Hot end metal oxide coating for glass substrates and containers

Abstract

A method of coating a glass substrate with a hot end coating is provided. The method includes the step of applying a composition comprising at least one metal organic salt onto a surface of a glass substrate to form a hot end coating on the glass substrate. The temperature of the glass surface is from about 450 DEG C to about 800 DEG C when a composition comprising at least one metal organic salt is applied to the glass surface. After application, the hot end coating comprises a metal oxide or a combination thereof. A coated glass article is also provided. The coating on the glass article is a hot end coating comprising at least one of a group 3A oxide, a group 4A oxide, or a combination thereof.

Description

Technical Field

[0001] The present invention relates to hot end metal oxide coatings for glass articles and substrates (such as containers, bottles and flat glass), methods of applying hot end metal oxide coatings during the manufacture of glass articles and substrates, and to glass articles and substrates coated with such coatings. Background Art

[0002] Glass products, especially glass containers and bottles, often require coatings to be applied to their surfaces. The coating imparts desirable properties, such as improved adhesion to other coatings, thereby providing additional desirable characteristics (such as scratch resistance and durability). Glass containers, especially glass bottles, can be made by a variety of methods, but they generally involve the following steps:

[0003] 1. Melt the sand and modifier at a temperature above 1200°C to form droplets;

[0004] 2. Forming the hot drop into a container;

[0005] 3. Optionally, coat the hot container with a coating. If this coating is applied, it is called a "hot end" coating. The hot end coating protects the glass and acts as a primer for any optional additional coatings, while having suitable optical properties so that the resulting container remains clear and free of iridescence. The hot end coating also provides a surface to which any coatings applied later in the process, such as a cold end coating and / or a label or other marking, can adhere.

[0006] 4. Cooling of hot containers. Cooling is done under controlled conditions, as cooling the container too quickly can cause it to break; and

[0007] 5. Optionally, a coating is applied to the cooled glass container. If such a coating is applied, it is called a "cold end" coating and typically comprises a wax. These cold end coatings can impart properties such as improved lubricity (e.g., for easier automated handling), scratch resistance, improved durability and strength, and / or improved label adhesion.

[0008] There is a desire to improve the efficiency and safety of hot-end coating processes. Currently, some hot-end precursors (such as monobutyltin trichloride, tin tetrachloride, or titanium isopropoxide) are applied to hot glass substrates using chemical vapor deposition. In chemical vapor deposition, the coating material is volatilized, typically by evaporation of a liquid, typically at high temperature and atmospheric pressure. The vapor is deposited on and / or reacts with the hot glass surface. This coating (the hot-end coating) protects the glass container and serves as a primer for the subsequently deposited cold-end coating, which adheres to the metal oxide surface, protects the glass from scratches, and helps maintain glass strength. Tin precursors are highly acidic, and the HCl released by the CVD reaction can corrode the coating equipment used to apply them. Alternatives to traditional tin precursors, such as titanium isopropoxide, are flammable and can be harmful to health. During the CVD process, fouling can occur on the coating equipment over time, requiring the process to be stopped for regular maintenance and cleaning of the equipment, which is inefficient and costly.

[0009] Aluminum acetylacetonate, also known as Al(acac)3, can be used in certain processes, particularly CVD, to produce aluminum oxide as a hot-end coating on glass substrates. However, it is insoluble in water and has a low vapor pressure. For use in CVD, it must be dissolved in an organic solvent with a low flash point, making it relatively hazardous. Other aluminum oxide precursors also have undesirable environmental and practical limitations for hot-end coating processes. Trialkylaluminum compounds are pyrophoric. Aluminum alkoxides tend to polymerize and form gels when exposed to moisture.

[0010] Other coating methods are described in EP 3 024 792; WO 2012 / 053919; and Processing, Properties, and Applications of Glass and Optical Materials: Ceramic Transactions, by Arun K.

[0011] Varshneya, Helmut A. Schaeffer, Kathleen A. Richardson, Marlene Wightman, and L. David Pye (eds.) (2012). This publication discloses a method for applying Al(OH)3 powder to hot and / or cold glass containers to form a coating. The process described involves dry grinding the starting material using a mill to apply the nanopowder to the glass. However, the mill can easily contaminate the powder and, in turn, the resulting coating. However, applying a powdered coating to hot glass surfaces can also present undesirable environmental and safety limitations due to the need to contain the powder.

[0012] WO 2006 / 060510 describes an aluminum oxide dispersion.

[0013] US Pat. No. 2,617,741 describes a method of spraying various metal compositions onto a glass substrate to prepare an intermediate oxide film, and subsequently coating the oxide film with tin, cadmium, or indium oxide to provide a conductive coating.

[0014] JP H08239240A discloses the use of ultrasonic spraying at high temperatures to coat glass with aqueous solutions of halogen (e.g., chlorine) compounds, acetates, sulfates, or nitrates of tin, titanium, or zirconium. Deposition is achieved by mist (ultrasonic crystal or fan / blower) at high temperatures to coat the glass with a metal oxide film.

[0015] Therefore, there is a need for a method of applying a hot end coating to a glass substrate that is non-corrosive, non-hazardous, produces virtually no harmful emissions, and avoids buildup on equipment, while being efficient, cost-effective, safe, environmentally friendly, and achieving the desired properties and characteristics of the hot end coating, such as being substantially transparent, substantially colorless, and lacking iridescence. Summary of the Invention

[0016] The inventors have surprisingly discovered that a composition comprising at least one metal organic salt can be applied directly to the heated surface of a glass substrate to form a hot end coating. The surface temperature of the glass substrate is between about 450°C and about 1000°C before, during, or after application of the composition. The inventors have also discovered that spraying or applying an aqueous composition comprising at least one metal organic salt using chemical vapor deposition ("CVD") is a suitable method for applying the hot end coating to the heated surface of the glass substrate. After spraying or CVDing the aqueous composition onto the hot glass, a coating comprising a metal oxide is formed on the glass substrate. The deposited metal oxide coating is substantially transparent or clear, substantially colorless or colorless, and / or substantially non-iridescent or non-iridescent to the naked eye. After applying the hot end coating according to the present invention to the glass surface, an additional cold end coating (preferably in the form of a polymeric formulation) can optionally be deposited onto the hot end coating and adhered thereto.

[0017] Therefore, a method for coating a glass substrate with a coating is provided. The coating is a hot end coating. The hot end coating can be inorganic. The method comprises the following steps.

[0018] a) Applying a composition comprising at least one metal-organic salt onto the surface of a glass substrate, the temperature of the surface being from about 450 °C to about 1000 °C, thereby forming a hot-end coating on the glass substrate. In various embodiments, before, at the first application, during or after applying the composition comprising at least one metal-organic salt, the temperature of the surface is 450 °C to 800 °C. After applying the composition comprising at least one metal-organic salt, the hot-end coating comprises one or more oxides of one or more metals or a combination thereof.

[0019] There is also provided a coated glass article. The article comprises a glass substrate and a hot-end coating on the glass substrate. The coating comprises at least one of Group 3A oxides, Group 4A oxides or a combination thereof; preferably TiO2, TiO, Ti2O3, Ti z O a (0 < z ≤ 2 and 0 < a ≤ 3), ZrO2, Zr b O c (0 < b ≤ 1 and 0 < c ≤ 2), Al2O3, Al2O, AlO, Al x O y (0 < x ≤ 2 and 0 < y ≤ 3), or a combination thereof; more preferably Al2O3, Al2O, AlO, Al x O y (0 < x ≤ 2 and 0 < y ≤ 3) or a combination thereof. Detailed Description

[0020] There is provided a method of coating a glass substrate. The coating is a "hot-end" coating, and optionally a "cold-end" coating is applied thereon.

[0021] The method comprises the following steps:

[0022] a) Applying a composition comprising at least one metal-organic salt onto the surface of a glass substrate, the temperature of the surface being from about 450 °C to about 1000 °C, thereby forming a hot-end coating on the glass substrate. After applying the composition comprising at least one metal-organic salt, the hot-end coating comprises one or more metal oxides or a combination thereof.

[0023] According to one embodiment, the method may further comprise the following steps:

[0024] b) Optionally cooling the glass substrate and the hot-end coating to a temperature of from about 80 °C to about 350 °C, preferably from about 100 °C to about 250 °C, more preferably from about 100 °C to about 200 °C; and

[0025] c) Applying a cold-end coating composition on the hot-end coating to provide a cold-end coating on the hot-end coating.

[0026] According to another embodiment, the composition comprising the metal organic salt is in the form of an aqueous composition applied by spraying. Spraying can be performed with a sprayer equipped with a nozzle, by which the composition or aqueous solution can be atomized at a pressure of about 2 to about 250 psi, or about 10 to about 250 psi, or about 2 to about 100 psi, or about 2 to about 70 psi, or about 10 to about 30 psi. The type of sprayer is not particularly limited, but for example, compressed gas, such as nitrogen, or oxygen or air can be used as a propellant. The sprayer can be an airless type, in which case the composition comprising at least one metal organic salt is pressurized and no propellant is used. Non-limiting examples of operable sprayers are hydraulic, pneumatic or mechanical atomizers, or a combination thereof. Other non-limiting examples of operable sprayers are ultrasonic atomizers, rotary atomizers, airless atomizers or electrostatic atomizers, and such sprayers can also be characterized by the geometry and configuration of the nozzle and orifice, spray pattern, droplet size and the droplet size distribution that may be produced. Several such techniques are discussed in Atomization and Sprays, 2nd edition, by Arthur Lefebvre and Vincent McDonell (CRC Press, 2017) and in Classification of Atomization Devices, by A. Yu Vasilyev, E.S. Domrina, S.V. Kaufman, and A. I. Maiorova, Journal of Physics: Conference Series 1359 (2019) 012131, which are incorporated herein.

[0027] The viscosity of the composition comprising the metal organic salt may be about 1×10 -5 Pa·s to about 100,000 Pa·s, preferably about 1×10 -4 to about 10,000 Pa·s, more preferably about 1×10 -4 to about 1,000 Pa·s at 0.1s at 25°C -1 The composition comprising the metal organic salt may be a Newtonian fluid or a non-Newtonian fluid.

[0028] According to one embodiment, applying the composition comprising the metal organic salt onto the surface of the hot glass substrate is performed in air and under atmospheric pressure. The atmospheric pressure refers to the pressure surrounding the hot glass substrate, not the pressure used to spray the composition comprising the metal organic salt.

[0029] According to another embodiment, the composition comprising the metal organic salt can be applied by a chemical vapor deposition (CVD) process at a pressure of about 1 atm or less. The composition is at ambient temperature and fed into a CVD apparatus through which hot glass passes. The temperature is typically between about 125°C and about 300°C, which causes the solution to evaporate and form a coating on the glass.

[0030] According to another embodiment, the composition comprising the metal organic salt is in the form of a granular solid powder and is applied by spraying or blowing the composition, optionally using a gas. The gas may optionally be pressurized.

[0031] Glass substrate:

[0032] Non-limiting examples of suitable glass substrates can be silicate glass, quartz glass, borosilicate glass, soda-lime glass, crystal glass, aluminosilicate glass, germanosilicate glass, phosphosilicate glass, or crown glass. The glass substrate can include 1 to 100% by weight SiO2. The glass substrate can contain other elements such as sodium, calcium, aluminum, iron, magnesium, boron, lead, sulfur, carbon, selenium, chromium, cobalt, nickel, manganese, phosphorus, germanium, and / or potassium. The glass substrate can include 0 to 100% by weight recycled glass.

[0033] Compositions containing metal organic salts

[0034] The composition comprising the metal organic salt can be an aqueous composition, i.e. it can also comprise water. It should be understood that it is water rather than water of hydration. The composition comprising the metal organic salt can be a solution, dispersion, emulsion, suspension, saturated solution or colloidal form. The composition comprising the metal organic salt can include a polar solvent or suspending agent, such as water, C1 to C4 alcohol, acetone, acetonitrile, dimethylformamide (DMF) or dimethyl sulfoxide (DMSO) or its mixture. Preferred solvents are water or aqueous mixtures.

[0035] The composition comprising the metal organic salt may be in the form of a solid, a powder, or particles (eg, a granular solid).

[0036] The composition may comprise from about 2 wt% to about 100 wt% of a metal-organic salt, based on the weight of the composition. The composition may comprise at least about 5, about 10, about 15, about 20, about 25, about 30, about 35, about 40, about 45, about 50, about 55, about 60, about 65, about 70, about 75, about 80, about 85, about 90, about 95 or at least about 100 wt% of a metal-organic salt, based on the weight of the composition. The composition may comprise at most about 99, about 95, about 90, about 85, about 80, about 75, about 70, about 65, about 60, about 55, about 50, about 45, about 40, about 35, about 30, about 25, about 20, about 15, about 10 or at most about 5 wt% of a metal-organic salt, based on the weight of the composition. According to one embodiment, the composition may comprise from about 1 to about 80 wt%, preferably from about 5 to about 60 wt%, more preferably from about 10 to about 40 wt%, and most preferably from about 10 to about 35 wt% of a metal-organic salt, based on the weight of the composition. According to one embodiment, the composition comprises from about 1 to about 80 wt%, preferably from about 5 to about 60 wt%, and most preferably from about 10 to about 60 wt% of a metal-organic salt, based on the weight of the composition.

[0037] According to one embodiment, the metal-organic salt comprises at least one or a combination of Group 3A C1-C10 organic salts, Group 4 C1-C10 organic salts, including but not limited to mixtures of said organic salts and other precursors suitable for CVD (such as MBTC); preferably titanium stearate, titanium lactate, titanium formate, titanium acetate, zirconium stearate, zirconium lactate, zirconium formate, zirconium acetate, aluminum stearate, aluminum lactate, aluminum formate, aluminum acetate or a combination thereof; more preferably titanium lactate, zirconium lactate, aluminum lactate or a combination thereof; most preferably aluminum lactate; and / or wherein after application, the hot-end coating comprises a metal oxide, the metal oxide comprising at least one or a combination of Group 3A oxides, Group 4A oxides; preferably Al x O y (0 < x ≤ 2 and 0 < y ≤ 3), TiO2, TiO, Ti2O3, Ti z O a (0 < z ≤ 2 and 0 < a ≤ 3), ZrO2, Zr b O c (0 < b ≤ 1 and 0 < c ≤ 2), Al2O3, Al2O, AlO or a combination thereof; more preferably Al2O3, Al2O, AlO, Al x O y (0 < x ≤ 2 and 0 < y ≤ 3) or a combination thereof; most preferably γAl2O3 and Al x O[[ID=②2]] y (0 < x ≤ 2 and 0 < y ≤ 3).

[0038] As described above, when sprayed or otherwise applied to the surface of the glass substrate, the temperature of the composition comprising the metal organic salt can be from about 10°C to about 70°C, from about 15°C to about 60°C, and preferably from about 20°C to about 50°C. Surprisingly, despite the large temperature difference between the composition comprising the metal organic salt and the surface of the glass substrate, the glass substrate does not break or weaken. This effect is particularly surprising when the composition is in the form of a solution, saturated solution, dispersion, emulsion, or colloid containing water or other solvents or carriers, as additional solvents or carriers are required to increase the heat capacity to provide sufficient coverage of the metal organic salt to produce an adequate hot end coating.

[0039] The pH of the composition comprising the metal organic salt is less than about 11, or less than about 10, or less than about 9, or less than about 8, preferably from about 1 to about 7, more preferably from about 2 to about 7, even more preferably from about 3 to about 7, and most preferably from about 2 to about 5.

[0040] According to one embodiment, the composition comprising the metal organic salt may be formed using deionized water. According to one embodiment, the composition comprising the metal organic salt may be formed using tap water.

[0041] In addition to the metal organic salt, the composition may further comprise at least one salt. The additional salt may comprise at least one of a Group 3A or Group 4 element, or a combination thereof, more preferably an aluminum salt, and even more preferably at least one salt comprising at least one of aluminum nitrate (Al(NO3)3), aluminum sulfate (Al2(SO4)3), or a combination thereof. The composition comprising the metal organic salt may comprise from about 1 to about 20% by weight of the salt, from about 1 to about 10% by weight of the salt, preferably from about 3 to about 8% by weight of the salt, and more preferably from about 4 to about 8% by weight of the salt, based on the weight of the composition comprising the metal organic salt.

[0042] According to one embodiment, the composition comprising the metal organic salt is measured at 25°C with a shear rate of 0.1s -1 The viscosity of the fluid may be Newtonian or non-Newtonian.

[0043] Other additives:

[0044] The composition comprising the metal organic salt may also include additional additives as are known and used in the art. For example, the composition comprising the metal organic salt may include one or more of a wetting agent, a surfactant, a viscosity modifier, a preservative, a cosolvent, a stabilizer, or an antimicrobial additive.

[0045] Hot end coating:

[0046] After being applied to the hot surface of a glass substrate, the resulting coating (the "hot end" coating) comprises one or more metal oxides. These metal oxides include at least one or a combination of Group 3A oxides and Group 4A oxides; preferably Al x O y (0 < x ≤ 2 and 0 < y ≤ 3), TiO2, TiO, Ti2O3, Ti z O a (0 < z ≤ 2 and 0 < a ≤ 3), ZrO2, Zr b O c (0 < b ≤ 1 and 0 < c ≤ 2), Al2O3, Al2O, AlO, Al x O y (0 < x ≤ 2 and 0 < y ≤ 3), or a combination thereof; more preferably Al2O3, Al2O, AlO, Al x O y (0 < x ≤ 2 and 0 < y ≤ 3), or a combination thereof; most preferably γAl2O3 or Al x O y (0 < x ≤ 2 and 0 < y ≤ 3). The hot end coating may comprise γAl2O3 or Al x O y (0 < x ≤ 2 and 0 < y ≤ 3).

[0047] The hot end coating can be an inorganic coating. According to certain embodiments, the hot end coating formed from a composition comprising a metal organic salt is substantially free of halides, preferably substantially free of Cl. Substantially free of halides means that based on the weight of the hot end coating, the content of halides is less than 10 wt%, or less than 5 wt%, or 1 wt% or less, or 5000 ppm or less, or 1000 ppm or less, or 500 ppm or less, or 100 ppm or less, or 50 ppm or less, or 10 ppm or less.

[0048] According to one embodiment, the hot end coating is substantially free of carbon. Substantially free of carbon means that based on the weight of the hot end coating, the content of carbon is less than 10 wt%, or less than 5 wt%, or 1 wt% or less, or 5000 ppm or less, or 1000 ppm or less, or 500 ppm or less, or 100 ppm or less, or 50 ppm or less, or 10 ppm or less.

[0049] According to certain embodiments, the hot end coating may be substantially free of metals other than aluminum. Substantially free of metals other than aluminum means that based on the weight of the hot end coating, the content of aluminum is less than 5 wt%, or less than 3 wt%, or less than 1 wt%, or less than 5000 ppm, or less than 1000 ppm, or less than 500 ppm, or 300 ppm or less.

[0050] According to one embodiment, the coating comprises Al x O y (0 < x ≤ 2 and 0 < y ≤ 3), Al2O3, Al2O, AlO, Al x O y (0 < x ≤ 2 and 0 < y ≤ 3) or a combination thereof; more preferably Al2O3, Al2O, AlO, Al x O y (0 < x ≤ 2 and 0 < y ≤ 3) or a combination thereof; most preferably Al x O y (0 < x ≤ 2 and 0 < y ≤ 3); and the coating is substantially free of halogens, optional carbon, and metals other than aluminum.

[0051] According to one embodiment, the resulting coating comprising (one or more) metal oxides is substantially transparent or transparent, substantially colorless or colorless, and / or substantially iridescent-free or iridescent-free to the naked eye. As defined herein, transparent means capable of transmitting light such that things can be seen through it by the naked eye. As defined herein, iridescence refers to the coating having a rainbow effect or appearance observable by the naked eye. As defined herein, colorless means that no color can be distinguished by the naked eye. According to one embodiment, the resulting hot-end coating comprising (one or more) metal oxides is uniform. As defined herein, uniform means that the hot-end coating and / or the (one or more) metal oxides comprised by the hot-end coating have a visually uniform appearance. According to one embodiment, the hot-end coating forms a continuous or discontinuous film when and / or after a composition comprising a metal organic salt is applied to a hot glass substrate.

[0052] According to one embodiment, the cold-end coating can adhere to the hot-end coating comprising (one or more) metal oxides.

[0053] Coated glass products:

[0054] There is provided a coated glass substrate produced by the method disclosed herein. The coated glass article comprises:

[0055] a glass substrate and

[0056] a hot-end coating on the glass substrate,

[0057] the hot-end coating comprises at least one or a combination of Group 3A oxides and Group 4A oxides; preferably TiO2, TiO, Ti2O3, Ti z O a (0 < z ≤ 2 and 0 < a ≤ 3), ZrO2, Zr b O c (0 < b ≤ 1 and 0 < c ≤ 2), Al2O3, Al2O, AlO, Alx O y (0 < x ≤ 2 and 0 < y ≤ 3), or a combination thereof; more preferably Al2O3, Al2O, AlO, Al x O y (0 < x ≤ 2 and 0 < y ≤ 3) or a combination thereof, most preferably Al x O y (0 < x ≤ 2 and 0 < y ≤ 3).

[0058] According to one embodiment, the hot-end coating is substantially free of halides, preferably substantially free of Cl. As used herein, substantially free means that based on the weight of the hot-end coating, the content of halides is less than 1 wt%, or less than 5000 ppm, or less than 1000 ppm, or less than 500 ppm, or less than 100 ppm, or less than 50 ppm, or less than 10 ppm. According to one embodiment, deionized water can be used to form a composition containing a metal organic salt. According to one embodiment, tap water can be used to form a composition containing a metal organic salt. According to one embodiment, the hot-end coating is substantially free of carbon. According to certain embodiments, the hot-end coating may be substantially free of metals other than aluminum. Substantially free means that based on the weight of the hot-end coating, the content of metals other than aluminum is less than 1 wt%, or less than 5000 ppm, or less than 1000 ppm, or less than 500 ppm, or less than 100 ppm, or less than 50 ppm, or less than 10 ppm.

[0059] According to one embodiment, the hot-end coating contains Al x O y (0 < x ≤ 2 and 0 < y ≤ 3), Al2O3, Al2O, AlO, Al x O y (0 < x ≤ 2 and 0 < y ≤ 3), at least one of γAl2O3 or a combination thereof; more preferably Al2O3, Al2O, AlO, Al x O y (0 < x ≤ 2 and 0 < y ≤ 3) or a combination thereof; most preferably Al x O y (0 < x ≤ 2 and 0 < y ≤ 3); and the coating is substantially free of metals other than aluminum. Substantially free means that based on the weight of the hot-end coating, the content of metals other than aluminum is less than 1 wt%, or less than 5000 ppm, or less than 1000 ppm, or less than 500 ppm.

[0060] According to one embodiment, the coated glass article further includes a cold-end coating on the hot-end coating.

[0061] According to one embodiment, the coated glass article includes at least one of a hollow glass container, a bottle, or a flat glass.

[0062] Emissions from the coating process:

[0063] According to one embodiment, the coating process results in the release (emission) of substantially only water. As used herein, "substantially only water" means that the emission of halogen and / or carbon resulting from the coating process is < 10%, or

[0064] < 5%, < 3%, < 2%, < 1%, < 0.5%, based on the weight of the aqueous dispersion composition (applied to the hot surface of the glass substrate to produce a hot-end coating of metal oxide on the surface of the glass substrate).

[0065] Exemplary aspects of the present invention can be summarized as follows.

[0066] Aspect 1: A method for coating a glass substrate with a hot-end coating, comprising:

[0067] a) applying a composition comprising at least one metal organic salt to the surface of the glass substrate, the temperature of the surface being from about 450 °C to about 800 °C, thereby forming a hot-end coating on the glass substrate, the hot-end coating preferably being an inorganic coating;

[0068] wherein, after application, the hot-end coating comprises a metal oxide or a combination thereof.

[0069] Aspect 2: The method according to aspect 1, wherein the composition comprising the metal organic salt is in the form of an aqueous composition.

[0070] Aspect 3: The method according to aspect 1 or aspect 2, wherein the metal organic salt comprises at least one of a Group 3A C1-C10 organic salt, a Group 4 C1-C10 organic salt or a combination thereof; preferably titanium stearate, titanium lactate, titanium formate, titanium acetate, zirconium stearate, zirconium lactate, zirconium formate, zirconium acetate, aluminum stearate, aluminum lactate, aluminum formate, aluminum acetate or a combination thereof; more preferably titanium lactate, zirconium lactate, aluminum lactate or a combination thereof; most preferably aluminum lactate; and / or

[0071] wherein, after application, the hot-end coating comprises a metal oxide, the metal oxide comprising at least one of a Group 3A oxide, a Group 4A oxide or a combination thereof; preferably Al x O y (0 < x ≤ 2 and 0 < y ≤ 3), TiO2, TiO, Ti2O3, Ti z O a (0 < z ≤ 2 and 0 < a ≤ 3), ZrO2, Zr b O c (0 < b ≤ 1 and 0 < c ≤ 2), Al2O3, Al2O, AlO, Al x O y (0 < x ≤ 2 and 0 < y ≤ 3), or a combination thereof; more preferably Al2O3, Al2O, AlO, Alx O y (0 < x ≤ 2 and 0 < y ≤ 3), or a combination thereof; most preferably Al x O y (0 < x ≤ 2 and 0 < y ≤ 3).

[0072] Aspect 4: The method according to any one of Aspects 1 - 3, wherein the pH of the composition is less than about 8, preferably about 1 to about 7, more preferably about 2 to about 7, even more preferably about 3 to about 7, and most preferably about 3 - 5.

[0073] Aspect 5: The method according to any one of Aspects 1 - 4, wherein the composition comprises from about 1 to about 80% by weight, preferably from about 5 to about 70% by weight, and most preferably from about 10 to about 60% by weight of a metal - organic salt based on the weight of the composition.

[0074] Aspect 6: The method according to any one of Aspects 1 - 5, wherein the composition further comprises at least one salt, preferably aluminum nitrate (Al(NO3)3), or aluminum sulfate (Al2(SO4)3), or a combination thereof.

[0075] Aspect 7: The method according to any one of Aspects 1 - 6, further comprising:

[0076] b) optionally cooling the glass substrate and the hot - side coating to a temperature of about 80°C to about 350°C, preferably about 100°C to about 250°C, more preferably about 100°C to about 200°C; and

[0077] c) applying a cold - side coating composition onto the hot - side coating to provide a cold - side coating on the hot - side coating.

[0078] Aspect 8: The method according to any one of Aspects 1 - 7, wherein the composition is in the form of an aqueous solution and the aqueous solution is applied by spraying, optionally using a sprayer, and the optional solution pressure is about 1 to about 250 psi, or about 2 to about 100 psi, or about 2 to about 70 psi, or about 10 to about 30 psi.

[0079] Aspect 9: The method according to any one of Aspects 1 - 8, wherein the composition is applied by a chemical vapor deposition (CVD) process at about atmospheric pressure.

[0080] Aspect 10: The method according to any one of Aspects 1, 3 - 7, and 9, wherein the composition is in the form of a particulate solid powder and the composition is applied by spraying or using gas to blow the composition.

[0081] Aspect 11: The method according to any one of Aspects 1 - 10, wherein the hot - side coating is substantially free of halides, preferably substantially free of Cl.

[0082] Aspect 12: The method according to any one of aspects 1 - 11, wherein the hot-end coating comprises at least one of Group 3A oxides and Group 4A oxides or a combination thereof; preferably TiO2, TiO, Ti2O3, Ti z O a (0 < z ≤ 2 and 0 < a ≤ 3), ZrO2, Zr b O c (0 < b ≤ 1 and 0 < c ≤ 2), Al2O3, Al2O, AlO, Al x O y (0 < x ≤ 2 and 0 < y ≤ 3), or a combination thereof; more preferably Al2O3, Al2O, AlO, Al x O y (0 < x ≤ 2 and 0 < y ≤ 3), or a combination thereof; most preferably Al x O y (0 < x ≤ 2 and 0 < y ≤ 3).

[0083] Aspect 13: The method according to any one of aspects 8 - 14, wherein the cold-end coating is applied onto the hot-end coating.

[0084] Aspect 14: The method according to any one of aspects 1 - 13, wherein the hot-end coating is substantially transparent, colorless, and / or non-iridescent to the naked eye.

[0085] Aspect 15: The method according to any one of aspects 1 - 14, wherein the hot-end coating is uniform.

[0086] Aspect 16: The method according to any one of aspects 1 - 15, wherein the composition further comprises one or more of a wetting agent, a surfactant, a viscosity modifier, a preservative, a stabilizer, a co-solvent, and / or an antibacterial additive.

[0087] Aspect 17: A coated glass substrate prepared by the method according to any one of aspects 1 - 16.

[0088] Aspect 18: A coated glass article comprising:

[0089] a glass substrate and

[0090] a hot-end coating on the glass substrate,

[0091] wherein the glass substrate comprises SiO2 (silicon dioxide), and the hot-end coating comprises at least one of Group 3A oxides and Group 4A oxides or a combination thereof; preferably TiO2, TiO, Ti2O3, Ti z O a (0 < z ≤ 2 and 0 < a ≤ 3), ZrO2, Zr b Oc (0 < b ≤ 1 and 0 < c ≤ 2), Al2O3, Al2O, AlO, Al x O y (0 < x ≤ 2 and 0 < y ≤ 3), or a combination thereof; more preferably Al2O3, Al2O, AlO, Al x O y (0 < x ≤ 2 and 0 < y ≤ 3), or a combination thereof; most preferably Al x O y (0 < x ≤ 2 and 0 < y ≤ 3).

[0092] Aspect 19: The coated glass article according to aspect 18, wherein the hot-end coating is substantially free of halides, preferably substantially free of Cl.

[0093] Aspect 20: The coated glass article according to aspect 18 or aspect 19, further comprising a cold-end coating on the hot-end coating.

[0094] Aspect 21: The coated glass article according to any one of aspects 18 - 20, wherein the coated glass article comprises at least one of a hollow glass container or a flat glass.

[0095] In this specification, the embodiments have been described in a manner that enables a clear and concise description, but it is intended and should be understood that the embodiments can be combined or separated in various ways without departing from the present invention. For example, it should be understood that all the preferred features described herein apply to all aspects of the present invention described herein.

[0096] In some embodiments, the invention herein can be construed as not including any element or process step that does not materially affect the basic and novel characteristics of the composition, the method of making the composition, the method of using the composition, and the article prepared from the composition. Additionally, in some embodiments, the present invention can be construed as not including any element or method not specified herein.

[0097] Although the present invention has been shown and described herein with reference to specific embodiments, the present invention is not intended to be limited to the details shown. Instead, various modifications can be made in the details within the scope of equivalents of the claims without departing from the present invention.

[0098] Examples

[0099] method :

[0100] The temperature of the glass substrate was measured by a pyrometer (the emissivity of the coated soda-lime glass surface was 0.95).

[0101] Scanning electron microscope measurements were performed using a Hitachi SU 8010 instrument.

[0102] First, a 20 wt% aqueous solution of aluminum lactate was prepared. The aluminum lactate solution was prepared by slowly adding aluminum to deionized water to prepare an aqueous solution containing 20 wt% (based on the weight of the aqueous solution) of aluminum lactate. During the preparation, the solution was continuously stirred, even after the aluminum lactate was completely dissolved in the water. A piece of clean soda-lime glass was annealed on a hot plate to a temperature above 400°C (530°C to 540°C), as measured using a pyrometer. When the glass temperature reached 400°C or higher (i.e., 530°C to 540°C), the prepared aqueous solution was sprayed onto the hot glass surface 1-3 times using a spray gun (Grex, Model Tritium) equipped with a crown nozzle. The air pressure in the spray gun was varied between 10 and 40 psi. After applying the aqueous solution, the glass substrate and its hot end coating were cooled to 125°C. The coating was transparent, colorless, and had no iridescence. When the glass substrate and its hot end coating reached 125℃, the wax emulsion cold end coating was sprayed on the hot end coating using the same spray gun at 15psi air pressure (nozzle fully open). RP-40, Arkema).

[0103] The metal oxide coating can be in the form of "islands" substantially uniformly distributed on the surface of the soda-lime glass substrate. The composition of these islands can be substantially homogeneous or heterogeneous. The volume average particle size of these islands can be the volume average particle size of the metal oxide layer. The metal oxide coating can form a continuous film.

Claims

1. A method of coating a glass substrate with a hot end coating, comprising: a) applying a composition comprising at least one metal organic salt to a surface of a glass substrate, said surface having a temperature of about 450° C. to about 800° C., thereby forming a hot end coating on the glass substrate, said hot end coating being preferably an inorganic coating; Wherein, after application, the hot end coating comprises a metal oxide or a combination thereof.

2. The method of claim 1, wherein the composition comprising the metal organic salt is an aqueous composition.

3. The method of claim 1 or claim 2, wherein the metal organic salt comprises at least one of a Group 3A C1-C10 organic salt, a Group 4 C1-C10 organic salt, or a combination thereof; preferably titanium stearate, titanium lactate, titanium formate, titanium acetate, zirconium stearate, zirconium lactate, zirconium formate, zirconium acetate, aluminum stearate, aluminum lactate, aluminum formate, aluminum acetate, or a combination thereof; more preferably titanium lactate, zirconium lactate, aluminum lactate, or a combination thereof; most preferably aluminum lactate; and / or in, After application, the hot-end coating includes metal oxides, the metal oxides comprising at least one of Group 3A oxides and Group 4A oxides, or a combination thereof; preferably Al x O y (0 < x ≤ 2 and 0 < y ≤ 3), TiO2, TiO, Ti2O3, Ti z O a (0 < z ≤ 2 and 0 < a ≤ 3), ZrO2, Zr b O c (0 < b ≤ 1 and 0 < c ≤ 2), Al2O3, Al2O, AlO, or a combination thereof; more preferably Al2O3, Al2O, AlO, Al x O y [[ID=十六]](0 < x ≤ 2 and 0 < y ≤ 3), or a combination thereof; most preferably γAl2O3.

4. The method of any one of claims 1 to 3, wherein the pH of the composition is less than about 8, preferably about 1 to about 7, more preferably about 2 to about 7, even more preferably about 3 to about 7, and most preferably about 3 to about 5.

5. The method of any one of claims 1 to 4, wherein the composition comprises from about 1 to about 80 weight percent, preferably from about 5 to about 70 weight percent, and most preferably from about 10 to about 60 weight percent of the metal organic salt, based on the weight of the composition.

6. The method of any one of claims 1 to 5, wherein the composition further comprises at least one salt, preferably aluminum nitrate (Al(NO3)3), or aluminum sulfate (Al2(SO4)3), or a combination thereof.

7. The method of any one of claims 1 to 6, further comprising: b) optionally cooling the glass substrate and the hot end coating to a temperature of about 80° C. to about 350° C., preferably about 100° C. to about 250° C., more preferably about 100° C. to about 200° C.; and c) applying a cold end coating composition onto the hot end coating.

8. The method of any one of claims 1 to 7, wherein the composition is an aqueous solution applied by spraying, optionally at a solution pressure of about 10 to about 250 psi, or about 2 to about 100 psi, or about 2 to about 70 psi, or about 10 to about 30 psi.

9. The method of any one of claims 1 to 8, wherein the composition is applied by a chemical vapor deposition (CVD) process at about atmospheric pressure.

10. The method of any one of claims 1, 3-7 and 9, wherein the composition is in solid form, preferably granules and / or powder, and the composition is applied by spraying or blowing the composition using a gas.

11. The method of any one of claims 1 to 10, wherein the hot end coating is substantially free of halides, preferably substantially free of Cl.

12. The method according to any one of claims 1-11, wherein the hot-end coating comprises at least one of Group 3A oxides and Group 4A oxides, or a combination thereof; preferably TiO2, TiO, Ti2O3, Ti z O a (0 < z ≤ 2 and 0 < a ≤ 3), ZrO2, Zr b O c (0 < b ≤ 1 and 0 < c ≤ 2), Al2O3, Al2O, AlO, Al x O y (0 < x ≤ 2 and 0 < y ≤ 3), or a combination thereof; more preferably Al2O3, Al2O, AlO, Al x O y (0 < x ≤ 2 and 0 < y ≤ 3), or a combination thereof; most preferably γAl2O3.

13. The method of any one of claims 8-14, wherein a cold end coating is applied to the hot end coating adhered to the coated glass surface.

14. The method of any one of claims 1 to 13, wherein the hot end coating is transparent, colorless, and / or non-iridescent to the naked eye.

15. The method of any one of claims 1-14, wherein the hot end coating is uniform.

16. The method of any one of claims 1-15, wherein the composition further comprises one or more of a wetting agent, a surfactant, a viscosity modifier, a preservative, a stabilizer, a co-solvent, and / or an antimicrobial additive.

17. A coated glass substrate prepared by the method according to any one of claims 1 to 16.

18. A coated glass article comprising: Glass substrate and Hot end coating on glass substrate, wherein the glass substrate includes SiO2 (silicon dioxide), and the hot-end coating contains at least one of Group 3A oxides and Group 4A oxides, or a combination thereof; preferably TiO2, TiO, Ti2O3, Ti z O a (0 < z ≤ 2 and 0 < a ≤ 3), ZrO2, Zr b O c (0 < b ≤ 1 and 0 < c ≤ 2), Al2O3, Al2O, AlO, Al x O y (0 < x ≤ 2 and 0 < y ≤ 3), or a combination thereof; more preferably Al2O3, Al2O, AlO, Al x O y (0 < x ≤ 2 and 0 < y ≤ 3), or a combination thereof; most preferably γAl2O3.

19. The coated glass article of claim 18, wherein the hot end coating is substantially free of halides, preferably substantially free of Cl.

20. The coated glass article of claim 18 or claim 19, further comprising a cold end coating on the hot end coating.

21. The coated glass article of any one of claims 18-20, wherein the coated glass article comprises at least one of a hollow glass container or flat glass.