellent and oil-repellent coatings using inorganic glass. Generally speaking, the water-repellent and oil-repellent effect can achieve an initial water droplet angle of 110° or more, approximately 115°, and the water droplet angle can still be maintained at 100° or more even after 5000 friction cycles. However, even with microcrystalline glass with a crystallinity greater than 60%, the effect is very poor when applied according to the principles and methods of the prior art (activating Si-O using surface activation to enhance the bonding ability of the hydrophobic and oil-repellent coating layer). The initial water droplet angle can generally only be achieved up to about 100°, and after 2500 friction cycles, the water droplet angle is only about 60°. Microcrystalline glass is a type of glass, and its Si-O content is not less than that of ordinary inorganic glass. However, the reason for this significant difference is that conventional methods have all been developed for water-repellent and oil-repellent coating layers at interfaces rich in Si-O structures. These solutions cannot function effectively in situations of high crystallinity or when the interface lacks a glass phase or Si-O structure.

[0013] To solve the conventional technical problems described above, the present invention provides the following technical solutions. [Means for solving the problem]

[0014] A microcrystalline glass containing a water-repellent and oil-repellent composite coating layer on its surface, wherein the microcrystalline glass comprises, in order from the outermost surface, a water-repellent and oil-repellent layer, an intermediate layer, and a primer layer, wherein the intermediate layer is an ionic crystal intermediate layer containing a crystal lattice energy of 700 to 3000 kJ / mol, and the primer layer contains a compound or mixed silicon oxide layer containing Si-O bonds.

[0015] Preferably, for any of the above microcrystalline glasses, the degree of crystallinity may be greater than 60%, greater than 70%, or greater than 80%.

[0016] Preferably, for any of the above microcrystalline glasses, the intermediate layer is formed using an ionic crystal having a crystal lattice energy of 725 to 3000 kJ / mol, more preferably 770 to 3000 kJ / mol, as the original coating film material. Alternatively, it is a fluoride intermediate layer formed using a compound with a crystal lattice energy of 9400 to 11400 kJ / mol, preferably silica fluoride, as the original coating film material.

[0017] Preferably, for any of the microcrystalline glasses described above, the intermediate layer contains alkali metal fluorides or alkaline earth metal fluorides, or is an intermediate layer formed from ionic crystals selected from alkali metal silicofluorides and alkaline earth metal silicofluorides as the original coating film material.

[0018] Preferably, for any of the above microcrystalline glasses, the intermediate layer is an ionic crystal intermediate layer with a crystal lattice energy less than 1050 kJ / mol, preferably less than 940 kJ / mol.

[0019] Preferably, for any of the above microcrystalline glasses, the intermediate layer is a crystal formed with at least one ionic crystal of LiF, NaF, and / or KF as the original coating film material, or an intermediate layer formed with at least one of MgF2, CaF2, SrF2, or BaF2 as the original coating film material, or a fluoride intermediate layer formed with at least one of Li2SiF6, Na2SiF6, K2SiF6, Rb2SiF6, Cs2SiF6, BeSiF6, MgSiF6, CaSiF6, SrSiF6, or BaSiF6 as the original coating film material coating film, with an intermediate layer formed with an ionic crystal of NaF or KF as the original coating film material being preferred.

[0020] Preferably, in any of the above microcrystalline glasses, the intermediate layer is a polar or nonpolar compound, and is preferably a polar compound.

[0021] Preferably, for any of the above microcrystalline glass materials, the thickness of the intermediate layer is 1 to 5 nm, and more preferably 1 to 2 nm.

[0022] Preferably, for any of the above microcrystalline glass, the thickness of the undercoat layer is 3 to 15 nm, more preferably 5 to 10 nm, and more preferably 5 to 8 nm.

[0023] Preferably, for any of the above-mentioned microcrystalline glass, the thickness of the water-repellent and oil-repellent layer is 10 nm or more, preferably 15 nm or more, and may be 10 nm to 25 nm.

[0024] Preferably, for any of the above microcrystalline glass, if the undercoat layer is multilayered, the compound containing the Si-O bond or the mixed silicon oxide layer is used as the outermost undercoat layer, and the mixed silicon oxide is silicon oxide SiO x A mixture of (x is 2 or less) and an oxide of at least one element other than silicon and / or magnesium fluoride, The other elements are preferably aluminum, tin, magnesium, phosphorus, cerium, zirconium, titanium, cesium, barium, strontium, niobium, zinc, or boron, and the mixed silicon oxide is silicon oxide SiO x It is more preferable that it be a mixture of aluminum oxide.

[0025] Preferably, for any of the above microcrystalline glasses, the compound containing the Si-O bond is SiOx (x is 2 or less), or a hydrogen bond formed in any ratio with one of the substances from SiOC, SiON, SiCN and / or Si3N4, or with one of the substances from SiOC, SiON and / or SiCN.

[0026] Preferably, for any of the above-mentioned microcrystalline glass, the water-repellent and oil-repellent layer is a fluorine-based polymer layer, preferably a fluorine-containing polyether silicon oxide layer with a molecular weight of 2000 or more, and the thickness of the coating layer is 10 nm or more.

[0027] Preferably, for any of the above microcrystalline glass, the composition of the microcrystalline glass is an oxide in the following mol% ratios. 40-75%, preferably 45-72%, SiO2 2-20%, preferably 4-15%, Al2O3, 0-20%, preferably 0.4-1.6%, of B2O3, 0-10%, preferably 0.8-1.5%, of P2O5, 0-15%, preferably 0.9-4%, of ZrO2 + TiO2, 0-5%, preferably 0.1-2%, MgO and 0-4%, preferably 0.9-3.0% ZnO, 0-5%, preferably 0.01-1%, of rare earth oxides, 0-5.5% Na2O, 0-4% K2O and 2-34%, preferably 10-34%, Li2O, It contains 4-40%, preferably 15-40%, of Na2O+K2O+Li2O.

[0028] Preferably, for any of the microcrystalline glasses described above, the rare earth oxide is one or more selected from CeO2, Y2O3, La2O3, Ta2O3, Tm2O5, and Nd2O5.

[0029] Preferably, in any of the above microcrystalline glass materials, the microcrystalline glass may further contain a coloring additive, and the coloring additive is preferably one or more selected from Nd2O3, Fe2O3, CoO, NiO, V2O5, MnO2, TiO2, CuO, and Cr2O3.

[0030] Preferably, for any of the microcrystalline glasses described above, the molar content of the coloring additive relative to the total components of the glass does not exceed 5%, and it is preferable that the coloring additive contains 0.5 mol% or more of CoO and / or Cr2O3 relative to the total components of the glass, and more preferably contains 1 mol% or more of one or more selected from Fe2O3, NiO, or MnO2.

[0031] Preferably, in any of the above microcrystalline glass materials, the microcrystalline glass contains a clarifying agent, and the clarifying agent is As2O3, Sb2O3, SnO2, chloride, fluoride, SO3 - Containing compounds and NO3 - Preferably, it is one or more compounds selected from the contained compounds, such as SnO2 and SO3. - Contains compounds, chlorides, and NO3 - It is preferable that the clarifying agent is one or more compounds selected from the contained compounds, and the content of the clarifying agent is preferably 0 to 2 mol%.

[0032] Preferably, for any of the above microcrystalline glasses, the main crystalline phase of the microcrystalline glass is one or more selected from β-quartz solid solution, β-spodumene solid solution, β-eucryptite, spinel, rutile, mullite, olivine, enstatite, cordierite, feldspar, lithium silicate, lithium disilicate, quartz, zirconia, and magnetite, and the average grain size is preferably less than 100 nm, more preferably 50 nm or less, and particularly preferably 30 nm or less.

[0033] Preferably, in the case of any of the above microcrystalline glass, the microcrystalline glass is either ion-exchanged or ion-exchanged glass.

[0034] More preferably, in any of the above microcrystalline glass materials, the microcrystalline glass is a glass ceramic with a crystallinity of less than 60%.

[0035] The present invention further provides a method for producing any of the above-described microcrystalline glass, which is: Step 1) involves coating microcrystalline glass with a Si-O-containing oxide or mixed silicon oxide layer to form an undercoat layer on the surface of the microcrystalline glass, Step 2) involves coating the surface of the undercoat layer obtained in Step 1) with an intermediate layer, Step 3) involves coating the surface of the intermediate layer obtained in step 2) with a water-repellent and oil-repellent layer.

[0036] Preferably, in the above manufacturing method, a vacuum deposition method is employed for the coating.

[0037] Preferably, in any of the above manufacturing methods, the microcrystalline glass is ion-exchanged microcrystalline glass.

[0038] Preferably, in any of the above manufacturing methods, the microcrystalline glass is coated with the undercoat layer, intermediate layer and water-repellent / oil-repellent layer before the coating is applied. Step (I) involves melting each glass raw material at a high temperature of 1600±50℃, then annealing it at 400~650℃ to obtain a homogenized raw glass plate. Step (II) of obtaining a formed raw glass sheet from the raw glass sheet by the overflow downdraw method, the float method, or the rolling method, The molded glass plate is microcrystallized by two heat treatments to obtain a microcrystalline glass preform, which is then used as the raw material for microcrystalline glass, either by ion exchange or without ion exchange, to sequentially coat the surface with the necessary undercoat layer, intermediate layer and water-repellent and oil-repellent layer, wherein the first heat treatment temperature is 500 to 1000°C and the second heat treatment temperature is 550 to 1100°C.

[0039] Preferably, the microcrystalline glass described above, or microcrystalline glass obtained by any of the above manufacturing methods, is applied to displays of mobile phones, tablets, notebooks, portable game consoles, portable digital devices, in-car displays, windshields, or cameras.

[0040] The present invention enables the formation of a robust, durable, and high-performance water- and oil-repellent coating film even when the Si-O structure is very small in the coating interface of microcrystalline glass or glass ceramics, and can achieve excellent water- and oil-repellent properties regardless of whether the highly crystallinity glass has undergone ion exchange or not. [Brief explanation of the drawing]

[0041] [Figure 1] This is a diagram illustrating the reaction process in which PFPE hydrolysis products connect to glass. [Modes for carrying out the invention]

[0042] The composition of microcrystalline glass appears to be very similar to that of general inorganic glass, with approximately SiO2 < 70 wt% in all cases. While it seems possible to produce very good water-repellent and oil-repellent films according to conventional coating methods, microcrystalline glass contains a large amount of crystals internally. Typically, during the formation of microcrystalline glass, SiO2 enters the crystals, changing the structure. This prevents Si-O from being properly released and bonding with the water-repellent and oil-repellent layer. The ratio of these fine crystals is usually 20-100%. In other words, when the crystal ratio is high, the main reason for the deterioration of the quality of the water-repellent and oil-repellent coating layer is the reduction of the glass phase in the microcrystalline glass, resulting in a significant decrease in Si-O at its interface. This invention provides a solution to this "rootless" problem.

[0043] Specifically, the present invention provides the following technical solutions.

[0044] A composite coating design for a water-repellent and oil-repellent film on the surface of highly crystallized microcrystalline glass or glass ceramics, wherein a water-repellent and oil-repellent layer, an intermediate layer, and a primer layer are formed on the glass in order from the outermost surface, that is, the primer layer is on the inside of the microcrystalline glass or glass ceramics and the water-repellent and oil-repellent layer is on the outermost surface.

[0045] In other words, the method of the present invention makes it possible to form a water-repellent and oil-repellent film even 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 may be 60% or more, 70% or more, or especially 80% or more. Of course, since the present invention solves the water-repellent and oil-repellent problem of microcrystalline glass or glass ceramic with a high crystallinity of 60% or more, which makes it difficult to form a water-repellent and oil-repellent film, it is natural that the method of the present invention can also form a composite coating layer of an excellent water-repellent and oil-repellent film on microcrystalline glass or glass ceramic with a crystallinity of 60% or less.

[0046] Here, preferably, the intermediate layer is an ionic crystal with a crystal lattice energy of 700 to 3000 kJ / mol (depending on the magnitude of the crystal lattice energy, the composition of the ionic crystal layer as the intermediate layer is preferably limited to alkali metal fluorides and alkaline earth metal fluorides), preferably 725 kJ / mol or more, and more preferably 770 kJ / mol (excluding radioactive substances) or more.

[0047] The crystal lattice energy of some common ionic crystals / (kJ·mol) -1 The following is shown in Table A.

[0048] [Table 1A]

[0049] Here, preferably, the crystal lattice energy of the ionic crystal is less than 1050 kJ / mol (basically, it is preferable to limit the ionic crystal layer to three types of alkali metal fluorides: LiF / NaF / KF), and more preferably less than 940 kJ / mol (basically, it is preferable to limit the ionic crystal layer to two types: NaF / KF). Alkali metal silicofluorides and alkaline earth metal silicofluorides such as Li2SiF6, Na2SiF6, and K2SiF6 may be used as the intermediate layer.

[0050] Here, preferably, the intermediate layer is a polar and a nonpolar compound (alkali metal fluorides - nonpolar and alkaline earth metal fluorides - polar is preferred), Here, more preferably, the compound is a nonpolar compound (alkali metal fluorides - preferably reduced to nonpolar), Here, preferably, the thickness of the intermediate layer is 1 to 5 nm, and more preferably 1 to 2 nm. Here, preferably, the undercoat layer contains or consists of a Si compound, and preferably the Si compound is selected from the following: -SiOx (x is 2 or less), in the case of a multilayer, at least the outermost or topmost layer contains or consists of silicon oxide. -SiOC, SiON, SiOCN and Si3N4, and SiOx (where x is 2 or less), hydrogen bonds formed in any ratio with SiOC, SiON and SiOCN (where "hydrogen bond" refers to a hydrogen bond formed between the silicon oxide of the glass and any component in the air, such as moisture), or, -A mixed silicon oxide, consisting of silicon oxide SiOx (x is 2 or less) and an oxide of at least one other element other than silicon and / or magnesium fluoride, wherein the other element is preferably at least one selected from aluminum, tin, magnesium, phosphorus, cerium, zirconium, titanium, cesium, barium, strontium, niobium, zinc, and boron, and is particularly preferably a mixture of silicon oxide SiOx (x is 2 or less) and an oxide of at least one element aluminum. Here, preferably, the total thickness of the undercoat layer is 3 to 15 nm, more preferably 5 to 10 nm, and more preferably 5 to 8 nm.

[0051] Here, the water-repellent and oil-repellent layer is also called the AF layer (anti-fingerprint layer), and the AF layer is a layer formed of a fluorine-based polymer, and the fluorine-based polymer may be selected from perfluoropolyether, vinylidene fluoride polymer, tetrafluoroethylene polymer, hexafluoropropylene polymer, chlorotrifluoroethylene polymer, and combinations thereof, and perfluoropolyether (abbreviated as PFPE) is preferred. More preferably, the water-repellent and oil-repellent layer is PFPE with a molecular weight of 2000 or more, and the thickness of the coating layer is 10 nm or more, preferably 15 nm or more, and may be 10 nm to 25 nm.

[0052] Preferably, the microcrystalline glass described above is transparent or opaque, is either pre-ion-exchanged or post-ion-exchanged, and is either prestressed or unprestressed.

[0053] Also, preferably, according to the method described in at least one of the above technical solutions, the microcrystalline glass is characterized in that it is a glass having or consisting of the following glass composition components (in mol%), 40 to 75%, preferably 45 to 72% of SiO2, and 2 to 20%, preferably 4 to 15% of Al2O3, and 0 to 20%, preferably 0.4 to 1.6% of B2O3, and 0 to 10%, preferably 0.8 to 1.5% of P2O5, and 0 to 15%, preferably 0.9 to 4% of ZrO2 + TiO2, and 0 to 5%, preferably 0.1 to 2% of MgO, and 0 to 4%, preferably 0.9 to 3.0% of ZnO, and 0 to 5%, preferably 0.01 to 1% of rare earth oxide, and 0 to 5.5% of Na2O, and 0 to 4% of K2O, and 2 to 34%, preferably 10 to 34% of Li2O, and 4 to 40%, preferably 15 to 40% of Na2O + K2O + Li2O.

[0054] Here, the rare earth oxide is one or more selected from CeO2, Y2O3, La2O3, Ta2O3, Tm2O5, and Nb2O5.

[0055] Also, in some preferred embodiments, the above glass composition components include, for example, additives of coloring oxides such as Nd2O3, Fe2O3, CoO, NiO, V2O5, MnO2, TiO2, CuO, and Cr2O3, and rare earth oxides having a content of 0 to 5 mol% or a content of 0 to 5 mol% in the case of "black glass", and, for example, As2O3, Sb2O3, SnO2, Cl - containing compounds, F - containing compounds, SO3 - containing compounds, NO3 - clarifying agents having a content of 0 to 2 mol% and being one or more of the containing compounds.

[0056] Furthermore, in some preferred embodiments, according to the method of any one of the above technical solutions, the main crystalline phase of the microcrystalline glass is preferably one or more selected from β-quartz solid solution, β-spodumene solid solution, β-eucryptite, spinel, rutile, mullite, olivine, enstatite, cordierite, feldspar, lithium silicate, lithium disilicate, quartz, zirconia, and magnetite, wherein the average grain size is preferably less than 100 nm, particularly preferably 50 nm or less, and very particularly preferably 30 nm or less.

[0057] The present invention uses a combination of an undercoat layer (for example, an SiO2 layer, an SiOx layer, or a silicon oxide-containing mixture layer (collectively referred to as the "silicon oxide layer," and although SiO2 is used as an example here, it is not actually limited to SiO2) + an intermediate layer (abbreviated as the "RF layer," and NaF is used as an example) + a water-repellent and oil-repellent layer such as PFPE. Here, the SiO2 layer must not be too thick, approximately 5 nm and not exceeding 15 nm. The SiO2 exhibits a net-like or chain-like structure at a microscopic level, and the 5 nm SiO2 coating layer is very thin, so that the mesh of its structure can be maintained in the SiO2 coating layer (if the coating is too thick, the SiO2 coating layers overlap each other and the mesh is lost). Subsequently, a thinner intermediate layer RF is coated, and the RF is a compound with a relatively low crystal lattice energy, especially a nonpolar compound. A compound with a relatively low crystal lattice energy is selected as the RF, and the RF reacts with water in the atmosphere to form R + F - H + , OH - It is prone to becoming like that. RF + H2O ⇔ R + +OH - +H + +F -

[0058] Because there are cavities in the undercoat layer, R + F - H + , OH -It can very easily penetrate to the interface of microcrystalline glass and react with the Si-O-Si structure of the crystal, and by opening up the Si-O in the crystal structure, it can react better with the water-repellent and oil-repellent layer, forming a base for film formation. ≡Si-O-Si≡+R + +OH - →≡Si-OH+RO-Si≡, ≡Si-O-Si≡+H + +F - →SiF4+H2O→H2SiO3+H2SiF6, When sufficient Si-O molecules that adhere closely to the microcrystalline glass base are generated in the microcrystalline glass interface and undercoat layer, sufficient valence bonds are formed during the reaction with the top layer of water- and oil-repellent PFPE, thereby significantly improving the performance and abrasion resistance of the water- and oil-repellent layer.

[0059] An intermediate layer with an appropriate crystal lattice energy is key to the operating principle of this invention. If the crystal lattice energy is slightly low, the intermediate layer is active and reactions occur easily. Only when the crystal lattice energy is appropriate can the stability of the material be maintained. Therefore, the intermediate layer of this invention requires that the crystal lattice energy be within a certain range. Intermediate layer materials within this crystal lattice energy range still have high hydrolytic properties and activity, and exhibit a certain degree of corrosiveness after hydrolysis. Therefore, they should not be coated thickly, as thick coatings can actually worsen the effect. Generally speaking, the thickness should not exceed 5 nm. If it is too thick, the reaction products cannot be fully consumed throughout the entire reaction process, leading to erosion of the glass, creating serious corrosion points on the glass surface, and also resulting in a decrease in the weather resistance of the coating layer.

[0060] Regarding the term "microcrystalline glass or glass ceramics" In the present invention, both "microcrystalline glass" and "glass ceramics" have the same meaning and refer to glass having a crystalline phase, unlike glass without a crystalline phase or amorphous glass. Therefore, the terms "microcrystalline glass or glass ceramics," "microcrystalline glass," and "glass ceramics" used in the specification of the present invention all have the same meaning.

[0061] About crystal lattice energy Crystal lattice energy refers to the energy absorbed when an ionic crystal becomes a positively charged or negatively charged ion gas under standard conditions, and is a parameter used to measure the stability of the crystal lattice. Factors that influence the magnitude of crystal lattice energy include ionic radius, ionic charge, and the electron layer configuration of the ions. Referring to the calculation method for crystal lattice energy in the book "Topological Study on Crystal Lattice Energy and Magnetic Susceptibility of Alkaline Earth Metal Halides" by Qin Zhenglong and Liu Changjun, the equation obtained by fitting is as follows: U=1129.1-441.8 0 F+3600.5 1 F, n F=Σ(E i ×E j ×E k ×…) -0.5 , n F is the topology exponential coefficient, and E is the valence electron energy level value.

[0062] The fluoride crystal lattice energies (kJ / mol) obtained by this method are shown in Table B.

[0063] [Table 1B]

[0064] The correlation of the regression equations obtained by applying this method and fitting them is good, and it can similarly be applied to the calculation of the crystal lattice energy of silicon fluoride, with the results shown in Table C.

[0065] [Table 1C]

[0066] It should be noted that the original material of the coating film and the material ultimately formed as the undercoat layer of the glass interface are not necessarily the same concept. Taking alkali metal tetrafluoroethylene (R2SiF6) calculated above as an example, R2SiF6 is normally a relatively stable solid at room temperature. When heated to around 300°C during coating, it decomposes into R2SiF6 -> 2RF + SiF4 (gas), which appears to be a material with high crystal lattice energy. However, in reality, once the film is formed, the material that plays an important role has already undergone a qualitative change, and its crystal lattice energy is within the optimal operating range claimed by this invention. For example, sodium tetrafluoroethylene (Na2SiF6) is an odorless, tasteless white particle or crystalline powder that decomposes into sodium fluoride (NaF) and silicon tetrafluoride (SiF4) after being heated to 300°C or higher.

[0067] Based on the above explanation of the principles of the present invention, whether or not the interface of the coated microcrystalline glass undergoes ion exchange does not affect the implementation and effect of the present invention. Small ions within the glass can only exchange with larger ions in the external salt bath when ion movement is possible. Temperature is a key factor in achieving ion movement, and generally speaking, the glass phase can achieve ion movement relatively easily at relatively low temperatures (e.g., below the strain point temperature, i.e., starting from around 200 degrees Celsius and going up to, for example, 360 degrees Celsius). Alkali metal elements in the microcrystalline phase are part of the crystal structure before becoming mobile ions, and can only move and become freely exchangeable ions after overcoming the constraints imposed by the crystal structure at higher energy, and this temperature is usually closer to the softening point of the glass (e.g., above 600 degrees Celsius). Therefore, most ion exchange usually occurs in the glass phase, and even when the salt bath temperature is extremely high, it occurs first in the glass phase and then in the crystal.

[0068] The glass phase in the highly crystallinity microcrystalline glass of the present invention is particularly small, with rare glass phases present. Even if ion exchange occurs, very few ions enter the glass phase. Therefore, the ability to change the structure and coordination of Si-O in the glass phase is extremely low and localized. Consequently, the influence on the formation of valence bonds in the coating described in the present invention is very small. In other words, highly crystallinity glass always lacks Si-O structures at its interface, regardless of whether ion exchange has occurred. The present invention was made for such application scenarios. When high temperatures are applied, ions within the crystal participate in ion exchange, meaning the crystal is destroyed. This causes the Si-O within the crystal to open, contributing only to the formation of valence bonds in the coating described in the present invention. The present invention aims to solve how to form a strong, durable, and high-performance water- and oil-repellent coating film when the Si-O structure at the interface of the coating film is very small. Highly crystallinity glass is not hard enough to affect the implementation of the present invention, regardless of whether ion exchange has occurred.

[0069] The method for producing microcrystalline glass or glass ceramics containing a water-repellent and oil-repellent composite coating layer on its surface, as described in the present invention, is as follows.

[0070] The constituent components are, 40-75%, preferably 45-72%, SiO2 2-20%, preferably 4-15%, Al2O3, 0-20%, preferably 0.4-1.6%, of B2O3, 0-10%, preferably 0.8-1.5%, of P2O5, 0-15%, preferably 0.9-4%, of ZrO2 + TiO2, 0-5%, preferably 0.1-2%, MgO and 0-4%, preferably 0.9-3.0% ZnO, 0-5%, preferably 0.01-1%, of rare earth oxides, 0-5.5% Na2O, 0-4% K2O and 2-34%, preferably 10-34%, Li2O, A glass containing 4-40%, preferably 15-40%, of Na2O+K2O+Li2O is fired by the following method to obtain microcrystalline glass or glass ceramics.

[0071] Here, the microcrystalline glass or glass ceramic is Step (I) involves melting each glass raw material at a high temperature of 1600±50℃, then annealing it at 400~650℃ to obtain a homogenized raw glass plate. Step (II) of obtaining a formed raw glass sheet from the raw glass sheet by the overflow downdraw method, the float method, or the rolling method, Step (III) involves microcrystallizing the molded glass plate through two heat treatments to obtain a microcrystallized glass preform, where the first heat treatment is performed at a temperature of 500-1000°C for 0.5-5 hours, and the second heat treatment is performed at a temperature of 550-1100°C for 0.5-6 hours. The microcrystalline glass preform is obtained by firing it in a manner that includes step (IV), in which it is used to sequentially coat the surface with the necessary undercoat layer, intermediate layer and water-repellent / oil-repellent layer, either by ion exchange or without ion exchange.

[0072] Here, the ion exchange may be carried out by a conventional method. For example, a mixed molten salt containing 10-75 wt% NaNO3 and 25-90 wt% KNO3 may be used, according to the mass standard, and the ion exchange may be performed for 5-10 hours at a temperature range of 380-500°C.

[0073] Specifically, this firing method involves first weighing the glass raw materials and melting them at a high temperature such as 1600±50℃, then annealing them at approximately 400℃~650℃, homogenizing the glass, and forming a microcrystalline glass substrate. The microcrystalline glass substrate, also called a raw glass plate, is a glass plate that has not yet 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 the overflow down-draw method, the float method, or the rolling method, and the thickness of the obtained raw glass plate is between 0.1 and 5 mm. Furthermore, it can be formed into a plate shape by forming it into a block, annealing it, and then cutting it.

[0074] After the microcrystalline glass substrate is formed, it can be subjected to two heat treatments to further microcrystallize it, thereby producing a microcrystalline glass preform. The first heat treatment is performed at a temperature of approximately 500-1000°C for 0.5-5 hours, and the second heat treatment is performed at a temperature of approximately 550-1100°C for 0.5-6 hours. After crystallization, the required microcrystalline glass or glass ceramic is formed, and then, either after ion exchange or without ion exchange, it is entered into a vacuum coating machine (PVD). The coating parameters are set, and the undercoat, intermediate layer, and water- and oil-repellent layer are coated in that order. The flow within the vacuum coating machine is glass loading - vacuuming - plasma cleaning - deposition - release to atmosphere (from vacuum to atmospheric pressure) - unloading.

[0075] The manufacturing method of the chemically strengthened glass of the present invention and the stress performance characteristics of the chemically strengthened glass of the present invention will be described in detail below with reference to examples.

[0076] [Example of Part 1: Glass Manufacturing Example] Using Example 1 as an example, we will explain how to manufacture a glass substrate.

[0077] (1) Mix the materials of Example 1 shown in Table 1, place the mixed material in a platinum crucible, and melt it in a lift-type high-temperature furnace at 1600°C for 5 hours while maintaining the temperature. Subsequently, pour it into a preheated stainless steel mold, place it in an annealing furnace, and anneal it at 580°C for 24 hours to remove internal stress in the glass. After annealing, cut the glass block, leaving excess material on all six sides, to obtain a glass block. Then, using a wire cutting machine, CNC engraving machine, surface grinding machine, and buffing machine, perform precise size cutting, surface grinding, and edge sweeping to obtain a raw glass sheet with dimensions of 155mm × 78mm × 0.65mm.

[0078] Here, we will explain the model numbers of the equipment used in the above process. Multi-wire cutting machine: CH5625, Taizhou Chenhong CNC Equipment Manufacturing Co., Ltd. CNC machine tool carving machine: CN-650, Shandong Chinuo CNC Equipment Co., Ltd. Surface grinding machine: YJ-13B6LD, Hunan Ningjing Machinery Co., Ltd., and The buffing machine is model YJ-13B6PD, manufactured by Hunan Ningjing Machinery Co., Ltd.

[0079] (2) First, a raw glass plate is subjected to a first heat treatment at 650°C for 3 hours in a lift-type high-temperature furnace to form crystal nuclei, and then a second heat treatment at 730°C for 3 hours is performed to precipitate crystals, thereby producing glass ceramics. Crystallographic analysis is performed on the glass ceramics, including the degree of crystallinity, the crystal type (main crystal phase and subcrystal phase type), the ratio of the main crystal phase to the subcrystal phase, and the average crystal grain size. The Vickers hardness, fracture toughness, average visible light transmittance, and haze of the glass ceramics (hereinafter also called "non-ion-exchanged glass ceramics") are also tested.

[0080] (3) Ion exchange is performed on the glass ceramics using a mixed salt bath of 40 wt% NaNO3 and 60 wt% KNO3 as the molten salt, the strengthening temperature (i.e. ion exchange temperature) is 380°C, and the strengthening time is 9 hours. After the strengthening is complete, the glass ceramics are removed and washed to obtain strengthened glass ceramics (hereinafter also called "glass ceramics that have undergone ion exchange").

[0081] (4) Appropriate characteristic tests were performed on the acquired reinforced glass ceramics. These characteristic tests included haze, average visible light transmittance, surface compressive stress, depth of compressive stress, and Young's modulus. The specific test results are shown in Table 3.

[0082] Here, the definitions and test methods for crystallinity, principal crystal phase, secondary crystal phase, average grain size, Vickers hardness, fracture toughness, average visible light transmittance, haze, surface compressive stress, compressive stress depth, and Young's modulus will be explained in detail below.

[0083] Surface compressive stress, as used here, refers to the phenomenon where, after chemical strengthening, smaller-radius alkali metal ions are replaced by larger-radius alkali metal ions on the surface of the glass. The resulting crowding effect of the larger-radius alkali metal ions generates compressive stress on the glass surface, which is called surface compressive stress.

[0084] Crystallinity: A diffraction peak curve was obtained by analysis using an XRD diffraction instrument, where the incident angle range was 2Theta = 10 to 50 degrees, the scanning speed was 6 degrees / min, and the instrument used in this example was a Shimadzu XRD-6000. The crystallinity was calculated using equation (1-1),

number

[0085] Ratio of the main crystalline phase: In glass ceramics, this is the crystalline phase that accounts for the largest proportion of other crystalline phases by mass.

[0086] Ratio of subcrystal phases: In addition to the main crystal phase, one or more other crystal phases may be present in the ceramic portion of the glass ceramic, and the mass percentage of the subcrystal phases is smaller than the mass percentage of the main crystal phases.

[0087] Average crystal grain size: This is the average length of the crystal grains of the microcrystalline glass when observed at a magnification of 100,000 to 1,000,000 times. It is obtained by observation using a transmission electron microscope (model: Thermo Fisher Scientific (formerly FEI) Talos F200S). During measurement, a magnified photograph is taken of the crystal grains in a certain area, and a finite number of crystal grains are found within the area of ​​the magnified photograph. The size of the finite crystal grains is indicated by scale, and then the average value is calculated. In the embodiment of the present invention, the magnification during measurement is 500,000 times.

[0088] Vickers hardness: The Vickers hardness was tested using a Vickers hardness tester, in accordance with the standard "GB / T 37900-2019 Test Method for Hardness and Fracture Toughness of Ultrathin Glass, Small Load Vickers Hardness Indentation Method". The instrument used in this example is a digital display small load Vickers hardness tester VTD405 (Beijing Wowei Technology Co., Ltd.).

[0089] Fracture toughness: Represents the indentation measurement result. After polishing the test sample, a diamond indenter of a Vickers hardness tester is used to press the sample with a load p of 300 N for 10 seconds to create an indentation. A corresponding crack is formed at the apex of the indentation, and the fracture toughness value K is calculated based on the indentation load P and the length of crack expansion C. ICThe fracture toughness is calculated. The specific fracture toughness is obtained by testing and calculating according to the standard "GB / T 37900-2019 Test Method for Ultrathin Glass Hardness and Fracture Toughness: Small Load Vickers Hardness Indentation Method".

[0090] Surface compressive stress (MPa): The surface compressive stress of the glass sample is tested using the FSM-6000LE waveguide optical stress meter manufactured by ORIHARA Corporation of Japan.

[0091] Depth of compressive stress (μm): This is the distance from the surface of the glass being measured to the point where the compressive stress is zero.

[0092] Haze: This is the percentage of the total transmitted light intensity that is shifted by more than 2.5° from the incident light, and is measured using a colorimeter (model CM~3600A).

[0093] Visible light transmittance: Within the wavelength range of visible light, this is the ratio of the radiant energy projected and transmitted to an object to the total radiant energy projected to the object as the incident light beam exits one side of the irradiated surface or medium from the other side.

[0094] Average visible light transmittance: This value is obtained by measuring the transmittance at each wavelength at 10 nm intervals within a specific wavelength range, and then dividing the sum of the measured transmittances at each wavelength by the number of transmittances measured for each wavelength. For example, to calculate the average transmittance for wavelengths from 360 to 400 nm, the transmittances at wavelengths of 360 nm, 370 nm, 380 nm, 390 nm, and 400 nm are measured, and the number of measured transmittances for 360 to 400 nm is 5. The sum of these transmittances is then divided by 5 to obtain the average transmittance for wavelengths from 360 to 400 nm.

[0095] Young's modulus (GPA): The Young's modulus of the sample is obtained by testing using the sound wave method, and the instrument used is the IET-1600P high-temperature modulus tester.

[0096] [Examples 2-13] The steps of the manufacturing method are the same as in Example 1, where details of the differences can be found in Tables 1, 2, and 3. Specifically, Tables 1, 2, and 3 show the composition of each raw material in the specific glass recipe, the heat treatment process conditions in step (2), the performance test results for the obtained glass ceramics, and the ion exchange process conditions in step (3) and the details of the performance test results for the obtained reinforced glass ceramics.

[0097] [Table 1]

[0098] [Table 2-1] [Table 2-2] [Table 2-3] [Table 2-4] [Table 2-5]

[0099] As can be seen from Table 2 above, the crystallinity of the glass ceramics obtained by heat-treating the raw glass obtained in the present invention ranges from a minimum of 61.2% to a maximum of 90.35%, the visible light transmittance is between 89% and 92%, the average grain size is between 15.7 nm and 25.5 nm, the haze is between 0.09% and 0.20%, the Vickers hardness is between 718 and 796 HV, and the fracture toughness is between 1.4 and 1.9 MPa·m. 1 / 2 That is the case.

[0100] [Table 3-1]

[0101] As can be seen from the composition of the glass described above, rare earth oxides may be included in the glass recipe. Specifically, the present invention may include one or more of the following selected from CeO2, Y2O3, La2O3, Ta2O3, Tm2O5, and Nb2O5, with the content of these rare earth oxides usually not exceeding 5 mol%, and colorants and fining agents may be added as needed. Specifically, in the composition of the glass described above, Nb2O3 acts as a colorant, and in the present invention, in addition to Nb2O3, Nd2O3 One or more of the following substances may be added as a coloring agent: Fe2O3, CoO, NiO, V2O5, MnO2, TiO2, CuO, CeO2, and Cr2O3. After adding a coloring agent, the visible light transmittance of the glass decreases. The more coloring agent added, the lower the transmittance. Generally, the addition ratio should not exceed 5 mol%. Adding 1 mol% or more will cause a significant change in the overall color and transmittance of the glass. Adding an excessive amount of coloring agent (for example, about 5 mol%) will affect the crystallinity and crystal size of the microcrystalline glass. In this invention, in addition to all the components of the above examples, adding 1 mol% of any combination of Fe2O3, NiO, MnO2 and other coloring agents in any ratio will cause the glass to appear black. Adding 0.5 mol% or more of any combination of CoO, Cr2O3 and other coloring agents in any ratio will cause the glass to appear black with a blue phase. If the amount of coloring agent used does not exceed 5 mol%, it will not affect other properties of the glass.

[0102] In the glass of the present invention, depending on the actual melting conditions, the clarifying agent may be used alone or in combination, and the clarifying agent may be As2O3, Sb2O3, SnO2, or SO3. - It is one or more selected from compounds, fluorides or salts, chlorides or salts, and nitrates. Here, as a clarifying agent, As2O3 and Sb2O3 have a very good clarifying effect but are undesirable due to their certain toxicity, and fluorides can also be used as a clarifying agent but are undesirable due to their corrosiveness, and usually SnO2, SO3 (e.g., Na2SO4), Cl compounds (e.g., NaCl), and NO3 -One or a combination of the contained compounds (e.g., NaNO3) is a conventional clarifying agent and generally does not exceed 1 mol%.

[0103] [Example of Part Two: Example of Manufacturing a Water-Repellent and Oil-Repellent Composite Coating Layer] 1. Form a composite coating layer using the ion-exchanged and ion-exchanged glass ceramics of Example 4 as glass substrates. Using the raw glass obtained in Example 4 of the first part, i.e., lots of glass ceramics that have not undergone ion exchange (i.e., have not undergone the ion exchange treatment in step (3)) (numbered #4-A1 to 4-A15 respectively), and using the ion-exchanged glass ceramics (i.e., those that have undergone the ion exchange treatment in step (3)) as glass substrates (numbered #4-B1 to 4-B15 respectively), a composite coating layer containing the SiO2, NaF, and AF film is formed. Using the above-mentioned un-ion-exchanged glass ceramics (numbered #4-A16 to 4-A18 respectively) and ion-exchanged glass ceramics as glass substrates (numbered #4-B16 to 4-B18 respectively), only a composite coating layer containing the SiO2 and AF film is formed, respectively. Specifically, using the vacuum coating equipment described in Table 4-1 and the coating conditions in Table 4-2 (Note: In each example, the coating time is controlled according to the target thickness of the coating layer, and the coating is stopped when the target thickness is achieved), a composite coating layer is formed according to the method described below, the glass substrate surface is cleaned by ultrasonic cleaning (or cleaning with a flat brush), and after cleaning the surface of the glass substrate, a basically uniform film layer is sequentially formed on the substrate surface using the vacuum coating method. Here, in the vacuum coating process, the glass sample to be coated is placed on an umbrella-shaped coating shelf, the umbrella-shaped coating shelf is placed in a table work holder, and the SiO2 and NaF coating materials are placed separately without mixing into the two electron gun crucibles of the vacuum coating machine (using a Hanil Vacuum 2050 type electron gun vacuum coating machine), filling the crucibles with the materials and leveling them with the surface of the crucible opening, and an AF film (Anti-Fingerprint) is placed inside the molybdenum boat to prevent deposition. To form the anti-fingerprint film on glass, an AF film material (600 ml of AF liquid is dropped into a crucible containing steel wool, and the crucible after the AF liquid has dried is called the AF film material) is placed inside, the vacuum chamber is closed, and vacuuming is started. When the vacuum level at the bottom reaches the vacuum level specified in Table 4-2 of the setting process, Ar gas is automatically flowed into the equipment at a rate of 28 sccm, and Hanil's own Ion Beam is used.The Source Hall ion source is operated to perform ion bombardment and cleaning of the surface of the sensitized glass. Subsequently, specific conditions such as the vacuum level, ion source voltage, ion source current, neutralization current, Ar and O2 gas ratio, electron gun operating current, deposition rate, and coating thickness (where the time parameters of the coating are controlled and adjusted when plasma cleaning is performed before coating) are controlled as shown in Table 4-2. SiO2 and NaF (both raw materials SiO2 and NaF are in particulate form) are coated in sequence according to these conditions. Subsequently, specific conditions such as the vacuum level, evaporation prevention operating current, deposition rate, and coating thickness are controlled as shown in Table 4-2, and AF is coated according to these conditions. Here, L5 type SiO2 from Merck AG of Germany is used as the coating material for the SiO2 film.

[0104] The NaF film is used as a coating material with NaF supplied by Nanyang Yingfu Kang Optoelectronic Materials Co., Ltd., and the AF film (Anti-Fingerprint Glass) is used as a coating material (abbreviated as "PFPE" film) with AF main component (manufactured by Shin-Etsu Chemical Co., Ltd.) using KyY1905-1 type fluorine-containing polyether manufactured by Shin-Etsu Chemical Co., Ltd. of Japan.

[0105] After the coating was completed, a contact angle test was performed on the outer surfaces of the non-ion-exchanged and ion-exchanged glass ceramics. The thickness of each of the formed SiO2, NaF, and AF film layers and the contact angle test results for each film layer are shown in Tables 5-1 and 5-2.

[0106] After coating, the water contact angle, oleic acid contact angle, and water droplet angle after wear are measured on the coated surface to assess the coating quality and durability.

[0107] Here, the water contact angle (°) on the AF film surface is measured using the method based on JIS R 3257 (1999).

[0108] Here, the method for measuring the oleic acid contact angle on the AF film surface involves dropping 7 μL of liquid onto a sample of the horizontally coated film and measuring the resulting cut-off angle.

[0109] Using hexadecane instead of water, the contact angle of oleic acid was tested by dropping it onto non-ion-exchanged glass ceramics. The test results for glass ceramics numbered #4-A10, #4-A11, and #4-A12 are as follows: [Table 3-2]

[0110] Abrasion resistance test: 1cm 2 A wear-resistant indenter was made using a Korean minoan solid eraser (6mm diameter, Type A) (manufactured by MIRAE SCIENCE, minoan) as the indenter. Under a load of 1kgf, the surface of the AF film formed on the surface of a glass substrate was rubbed back and forth 2500 times (or more) under conditions of a stroke width of 40mm and a speed of 40mm / second. Subsequently, the AF film surface was cleaned by dry wiping with a cloth [Ozu Sangyo Co., Ltd., DUSPER® registered trademark]. After the abrasion resistance test of the AF film, the water contact angle (°) was measured at three positions on the surface, and the measurement was repeated three times at each position to measure the average water contact angle (°) at a total of nine positions.

[0111] [Table 4-1] Note: Coatings are applied to create the necessary vacuum conditions, and those skilled in the art can select and use some or all of the pumps listed in Table 4-1 above according to conventional means as needed. Here, a mechanical pump, also called a back pump, continuously changes the volume of the suction cavity inside the pump by mechanical means while maintaining a sealing effect using oil, and a vacuum is created as the volume of gas in the aspirated container continues to expand. A Roots pump is a pressure booster pump that functions to increase the pressure difference between the intake port and the exhaust port, and it uses a mechanical pump as a back pump. A diffusion pump is a pump used to obtain a high vacuum, and when using a diffusion pump, a mechanical pump and a Roots pump are used as back pumps. A Polycold is a cryogenic water gas pump used to capture residual gas present in a high vacuum environment when using a diffusion pump, and its operating principle is to place a refrigeration coil that can reach below -120°C at the pump port of the diffusion pump, and rapidly capture residual gas in the vacuum system by the low-temperature condensation effect on its surface.

[0112] [Table 4-2]

[0113] [Table 5-1]

[0114] [Table 5-2]

[0115] 2. Form a composite coating layer using the ion-exchanged and ion-exchanged glass ceramics from Example 8 as a glass substrate.

[0116] This procedure is similar to the one described in Example 4 of Section 1 above, where a composite coating layer is formed using the glass ceramics formed in Example 4 as a glass substrate. The difference is that in this section, the glass ceramics that have not been ion-exchanged (numbered #8-A1 to #8-A15, respectively) and the glass ceramics that have been ion-exchanged (numbered #8-B1 to #8-B15, respectively) are used as glass substrates to form a composite coating layer containing SiO2, NaF, and AF films, and a composite coating layer containing only SiO2 and AF films (numbered #8-A16 to #8-A18 for the non-ion-exchanged glass ceramics, and #8-B16 to #8-B18 for the ion-exchanged glass ceramics). The results of the water contact angle test on the outer surface of the coating layer are shown in Tables 6-1 and 6-2.

[0117] [Table 6-1]

[0118] [Table 6-2]

[0119] 3. Form a composite coating layer using the ion-exchanged and ion-exchanged glass ceramics from Example 12 as a glass substrate. The procedure is similar to that in Example 4 of Section 1 above, where a composite coating layer is formed using the glass ceramics formed in Example 4 as a glass substrate. The difference is that in this section, the glass ceramics that have not been ion-exchanged (numbered #12-A1 to #12-A15, respectively) and the glass ceramics that have been ion-exchanged (numbered #12-B1 to #12-B15, respectively) in Example 12 are used as glass substrates to form a composite coating layer containing SiO2, NaF, and AF films, and a composite coating layer containing only SiO2 and AF films (numbered #12-A16 to #12-A18 for the non-ion-exchanged glass ceramics, and #12-B16 to #12-B18 for the ion-exchanged glass ceramics). The results of the water contact angle test on the outer surface of the coating layer are shown in Tables 7-1 and 7-2.

[0120] [Table 7-1]

[0121] [Table 7-2]

[0122] 4. Form a composite coating layer using the ion-exchanged and ion-exchanged glass ceramics from Example 13 as a glass substrate. The procedure for forming a composite coating layer using the glass ceramics formed in Example 4 of Section 1 above as a glass substrate is similar, but different in that in this section, the glass ceramics that have not been ion-exchanged (numbered #13-A1 to #13-A15, respectively) and the glass ceramics that have been ion-exchanged (numbered #13-B1 to #13-B15, respectively) in Example 13 are used as glass substrates to form a composite coating layer containing SiO2, NaF, and AF films, and a composite coating layer containing only SiO2 and AF films (numbered #13-A16 to #13-A18 for the non-ion-exchanged glass ceramics, and #13-B16 to #13-B18 for the ion-exchanged glass ceramics, respectively). The results of the water contact angle test on the outer surface of the coating layer are shown in Tables 8-1 and 8-2.

[0123] [Table 8-1]

[0124] [Table 8-2]

[0125] As can be seen from the experimental results in Tables 5-1, 5-2, 6-1, 6-2, 7-1, 7-2, 8-1, and 8-2 above, four glass ceramics with different crystal ratios were selected from 13 glass ceramic recipes, and three coating layers were formed using both ion-exchanged and ion-exchanged versions of each as glass substrates. From this data, the following conclusions can be drawn.

[0126] 1) If the thickness of the undercoat layer is too thick and exceeds 20 nm, the abrasion resistance of the AF will be poor, so a thickness of no more than 15 nm is preferable.

[0127] 2) If the intermediate layer is too thick and exceeds 5 nm, the AF will have poor initial performance and wear resistance. However, in the absence of an 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, but the contact angle after 2500 friction cycles reaches a maximum of approximately 60 degrees.

[0128] 3) The primer layer should be of moderate thickness, the intermediate layer thin, and the AF layer should be either thick or thin; both are effective.

[0129] 4) The surface layer is 10 nm or thicker, and the resulting composite coating layer has good water and oil repellency and excellent abrasion resistance. A thickness of 15 nm or thicker is preferable, and the abrasion resistance increases with thickness. From a cost standpoint, the resulting coating layer is ideal in terms of both water and oil repellency and abrasion resistance unless it exceeds 25 nm.

[0130] 5) Even when a three-layer composite coating is directly formed on glass ceramics without ion exchange, i.e., prestressing treatment, its water-repellent and oil-repellent properties are excellent. When the three-layer composite coating is formed on ion-exchanged tempered glass, the results of the abrasion resistance test show that the contact angle is larger, meaning that the water-repellent and oil-repellent effect is even better.

[0131] In summary, the thickness of the undercoat layer is preferably 3 to 15 nm, the thickness of the intermediate layer is 1 to 5 nm, the thickness of the AF film layer is 10 nm or more, preferably 15 nm or more, and may be in the range of 10 to 25 nm, the intermediate layer is preferably 1 to 2 nm, and the undercoat layer is most effective when formed to 5 to 10 nm, with 5 to 8 nm being optimal.

[0132] 5. For the ion-exchanged glass ceramics in Example 4 of the first part (glass ceramics manufactured according to steps (1) and (2) based on recipe #4, without the ion exchange treatment in step (3)), composite coating layers (numbered #4-a1, #4-a2, and #4-a3 respectively) were formed on the surface according to the operating method and conditions described in Section 1 above, the only difference being that the thickness of each coating layer was different, as shown in Table 9 below. The coating quality and durability performance of the composite coating film formed on the surface were tested, and the results are summarized in Table 9 below.

[0133] For the ion-exchanged glass ceramics in Example 4 of Part 1, composite coating layers (also called tempered glass, numbered #4-b1, #4-b2, and #4-b3 respectively) were formed on the surface according to the operating method and conditions described in Section 1 above, the only difference being that the thickness of each coating layer was different, as shown in Table 9 below. The coating quality and durability of the composite coating film formed on the surface were tested, and the surface compressive stress and depth of compressive stress were tested according to the test method in Example 4 of Part 1. All test results are summarized in Table 9 below.

[0134] In each of the ion-exchanged glass ceramics in Example 4 of Part 1, a black coloring agent was mixed in, that is, based on Recipe 4, 0.5 mol% NiO, 1 mol% Fe2O3, and 0.3 mol% CoO were added, using the total moles of each substance in the original raw glass recipe as the base. Glass ceramics were then manufactured according to steps (1) and (2) in "Examples of Glass Manufacturing" of Part 1, and composite coating layers (also called ion-exchanged black glass or prestressed black glass, numbered #4-c1, #4-c2, and #4-c3 respectively) were formed on the surface according to the operating methods and conditions described in Section 1 above, the only difference being the thickness of each coating layer, as shown in Table 9 below. The coating quality and durability of the composite coating films formed on the surface were tested, and the results are summarized in Table 9 below. The obtained black glass has an opaque black appearance and exhibits a deep blue-black color when irradiated with strong white light.

[0135] [Table 9]

[0136] As can be seen from Table 9 above, the intermediate layer is thin and in the range of 1-3 nm, and regardless of whether or not ion exchange, i.e., glass prestressing treatment is performed, the AF film on the outer surface of the resulting composite coating layer has excellent bonding strength and abrasion resistance, and the bonding strength and abrasion resistance of the AF film are not affected even after the addition of a black coloring agent.

[0137] (Note) (Note 1) A microcrystalline glass containing a water-repellent and oil-repellent composite coating layer on its surface, wherein the microcrystalline glass comprises, in order from the outermost surface, a water-repellent and oil-repellent layer, an intermediate layer, and a primer layer, wherein the intermediate layer is an ionic crystal intermediate layer containing a crystal lattice energy of 700 to 3000 kJ / mol, and the primer layer contains a compound or mixed silicon oxide layer containing Si-O bonds. Microcrystalline glass characterized by the following features.

[0138] (Note 2) The degree of crystallinity may be greater than 60%, or greater than 70%, or greater than 80%. Microcrystalline glass as described in Appendix 1.

[0139] (Note 3) The aforementioned intermediate layer is formed using an ionic crystal having a crystal lattice energy of 725 to 3000 kJ / mol, more preferably 770 to 3000 kJ / mol, as the original coating film material. Alternatively, a fluoride intermediate layer is formed using a compound with a crystal lattice energy of 9400 to 11400 kJ / mol, preferably silica fluoride, as the original coating film material. Microcrystalline glass as described in Appendix 1 or Appendix 2.

[0140] (Note 4) The aforementioned intermediate layer contains alkali metal fluorides or alkaline earth metal fluorides, or is an intermediate layer formed using ionic crystals selected from alkali metal silicofluorides and alkaline earth metal silicofluorides as the original coating film material. Microcrystalline glass as described in Appendix 3.

[0141] (Note 5) The aforementioned intermediate layer is an ionic crystal intermediate layer with a crystal lattice energy less than 1050 kJ / mol, preferably less than 940 kJ / mol. Microcrystalline glass as described in any one of the appendices 1 to 3.

[0142] (Note 6) The intermediate layer is a crystal formed using at least one ionic crystal from LiF, NaF, and / or KF as the original coating film material, or an intermediate layer formed using at least one from MgF2, CaF2, SrF2, or BaF2 as the original coating film material, or a fluoride intermediate layer formed using at least one from Li2SiF6, Na2SiF6, K2SiF6, Rb2SiF6, Cs2SiF6, BeSiF6, MgSiF6, CaSiF6, SrSiF6, or BaSiF6 as the original coating film material. An intermediate layer formed using NaF or KF ionic crystals as the original coating film material is preferred. Microcrystalline glass as described in Appendix 5.

[0143] (Note 7) The thickness of the intermediate layer is 1 to 5 nm, preferably 1 to 2 nm, and / or The thickness of the aforementioned undercoat layer is 3 to 15 nm, preferably 5 to 10 nm, more preferably 5 to 8 nm, and / or The thickness of the water-repellent and oil-repellent layer is 10 nm or more, preferably 15 nm or more, and may be between 10 nm and 25 nm. Microcrystalline glass as described in any one of the appendices 1 to 6.

[0144] (Note 8) If the aforementioned undercoat layer is multilayered, the compound containing the Si-O bond or the mixed silicon oxide layer is used as the outermost undercoat layer, and the mixed silicon oxide is silicon oxide SiO x A mixture of (x is 2 or less) and an oxide of at least one element other than silicon and / or magnesium fluoride, The other elements are preferably aluminum, tin, magnesium, phosphorus, cerium, zirconium, titanium, cesium, barium, strontium, niobium, zinc, or boron, and the mixed silicon oxide is silicon oxide SiO x It is preferably a mixture of aluminum oxide. The compound containing the Si-O bond is more preferably SiOx (where x is 2 or less), or a hydrogen bond formed in any ratio with one of the substances from SiOC, SiON, SiCN and / or Si3N4, or with one of the substances from SiOC, SiON and / or SiCN. Microcrystalline glass as described in any one of the appendices 1 to 7.

[0145] (Note 9) The water-repellent and oil-repellent layer is a fluorine-based polymer layer, and a fluorine-containing polyether silicon oxide layer with a molecular weight of 2000 or more is preferred. Microcrystalline glass as described in any one of the appendices 1 to 8.

[0146] (Note 10) The composition of the aforementioned microcrystalline glass consists of oxides in the following mol% ratios. 40-75%, preferably 45-72%, SiO2 2-20%, preferably 4-15%, Al2O3, 0-20%, preferably 0.4-1.6%, of B2O3, 0-10%, preferably 0.8-1.5%, of P2O5, 0-15%, preferably 0.9-4%, of ZrO2 + TiO2, 0-5%, preferably 0.1-2%, MgO and 0-4%, preferably 0.9-3.0% ZnO, 0-5%, preferably 0.01-1%, of rare earth oxides, 0-5.5% Na2O, 0-4% K2O and 2-34%, preferably 10-34%, Li2O, It contains 4-40%, preferably 15-40%, of Na2O+K2O+Li2O, The microcrystalline glass is either ion-exchanged or ion-exchanged glass. Microcrystalline glass as described in any one of the appendices 1 to 9.

[0147] (Note 11) The rare earth oxide is one or more selected from CeO2, Y2O3, La2O3, Ta2O3, Tm2O5, and Nd2O5. Microcrystalline glass as described in Appendix 10.

[0148] (Note 12) The microcrystalline glass may further contain a coloring additive and / or a clarifying agent, the coloring additive is preferably one or more selected from Nd2O3, Fe2O3, CoO, NiO, V2O5, MnO2, TiO2, CuO and Cr2O3, the molar content of the coloring additive relative to the total components of the glass is more preferably not exceeding 5%, the coloring additive is more preferably containing 0.5 mol% or more of CoO and / or Cr2O3 in molar content relative to the total components of the glass, and more preferably containing 1 mol% or more of one or more selected from Fe2O3, NiO or MnO2, and / or The clarifying agent is As2O3, Sb2O3, SnO2, chloride, fluoride, SO3 - Containing compounds and NO3 - Preferably, it is one or more compounds selected from the contained compounds, such as SnO2 and SO3. - Contains compounds, chlorides, and NO3 - It is more preferable that the clarifying agent is one or more selected from the contained compounds, and it is even more preferable that the content of the clarifying agent is 0 to 2 mol%. Microcrystalline glass as described in any one of the appendices 1 to 11.

[0149] (Note 13) The main crystalline phase of the microcrystalline glass is one or more selected from β-quartz solid solution, β-spodumene solid solution, β-eucryptite, spinel, rutile, mullite, olivine, enstatite, cordierite, feldspar, lithium silicate, lithium disilicate, quartz, zirconia, and magnetite, and the average grain size is preferably less than 100 nm, more preferably 50 nm or less, and particularly preferably 30 nm or less. Microcrystalline glass as described in any one of the appendices 1 to 12.

[0150] (Note 14) Step 1) involves coating microcrystalline glass with a Si-O-containing oxide or mixed silicon oxide layer to form an undercoat layer on the surface of the microcrystalline glass, Step 2) involves coating the surface of the undercoat layer obtained in Step 1) with an intermediate layer, Step 3) involves coating the surface of the intermediate layer obtained in step 2) with a water-repellent and oil-repellent layer, For the coating, it is preferable to use a vacuum deposition method. A method for producing microcrystalline glass as described in any one of the appendices 1 to 13.

[0151] (Note 15) The aforementioned microcrystalline glass is coated with a primer layer, an intermediate layer, and a water-repellent and oil-repellent layer before the coating is applied. Step (I) involves melting each glass raw material at a high temperature of 1600±50℃, then annealing it at 400~650℃ to obtain a homogenized raw glass plate. Step (II) of obtaining a formed raw glass sheet from the raw glass sheet by the overflow downdraw method, the float method, or the rolling method, The molded glass plate is microcrystallized by two heat treatments to obtain a microcrystalline glass preform, which is then used as a raw material for microcrystalline glass, either by ion exchange or without ion exchange, to sequentially coat the surface with the necessary undercoat layer, intermediate layer, and water-repellent and oil-repellent layer, wherein the first heat treatment temperature is 500-1000°C and the second heat treatment temperature is 550-1100°C, and is obtained by firing in a method including step (III). The manufacturing method described in Appendix 14.

Claims

1. In a method for manufacturing microcrystalline glass, step 1) is to coat the microcrystalline glass with a compound containing Si-O bonds or a mixed silicon oxide layer to form an undercoat layer on the surface of the microcrystalline glass, Step 2) involves coating the surface of the undercoat layer obtained in Step 1) with an intermediate layer, Step 3) involves coating the surface of the intermediate layer obtained in step 2) with a water-repellent and oil-repellent layer, However, the intermediate layer is an ionic crystal intermediate layer containing a crystal lattice energy of 700 to 3000 kJ / mol, and in step 1) before coating the microcrystalline glass, 10 to 75 wt% by weight of NaNO ３ and 25-90 wt% KNO ３ Using a mixed molten salt, ion exchange is performed at a temperature range of 380 to 500°C for 5 to 10 hours. A method for producing microcrystalline glass, characterized by having a water-repellent and oil-repellent composite coating layer on its surface.

2. The microcrystalline glass is coated with the undercoat layer, the intermediate layer, and the water-repellent and oil-repellent layer. Before that, Step (I) involves melting each glass raw material at a high temperature of 1600 ± 50°C, then shaping it by the overflow down-draw method, float method, or rolling method, and annealing it at 400 to 650°C to obtain a homogenized molded glass sheet. The molded glass plate is microcrystallized by two heat treatments to obtain a microcrystalline glass preform, which is then used as the raw material for ion-exchanged microcrystalline glass to sequentially coat the surface with the necessary undercoat layer, intermediate layer, and water-repellent and oil-repellent layer, wherein the first heat treatment temperature is 500 to 1000°C and the second heat treatment temperature is 550 to 1100°C, and is obtained by firing in a method including step (III). The manufacturing method according to claim 1.

3. The degree of crystallinity of the aforementioned microcrystalline glass is greater than 60%. The manufacturing method according to claim 1 or claim 2.

4. The aforementioned intermediate layer is an intermediate layer formed using an ionic crystal with a crystal lattice energy of 725 to 3000 kJ / mol as the original coating film material, Alternatively, it is a fluoride intermediate layer formed using a compound with a crystal lattice energy of 9400 to 11400 kJ / mol as the original coating film material. The manufacturing method according to any one of claims 1 to 3.

5. The aforementioned intermediate layer contains alkali metal fluorides or alkaline earth metal fluorides, or is an intermediate layer formed using ionic crystals selected from alkali metal silicofluorides and alkaline earth metal silicofluorides as the original coating film material. The manufacturing method according to claim 4.

6. The aforementioned intermediate layer is an ionic crystal intermediate layer with a crystal lattice energy less than 1050 kJ / mol. The manufacturing method according to any one of claims 1 to 5.

7. The aforementioned intermediate layer is an ionic crystal intermediate layer with a crystal lattice energy less than 940 kJ / mol. The manufacturing method according to claim 6.

8. The intermediate layer is a crystal formed from at least one ionic crystal of LiF, NaF, and / or KF as the original coating film material, or MgF ２ , CaF ２ , SrF ２ or BaF ２ is an intermediate layer formed from at least one of them as the original coating film material, or Li ２ SiF ６ , Na ２ SiF ６ , K ２ SiF ６ , Rb ２ SiF ６ , Cs ２ SiF ６ , BeSiF ６ , MgSiF ６ , CaSiF ６ , SrSiF ６ , or BaSiF ６ is a fluoride intermediate layer formed from at least one of them as the original coating film material. The manufacturing method according to claim 6 or claim 7.

9. The intermediate layer is a polar or nonpolar compound. The manufacturing method according to any one of claims 1 to 8.

10. The thickness of the aforementioned intermediate layer is 1 to 5 nm. and / or, the thickness of the undercoat layer is 3 to 15 nm, and / or, The thickness of the water-repellent and oil-repellent layer is 10 nm or more. The manufacturing method according to any one of claims 1 to 9.

11. The thickness of the aforementioned intermediate layer is 1 to 2 nm, and / or, The thickness of the aforementioned undercoat layer is 5 to 10 nm, and / or, The thickness of the water-repellent and oil-repellent layer is 15 nm or more. The manufacturing method according to claim 10.

12. The thickness of the water-repellent and oil-repellent layer is 10 to 25 nm. The manufacturing method according to any one of claims 1 to 11.

13. The aforementioned undercoat layer is multilayered, and the outermost undercoat layer is a compound or mixed silicon oxide layer containing the Si-O bond, wherein the mixed silicon oxide is a mixture of silicon oxide (SiOx) and an oxide of at least one element other than silicon and / or magnesium fluoride, where x is 2 or less. The manufacturing method according to any one of claims 1 to 12.

14. The aforementioned other elements are those selected from aluminum, tin, magnesium, phosphorus, cerium, zirconium, titanium, cesium, barium, strontium, niobium, zinc, or boron. The compound containing the Si-O bond is SiOx, where x is 2 or less, or SiOC, SiON, SiOCN and / or Si ３ N ４ A hydrogen bond formed in any ratio with any one of the following substances or any one of the following substances: SiOx, SiOC, SiON, and / or SiOCN, where x is 2 or less. The manufacturing method according to claim 13.

15. The aforementioned water-repellent and oil-repellent layer is a fluorine-based polymer layer. The manufacturing method according to any one of claims 1 to 14.

16. The water-repellent and oil-repellent layer is a fluorine-containing polyether silicon oxide layer with a molecular weight of 2000 or more. The manufacturing method according to claim 15.

17. The composition of the aforementioned microcrystalline glass consists of oxides in the following mol% ratios. 40-75% SiO ２ and, 2-20% Al ２ O ３ and, 0-20% B ２ O ３ and, P 0-10% ２ O ５ and, 0-15% ZrO ２ +TiO ２ and, 0-5% MgO and 0-4% ZnO, 0-5% rare earth oxides, 0-5.5% Na ２ O and, 0-4% K ２ O and, 2-34% Li ２ O and, 4-40% Na ２ O+K ２ O+Li ２ O and, containing The manufacturing method according to any one of claims 1 to 16.

18. The composition of the aforementioned microcrystalline glass consists of oxides in the following mol% ratios. 45-72% SiO ２ and, 4-15% Al ２ O ３ and, 0.4-1.6% B ２ O ３ and, P-values ​​of 0.8-1.5% ２ O ５ and, 0.9-4% ZrO ２ +TiO ２ and, 0.1-2% MgO and 0.9-3.0% ZnO and 0.01-1% rare earth oxides, 0-5.5% Na ２ O and, 0-4% K ２ O and, 10-34% Li ２ O and, 15-40% Na ２ O+K ２ O+Li ２ O and, containing The manufacturing method according to claim 17.

19. The aforementioned rare earth oxide is CeO ２ , Y ２ O ３ La ２ O ３ Ta ２ O ３ , Tm ２ O ５ and Nd ２ O ５ One or more types selected from the following: The manufacturing method according to claim 17 or claim 18.

20. The microcrystalline glass further contains a coloring additive, the coloring additive being Nd ２ O ３ Fe ２ O ３ , CoO, NiO, V ２ O ５ MnO ２ , TiO ２ CuO and Cr ２ O ３ One or more of the following are selected from: The manufacturing method according to any one of claims 1 to 19.

21. The main crystalline phase of the microcrystalline glass is one or more selected from β-quartz solid solution, β-spodumene solid solution, β-eucryptite, spinel, rutile, mullite, olivine, enstatite, cordierite, feldspar, lithium silicate, lithium disilicate, quartz, zirconia, and magnetite. The manufacturing method according to any one of claims 1 to 20.

22. The average crystal grain size of the microcrystalline glass is less than 100 nm. The manufacturing method according to claim 21.

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