Visible-light-responsive photoactive coating, coated article, and method of making same
Abstract
The present invention provides a photoactive coating for forming a light absorption band in the visible region of the electromagnetic spectrum. The method includes depositing the precursor composition onto at least a portion of the float glass ribbon in the molten metal bath through a CVD coating device. The precursor composition includes a titanium dioxide precursor material and at least one selected from chromium (Cr), vanadium (V), manganese (Mn), copper (Cu), iron (Fe), magnesium (Mg), scandium (Sc), Yttrium (Y), niobium (Nb), molybdenum (Mo), ruthenium (Ru), tungsten (W), silver (Ag), lead (Pb), nickel (Ni), rhenium (Re), and other mixtures thereof Precursor material.
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Projected expiry passed 12 July 2022, 4.2 years ago.
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42 claims: 4 independent, 38 dependent
- 1一种形成涂层的方法,包括步骤:将前体组合物通过CVD涂覆设备沉积到至少一部分基材表面上,所述前体组合物包含:(a)金属氧化物前体材料;和(b)光吸收带改变前体材料。
- 2权利要求1的方法,其中金属氧化物前体材料是二氧化钛前体材料。
- 3权利要求2的方法,其中二氧化钛前体材料选自四氯化钛,钛醇盐,和其混合物。
- 4权利要求3的方法,其中二氧化钛前体材料选自异丙醇钛和四乙醇钛。
- 5权利要求1的方法,其中所述材料(b)包括选自铬(Cr),钒(V),锰(Mn),铜(Cu),铁(Fe),镁(Mg),钪(Sc),钇(Y),铌(Nb),钼(Mo),钌(Ru),钨(W),银(Ag),铅(Pb),镍(Ni),铼(Re),和其混合物或组合的至少一种金属。
- 6权利要求1的方法,其中所述材料(b)设计成改变涂层的光吸收带以包括不在没有材料(b)的涂层的光吸收带中的至少一部分可见电磁波谱。
- 7权利要求1的方法,其中所述材料(b)设计成改变涂层的光吸收带以包括至少一个在400nm-800nm范围内的波长。
- 8权利要求1的方法,其中所述材料(b)至少部分可溶于材料(a)。
- 9权利要求1的方法,其中所述基材是浮法玻璃带和所述方法包括将前体材料沉积到浮法玻璃带上。
- 10权利要求1的方法,其中所述基材是在熔融金属浴中的浮法玻璃带和所述方法包括将前体材料沉积到金属浴中的浮法玻璃带上。
- 11权利要求9的方法,其中浮法玻璃带位于熔融金属浴和退火炉之间。
- 12权利要求1的方法,其中涂层在暴露于在400nm-800nm范围内的电磁能量时是光催化的。
- 13权利要求1的方法,其中涂层在暴露于在400nm-800nm范围内的电磁能量时是光活性亲水的。
- 14一种形成其光吸收带包括电磁波谱的至少一部分可见区域的光活性涂层的方法,包括步骤:通过CVD涂覆设备将前体组合物沉积到熔融金属浴中的至少一部分浮法玻璃带上,所述前体组合物包含:二氧化钛前体材料;和具有选自铬(Cr),钒(V),锰(Mn),铜(Cu),铁(Fe),镁(Mg),钪(Sc),钇(Y),铌(Nb),钼(Mo),钌(Ru),钨(W),银(Ag),铅(Pb),镍(Ni),铼(Re),和其混合物的金属的至少一种其它前体材料。
- 15权利要求12的方法,其中二氧化钛前体材料选自四氯化钛和钛醇盐。
- 16权利要求15的方法,其中二氧化钛前体材料选自异丙醇钛和四乙醇钛。
- 17权利要求14的方法,包括将基材加热至足以使二氧化钛前体材料和其它前体材料分解形成光活性涂层的温度。
- 18权利要求14的方法,其中光活性涂层在暴露于400nm-800nm的电磁能量时是光催化的。
- 19权利要求14的方法,其中光活性涂层在暴露于400nm-800nm的电磁能量时是光活性亲水的。
- 20权利要求14的方法,包括沉积足够的前体组合物使得光催化涂层具有厚度约50埃-约2000埃。
- 21权利要求14的方法,包括在所述带和光催化涂层之间沉积中间层。
- 22权利要求21的方法,其中中间层是抗反射层。
- 23权利要求22的方法,其中抗反射层包含氧化铝,氧化锡,氧化铟,氧化硅,氧碳化硅,和氧氮化硅中至少一种。
- 24权利要求21的方法,其中中间层是钠离子扩散阻挡层。
- 25权利要求24的方法,其中阻挡层包括氧化硅,氮化硅,氧氮化硅,氧碳化硅,氧化铝,氟掺杂氧化铝,氮化铝,和其混合物中至少一种。
- 26一种制品,包括:具有至少一个表面的基材;和沉积到至少一部分该基材表面上的涂层,其中该涂层包含二氧化钛和选自铬(Cr),钒(V),锰(Mn),铜(Cu),铁(Fe),镁(Mg),钪(Sc),钇(Y),铌(Nb),钼(Mo),钌(Ru),钨(W),银(Ag),铅(Pb),镍(Ni),铼(Re),和其混合物中至少一种的其它的材料,和其中涂层通过化学气相沉积沉积到基材上。
- 27权利要求26的制品,其中基材选自玻璃,塑料,和陶瓷。
- 28权利要求26的制品,其中制品是绝热玻璃单元和基材是绝热玻璃单元的至少一个窗格。
- 29权利要求26的制品,其中基材选自退火玻璃,回火玻璃,和热增强玻璃。
- 30权利要求26的制品,其中制品是建筑上的透明体。
- 31权利要求26的制品,其中涂层直接在基材表面上沉积。
- 32权利要求26的制品,其中涂层包含至少部分为锐钛矿相的二氧化钛。
- 33权利要求26的制品,其中涂层包含至少部分为金红石相的二氧化钛。
- 34权利要求26的制品,其中基材包括至少一个其中扩散有锡的表面。
- 35权利要求26的制品,其中涂层具有厚度约50埃-约2000埃。
- 36权利要求26的制品,其中基材是浮法玻璃带。
- 37权利要求26的制品,包括位于基材表面和涂层之间的至少一中间层。
- 38权利要求37的制品,其中中间层是抗反射层。
- 39权利要求37的制品,其中中间层是钠离子扩散阻挡层。
- 40权利要求38的制品,其中抗反射层包含氧化铝,氧化锡,氧化铟,氧化硅,氧碳化硅,氧氮化硅,和其混合物中至少一种。
- 41权利要求39的制品,其中阻挡层包含氧化锡,氧化硅,氧化钛,氧化锆,氟-掺杂氧化锡,氧化铝,氧化镁,氧化锌,氧化钴,氧化铬,氧化铁,和其混合物中至少一种。
- 42一种形成涂层的方法,包括步骤:将钠离子扩散阻挡层沉积到至少一部分基材上;将光活性涂层沉积到至少一部分阻挡层上;和通过离子注入将至少一种所选金属注入光活性涂层以形成吸收带包括至少一个在400nm-800nm范围内的波长的光活性涂层。
Independent claims42
52 paragraphs, as filed
Visible light-responsive photoactive coating, coated product, and preparation method thereof
Cross-reference to related applications. This application is a partial continuation of U.S. Application No. 10/075,316 (Greenberg et al., entitled "Photocatalytically activated self-cleaning appliances", filed on February 14, 2002), the latter being in April 1999 Divisional of U.S. Application No. 09/282,943 (now U.S. Patent No. 6,413,581) filed on the 1st, the latter being the division of U.S. Application No. 08/899,257 (now U.S. Patent No. 6,027,766) filed on July 23, 1997 The latter claims the priority of U.S. Provisional Application Serial No. 60/040,566 filed on March 14, 1997, and all applications are hereby fully incorporated by reference into the present invention. This application also claims the priority of U.S. Provisional Application Serial No. 60/305,057 filed on July 13, 2001, which is also fully incorporated herein by reference.
1. Field of the present invention The present invention relates to a method of depositing a photoactive coating on a substrate (eg, a glass sheet or continuous float glass ribbon) to produce a photocatalytic and/or photoactive coating that exhibits photoactivity when irradiated with visible light. Water coating methods, and products made according to these methods.
2. Technical issues For many substrates, such as glass substrates such as architectural windows, automotive glass, and aircraft windows, it is ideal for good visibility that the surface of the substrate is basically free of surface contamination for the longest possible duration. Such as common organic and inorganic surface contaminants. Usually, this means that these surfaces are cleaned frequently. This cleaning operation is usually performed by manually wiping the surface with or without the help of chemical cleaning solutions. The solution is labor, time, and/or cost intensive. Therefore, there is a need for substrates with surfaces that are easier to clean than existing glass substrates, especially glass substrates, so as to reduce the need or frequency of these manual cleanings.
Some semiconducting metal oxides are known to provide photoactive (hereinafter "PA") coatings. The term "photoactive" or "photoactively" refers to the photogenerating effect of a hole-electron pair when irradiated with radiation having a specific frequency, usually ultraviolet ("UV") light. Above certain minimum thicknesses, these PA coatings are generally photocatalytic (hereinafter "PC"). "Photocatalysis" refers to a coating with self-cleaning properties, that is, when the coating is exposed to certain electromagnetic radiation, such as UV, it interacts with organic pollutants on the surface of the coating to degrade or decompose the organic pollutants. In addition to their self-cleaning properties, these PC coatings are also generally hydrophilic, that is, they are wetted by water with a water contact angle of generally less than 20 degrees. The hydrophilicity of the PC coating helps reduce fogging, that is, the accumulation of water droplets on the coating, and fogging reduces the visibility of visible light through and through the coated substrate.
The problem with these conventional PC coatings is that they are generally only photoactive or photocatalytic when exposed to ultraviolet (UV) light with a wavelength shorter than about 380 nanometers (nm). This means that the PC coating only uses about 3%-5% of the solar energy reaching the earth, which makes it necessary to use a UV light source (such as conventional mercury or ultraviolet lamps) to provide sufficient energy for photocatalysis.
In order to solve this problem, attempts have been made to modify conventional PC coatings to shift the light absorption band of the coating from the UV region of the electromagnetic spectrum to the visible region (400nm-800nm). For example, US Patent No. 6,077,492 to Anpo et al. discloses a method of shifting the light absorption band of a titanium oxide photocatalyst from the UV region to the visible light region by implanting high-energy ions of selected metal ions into the photocatalyst. Subsequent studies on the ion implantation method have shown that the movement of the light absorption band to the visible region not only requires high-energy ion implantation, but also requires calcination of metal ion-implanted titanium oxide (Use of Visible Light. Second-Generation Titanium Oxide Photocatalysts Prepared). By the Application of AnAdvanced Metal Ion-Implantation Method (application of visible light. The second generation of titanium oxide photocatalyst made by applying advanced metal ion implantation method), M.Anpo, PureAppl.Chem., Vol.72, No.9 , Pp.1787-1792(2000)). EP 1,066,878 discloses a sol-gel method in which titanium dioxide is doped with a small amount of selected metal ions to move the light absorption band of titanium dioxide to the visible region.
However, these ion implantation and sol-gel coating methods are economically or practically unsuitable for certain use conditions or substrates. For example, in the conventional float glass process, the float glass ribbon in the molten metal bath is too hot to accept the sol due to the evaporation or chemical reaction of the solvent used for the sol. Conversely, if the sol is applied to a substrate below the specific temperature used to form the catalyst in crystalline form, the sol-coated substrate is reheated. Reheating to a temperature sufficient to calcinate the coating or form a crystalline photocatalyst may require considerable investment in equipment, energy, and processing costs, and thus may significantly reduce production efficiency. In addition, the sodium-containing substrate, such as soda lime glass, is reheated to a temperature sufficient to calcinate the coating, which increases the possibility of sodium ions in the substrate to migrate to the coating. This migration can lead to what is commonly referred to as "sodium ion poisoning" of the deposited coating. These sodium ions can reduce or destroy the photocatalytic activity of the PC coating. In addition, ion implantation and sol-gel methods generally produce thick coatings, eg, a few microns thick, which can adversely affect the optical and/or aesthetic properties of the coated article. Generally, as the thickness of the PC coating increases, the transmittance and reflectance of the coating experience a series of minimum and maximum values due to optical interference effects. The reflection and transmission colors of the coating also change due to these optical effects. Therefore, coatings thick enough to provide the required self-cleaning properties may have undesirable optical properties.
Therefore, it is advantageous to provide a method for manufacturing a PA coating having light absorption in the visible region that is compatible with the conventional float glass process and/or to reduce or eliminate at least some of the above-mentioned defects.
The summary of the present invention provides a method for forming a coating by depositing a precursor composition on at least a part of the surface of a substrate by a CVD coating device. The precursor composition includes a photoactive coating precursor material, such as a metal oxide or semiconducting metal oxide precursor material, and a light absorption band change precursor material. In one embodiment, the coating is deposited on a ribbon of float glass in a bath of molten metal. In another embodiment, the coating is deposited on the float glass ribbon after leaving the molten metal bath but before entering the heat treatment equipment, such as an annealing furnace. The resulting coating leads at least to the hydrophilicity of the coating on the substrate, such as photoactive hydrophilicity, but also results in photocatalytic activity sufficient to become a photocatalytic coating.
Another method of forming a photoactive coating having a light absorption band in the visible region of the electromagnetic spectrum includes depositing a precursor composition onto at least a portion of the float glass ribbon in a molten metal bath by a CVD coating device. The precursor composition includes at least one titanium dioxide precursor material. In one embodiment, the titanium dioxide precursor material includes titanium and oxygen, such as alkoxides such as but not limited to titanium methoxide, titanium ethoxide, titanium propoxide, titanium butoxide, and the like or isomers thereof, such as but not limited to Limited to titanium isopropoxide, titanium tetraethoxide, and the like. In another embodiment, the titanium dioxide precursor material comprises titanium tetrachloride. The precursor composition also includes at least one material selected from the group consisting of chromium (Cr), vanadium (V), manganese (Mn), copper (Cu), iron (Fe), magnesium (Mg), scandium (Sc), yttrium (Y) ), niobium (Nb), molybdenum (Mo), ruthenium (Ru), tungsten (W), silver (Ag), lead (Pb), nickel (Ni), rhenium (Re), or one or more of them Any mixture or combination of other precursor materials. In one embodiment, the other precursor materials may be oxides, alkoxides, or mixtures thereof. All root mean square roughness values are those that can be determined by atomic force microscopy by measuring root mean square (RMS) roughness on a surface area of 1 square micrometer. In addition, any mention of "incorporating the present invention herein" shall be understood as fully incorporating the present invention.
Another method of the present invention includes depositing a sodium ion diffusion barrier layer on at least a portion of the substrate, depositing a photoactive coating on the barrier layer, and implanting one or more selected metal ions into the photoactive layer by ion implantation. Coating to form a photoactive coating having an absorption band including at least one wavelength in the range of 400nm-800nm.
The article of the present invention includes a substrate having at least one surface and a coating layer deposited on at least a portion of the surface of the substrate. The coating includes a photoactive coating material, such as titanium dioxide, and at least one selected from chromium (Cr), vanadium (V), manganese (Mn), copper (Cu), iron (Fe), magnesium (Mg), scandium (Sc), yttrium (Y), niobium (Nb), molybdenum (Mo), ruthenium (Ru), tungsten (W), silver (Ag), lead (Pb), nickel (Ni), rhenium (Re), or Other materials including any mixture or combination of one or more of them. In one embodiment, the coating is deposited on the substrate by chemical vapor deposition.
Description of the drawings Figure 1 is a cross-sectional view (not to scale) of a part of the substrate on which the photoactive coating of the present invention is deposited; Figure 2 is used to apply the photoactive metal oxide coating of the present invention to float The side view of the coating process on the glass ribbon in the molten metal bath of the French glass process (not to scale); and Figure 3 is the side view of the insulating glass unit incorporating the features of the present invention (not to scale).
Description of the present invention The spatial or directional terms used herein, such as "inner", "outer", "above", "below", "top", "bottom", etc., refer to the present invention as shown in the accompanying drawings. However, it can be understood that the present invention can present various alternative orientations, and therefore, these terms should not be considered as limiting. In addition, all numbers representing dimensions, physical properties, process parameters, component amounts, reaction conditions, etc. used in the specification and claims should be understood as being modified by the term "about" in all cases. Therefore, unless stated to the contrary, the numerical values given in the following description and claims are approximate values that can be varied according to the required performance to be obtained by the present invention. At least, and not intended to limit the application of the principle of equivalence to the scope of the claims, each value should at least be interpreted according to the recorded significant figures and through the application of ordinary rounding techniques. In addition, all ranges disclosed herein should be understood to include any and all sub-ranges contained therein. For example, the range "1-10" should be considered to include any and all sub-ranges between (and inclusive) a minimum value of 1 and a maximum value of 10; that is, starting with a minimum value of 1 or more and ending with 10. All subranges ending or lower, for example, 5.5-10. In addition, the term "deposited on" or "provided on" as used herein refers to depositing or providing on a surface but not necessarily in surface contact. For example, the coating "deposited on the substrate" does not exclude the presence of one or more other coating films with the same or different composition between the deposited coating and the substrate. In addition, all percentages disclosed herein are "weight" unless expressed to the contrary. All root mean square roughness values are those that can be determined by atomic force microscopy by measuring root mean square (RMS) roughness on a surface area of 1 square micrometer. In addition, all mentions of "incorporating the present invention as a reference" are hereby understood as being fully incorporated into the present invention.
Referring now to Figure 1, an article 20 having the features of the present invention is shown. The article 20 includes a substrate 22 having a first surface 21 and a second surface 60. The substrate 22 does not limit the present invention and may be any material having any desired characteristics, such as an opaque or transparent substrate. "Transparent" means that the visible light transmittance is greater than 0% to 100%. "Opaque" means having a visible light transmittance of 0%. "Visible light" refers to electromagnetic energy having a wavelength of 400 nanometers (nm) to 800 nm. Examples of suitable substrates include, but are not limited to, plastic substrates (such as polyacrylate, polycarbonate, and polyethylene terephthalate (PET)); metal substrates; glazed or ceramic substrates Material; glass substrate; or a mixture or combination thereof. For example, the substrate may be conventional uncolored soda lime glass, ie "clear glass", or may be colored or otherwise colored glass, borosilicate glass, leaded glass, tempered, untempered , Annealed, or thermally strengthened glass. The glass can be of any kind, such as conventional float glass, flat glass, or float glass ribbon, and can have any optical properties, such as any value of visible transmission, ultraviolet transmission, infrared transmission, and/or total solar energy transmission Any composition. The types of glass suitable for the present invention are described in, for example, U.S. Patent Nos. 4,746,347; 4,792,536; 5,240,886; 5,385,872; and 5,393,593, but this is not considered to be limiting. For example, the substrate 22 can be a float glass tape, a glass lattice of a building window, a skylight, a window pane of a heat-insulating glass unit, a mirror, a shower door, glassware (such as a glass table top, or a glass cabinet, etc.), or Laminates for conventional car windshields, side or rear windows, car roofs, or aircraft glass windows, to name a few.
The photoactive modified (hereinafter "PM") coating 24 of the present invention can be deposited on at least a portion of the substrate 22, for example, on all or a portion of the main surface of the substrate 22, such as on all or a portion of the surface 21 or the surface 60 . In the embodiment given, the PM coating 24 is on the surface 21 as shown. The term "photoactive modified" as used herein refers to a material or coating that is photoactive and includes at least one additive or dopant that is used for mobile and / Or widen the light absorption band of the material. "Light absorption band" refers to the range of electromagnetic radiation absorbed by a material to make the material photoactive. The PM coating 24 can be photocatalytic, photoactive hydrophilic, or both. "Photoactive hydrophilic" refers to a coating in which the contact angle of water droplets on the coating decreases with time due to exposure of the coating to electromagnetic radiation in the light absorption band of the material. For example, the contact angle can be reduced to less than 15 degrees, such as a value of less than 10 degrees, after 60 minutes of exposure to radiation in the light absorption band of the material having an intensity of 24 W/m2 on the surface of the PM coating, and can vary. It becomes super-hydrophilic, for example, drops below 5 degrees. Although photoactive, the coating 24 need not be photocatalytic, so that it is self-cleaning, that is, it is not sufficiently photocatalytic to decompose the organic material on the coating surface within a reasonable or economically useful time. Such as grime.
The PM coating 24 of the present invention includes (1) a photoactive coating material and (2) an additive or dopant, which widens or shifts the light absorption band of the coating compared to a coating without the dopant material . The photoactive coating material (1) includes at least one metal oxide, such as, but not limited to, one or more metal oxides or semiconducting metal oxides, such as various titanium oxide, silicon oxide, aluminum oxide, iron oxide, Silver oxide, cobalt oxide, chromium oxide, copper oxide, tungsten oxide, zinc oxide, zinc oxide/tin oxide, strontium titanate, and mixtures thereof. Metal oxides may include metal oxides, super-oxides or suboxides. The metal oxide may be crystalline or at least partially crystalline. In an exemplary coating of the present invention, the photoactive coating material is titanium dioxide. Titanium dioxide exists in an amorphous form and three crystalline forms, namely, anatase, rutile and brookite crystalline forms. Anatase titanium dioxide is particularly useful because of its strong light activity, while also having excellent chemical resistance and excellent physical durability. However, the combination of rutile phase or anatase and/or rutile phase with brookite and/or amorphous phase is also acceptable for the present invention.
The light absorption band widening or shifting material (2) can broaden or shift the light absorption band of the resulting coating to at least partially expand into, or further expand into the visible region of the spectrum (ie, broaden or shift the light absorption band to include at least A wavelength in the range of 400nm-800nm that is not in the light absorption band of the coating without dopant material (2)). In an exemplary embodiment, the material (2) includes at least one of chromium (Cr), vanadium (V), manganese (Mn), copper (Cu), iron (Fe), magnesium (Mg), scandium (Sc) , Yttrium (Y), niobium (Nb), molybdenum (Mo), ruthenium (Ru), tungsten (W), silver (Ag), lead (Pb), nickel (Ni), rhenium (Re), or any of them Any mixture or combination of one or more. The amount of material (2) present in the PM coating 24 is sufficient to widen or move the light absorption band of the coating 24 to at least partially expand into, or further expand into the visible area without adversely affecting the desired coating properties, such as, Reflectance, transmittance, color, etc. In addition, in the present invention, the material (2) does not have to be concentrated on or near the coating surface 21, but can be deposited such that it is dispersed or introduced into the body of the coating 24.
The PM coating 24 should be thick enough to provide an acceptable degree of photoactivity for the desired purpose, such as photocatalytic activity and/or photoactive hydrophilicity. There is no absolute value that makes the PM coating 24 "acceptable" or "unacceptable", because whether the PM coating 24 has an acceptable degree of photoactivity greatly depends on the purpose and conditions when the PM coated article is being used. And the selection of performance standards that match the purpose varies. However, the thickness required to achieve the photoactive hydrophilic PM coating 24 may be significantly lower than the thickness required to achieve a commercially acceptable level of photocatalytic self-cleaning activity. For example, in one embodiment, the PM coating 24 may have a thickness of 10 angstroms to 5000 angstroms, wherein a thicker coating in this range may have photocatalytic self-cleaning activity for at least a certain period of time, and hydrophilicity. As the coating becomes thinner within this range, the photocatalytic self-cleaning activity generally decreases in terms of performance and/or duration. As the thickness of the coating decreases in a range such as 50 angstroms to 3000 angstroms, such as 100 angstroms to 1000 angstroms, such as 200 angstroms to 600 angstroms, such as 200 angstroms to 300 angstroms, the photocatalytic self-cleaning activity may not be measurable but the photoactivity Hydrophilicity can still exist in the presence of selected electromagnetic radiation as within the light absorption band of the material.
In another aspect of the present invention, the outer surface 25 of the PM coating 24 of the present invention can be smoother than previous self-cleaning coatings, while still maintaining its photoactive hydrophilicity and/or photocatalytic activity. For example, the PM coating 24, especially the top or outer surface 25 of the coating, may have a diameter of less than 5 nm, such as less than 4.9 nm, such as less than 4 nm, such as less than 3 nm, such as less than 2 nm, such as Below 1nm, such as 0.3nm-0.7nm RMS surface roughness (even for the above range, such as thin coatings within 200 angstroms to 300 angstroms).
In another aspect of the invention, the PM coating 24 can become more dense than previously known hydrophilic, self-cleaning coatings. For example, the PM coating 24 may be substantially non-porous. "Substantially non-porous" means that the coating is dense enough so that the coating can withstand the conventional hydrofluoric acid test, in which a drop of 0.5% by weight (wt.%) hydrofluoric acid (HF) aqueous solution is placed on the coating at room temperature Top and cover with watch glass for 8 minutes (mins). The HF was then rinsed off and the coating was visually inspected for damage. Another HF immersion test is described in Industrial Engineering Chemistry & Research, Vol. 40, No. 1, page 26, 2001 (Charles Greenberg), which is incorporated herein by reference. The denser PM coating 24 of the present invention provides more protection against chemical attack to the underlying substrate than the previous more porous self-cleaning coating, and is harder than the previous self-cleaning coating using sol-gel And more scratch resistant.
The PM coating 24 can be directly deposited on the surface 21 of the substrate 22 shown in FIG. 1, that is, on the surface in contact therewith. Even for substrates containing sodium, such as soda lime glass, when the coating is applied by the following in-bath method, for example, the thin PM coating 24 of the present invention below 1000 angstroms should not change due to the sodium in the substrate. To be non-photoactive. Therefore, without using the sodium barrier layer between the glass and the PM coating 24 of the present invention, soda lime glass that can be cleaned more easily can be manufactured. If necessary, such a barrier layer can be used.
Alternatively, one or more other layers or coatings may be inserted between the PM coating 24 and the substrate 22. For example, the PM coating 24 may be the outer or outermost layer of a multi-layered coating that exists on the substrate 22 or the PM coating 24 may be embedded in such a multi-layered layer as one of the layers other than the outermost layer. Inside. "Outer layer" refers to a layer that receives sufficient excitation electromagnetic radiation, such as radiation within the light absorption band of the layer material, so as to provide sufficient photoactivity so that if it does not have to be photocatalytic, it is at least photoactive and hydrophilic. coating. In one embodiment, the PM coating 24 is the outermost coating on the substrate 22.
The PM coating 24 of the present invention can be formed on the substrate 22 by any conventional method, such as ion implantation, spray pyrolysis, chemical vapor deposition (CVD), or magnetron sputtering vacuum deposition (MSVD). In the ion implantation method, metal ions are injected into the coating by high-voltage acceleration. In the spray pyrolysis method, there are (1) metal oxide precursor materials, such as titanium dioxide precursor materials, and (2) at least one light absorption band change precursor material, that is, dopant materials (such as organic metal The organic or metal-containing precursor composition of the precursor material) is carried in an aqueous suspension, such as an aqueous solution, and directed to the surface of the substrate 22, while the substrate 22 is at a sufficiently high temperature to decompose the precursor composition And forming a PM coating 24 on the substrate 22. In the CVD method, the precursor composition is carried in a carrier gas, such as nitrogen, and directed toward the substrate 22. In the MSVD method, one or more metal-containing cathode targets are sputtered in an inert or oxygen-containing atmosphere under reduced pressure to deposit a sputter coating on the substrate 22. The substrate 22 may be heated during or after the coating process to crystallize the sputtered coating to form the PM coating 24. For example, one cathode can be sputtered to provide the metal oxide precursor material (1) and the other cathode can be sputtered to provide the dopant material (2). Alternatively, a single cathode that has been doped with the desired dopant material may be sputtered to form the PM coating 24.
Each method has advantages and limitations, depending on the required characteristics of the PM coating 24 and the type of glass manufacturing process. For example, in a conventional float glass process, molten glass is poured into a pool of molten metal (such as tin) in a bath of molten metal (such as tin) to form a continuous float glass ribbon. The temperature of the float glass ribbon in the tin bath is generally 1203°C (2200°F) (at the supply end of the bath) to 592°C (1100°F) (at the exit end of the bath). The float glass ribbon is taken out of the tin bath and annealed in an annealing furnace, that is, controlled cooling, and then cut into glass sheets having the desired length and width. The temperature of the float glass ribbon between the tin bath and the annealing furnace is generally 480°C (896°F) -580°C (1076°F) and the temperature of the float glass ribbon in the annealing furnace is generally 204°C (400°F) ) -557°C (1035°F) (peak). U.S. Patent Nos. 4,466,562 and 4,671,155 (herein incorporated by reference herein) provide a discussion of the float glass process.
CVD and spray pyrolysis methods are preferred over MSVD methods in float glass processes because they are more compatible with coating continuous substrates, such as float glass ribbons, at elevated temperatures. Exemplary CVD and spray pyrolysis coating methods are described in US Patent Nos. 4,344,986; 4,393,095; 4,400,412; 4,719,126; 4,853,257; and 4,971,843, which are incorporated herein by reference.
In the present invention, one or more CVD coating devices can be used at several points in the float glass ribbon manufacturing process. For example, the CVD coating device can be used when the float glass ribbon passes through the tin bath, after it leaves the tin bath, before it enters the annealing furnace, when it passes through the annealing furnace, or after it leaves the annealing furnace. Because the CVD method can coat float glass ribbons that are still subject to movement in the harsh environment associated with the manufacture of float glass ribbons, the CVD method is particularly suitable for providing a PM coating 24 on float glass ribbons in a molten tin bath. U.S. Patent Nos. 4,853,257; 4,971,843; 5,536,718; 5,464,657; 5,714,199; and 5,599,387 (herein incorporated by reference) describe CVD coatings that can be used in the present invention to coat float glass ribbons in molten tin baths Device and method.
For example, as shown in FIG. 2, one or more CVD applicators 50 may be located in the tin bath 52 above the molten tin pool 54. As the float glass ribbon 56 moves through the tin bath 52, the evaporated precursor composition (ie, the photoactive coating precursor material (1), such as the metal oxide precursor material, and the light absorption band changing material (2) For example, organometallic precursor materials) can be added to the carrier gas and on the top surface 21 of the guide belt 56. The precursor composition decomposes to form the PM coating 24 of the present invention. The material (2) can be at least partially soluble in the coating precursor material (1) under the required deposition conditions, such as completely soluble in the coating precursor material (1). Any required amount of material (2) to achieve the required movement of the light absorption band into the visible region can be added, mixed in, or dissolved in the coating precursor material (1). Alternatively, two separate precursors can be evaporated separately and combined.
Exemplary coating precursor materials (1) (eg, titanium dioxide precursor materials) that can be used in the present invention to form the titanium dioxide PM coating 24 by the CVD method include, but are not limited to, titanium oxides, suboxides, or Super-oxide. In one embodiment, the precursor material (1) may include one or more titanium alkoxides, such as but not limited to titanium methoxide, titanium ethoxide, titanium propoxide, titanium butoxide, and the like; or isomers thereof , Such as titanium isopropoxide, titanium tetraethoxide, and the like. Exemplary precursor materials suitable for the present invention include, but are not limited to, titanium tetraisopropoxide (Ti(OC3H7)4) (hereinafter "TTIP") and titanium tetraethoxide (Ti(OC2H5)4) (hereinafter "TTEt "). Alternatively, the titanium dioxide precursor material (1) may be titanium tetrachloride.
The light absorption band shifting material (2) can be any material that shifts or widens the light absorption band of the resulting coating to at least partially expand into, or further expand to the visible region (400nm-800nm) of the electromagnetic spectrum. The material may include one or more of chromium (Cr), vanadium (V), manganese (Mn), copper (Cu), iron (Fe), magnesium (Mg), scandium (Sc), yttrium (Y), niobium (Nb), molybdenum (Mo), ruthenium (Ru), tungsten (W), silver (Ag), lead (Pb), nickel (Ni), rhenium (Re), and/or any mixture or combination thereof. For example, the precursor material (2) may be a metal oxide or alkoxide. In one embodiment, the material (2) is at least partially soluble, eg, most of the precursor material (1) is soluble. Exemplary carrier gases that can be used in the CVD method of the present invention include, but are not limited to, air, nitrogen, oxygen, ammonia, and mixtures thereof. The concentration of the precursor composition in the carrier gas can vary with the specific precursor composition used. However, for a coating with a thickness of about 200 angstroms, it is expected that the concentration of the precursor composition in the carrier gas is usually 0.01% by volume to 0.1% by volume, for example, 0.01% by volume to 0.06% by volume, for example, 0.015% by volume to 0.06. % By volume; for example, 0.019% by volume -0.054% by volume. For thicker coatings, the precursor composition can be higher.
For the CVD method (and the spray pyrolysis method discussed below), the temperature during which the substrate 22 (such as float glass ribbon 56) forms the PM coating 24 thereon should be such that the metal-containing precursor composition decomposes and A coating having a desired amount of photoactivity, such as photocatalytic activity, photoactive hydrophilicity, or both, is formed. The lower limit of this temperature range is greatly affected by the decomposition temperature of the selected precursor composition. For the titanium-containing precursors described above, the lower limit of the temperature of the substrate 22 that provides sufficient decomposition of the precursor composition is generally in the range of 400°C (752°F) to 500°C (932°F). The upper limit of this temperature range is affected by the method of coating the coated substrate. For example, if the substrate 22 is a float glass ribbon 56 and the PM coating 24 is applied to the float glass ribbon 56 in the molten tin bath 50 during the manufacture of the float glass ribbon 56, the float glass ribbon 56 can reach more than 1000°C (1832°F) temperature. The float glass ribbon 56 can be thinned or changed in size (such as stretched or compressed) when the temperature exceeds 800°C (1472°F). If the PM coating 24 is applied to the float glass ribbon 56 before or during thinning, the PM coating 24 may crack or shrink accordingly when the float glass ribbon 56 is stretched or compressed. Therefore, the PM coating 24 can be applied when the float glass ribbon 56 is dimensionally stable (except for thermal shrinkage during cooling), for example, below 800°C (1472°F) (for soda lime glass), and makes the float glass ribbon 56 is at a temperature that decomposes metal-containing precursors, for example, over 400°C (752°F).
For spray pyrolysis, US Patent Nos. 4,719,126; 4,719,127; 4,111,150; and 3,660,061 (herein incorporated by reference herein) describe spray pyrolysis devices and methods that can be used in conventional float glass ribbon manufacturing processes. Although the spray pyrolysis method is very suitable for coating moving float glass ribbons like the CVD method, the spray pyrolysis has more complicated equipment than the CVD equipment and is usually used between the outlet end of the tin bath and the inlet end of the annealing furnace.
Exemplary metal-containing precursor compositions that can be used in the present invention to form PM coatings by spray pyrolysis methods include relatively water-insoluble organometallic reactants, especially metal acetylacetonates, which are spray-milled or wet-milled to particles The size is below 10 microns and is suspended in an aqueous medium through the use of chemical wetting agents. A suitable metal acetylacetonate precursor material for the formed PM coating containing titanium dioxide is titanyl acetylacetonate (TiO(C5H7O2)2). For example, the light absorption band changing material as described above can be mixed with or dissolved in the acetylacetonate precursor material. In one embodiment, the relative concentration of the metal acetylacetonate and the moving precursor material in the aqueous suspension is 5-40% by weight of the aqueous suspension. The wetting agent can be any relatively low foaming surfactant, including anionic, nonionic or cationic compositions. In one embodiment, the surfactant is non-ionic. The amount of wetting agent added is usually 0.24% by weight, but may be 0.01% to 1% or more. The aqueous medium can be distilled water or deionized water. Aqueous suspensions for pyrolytic deposition of metal-containing films are described in U.S. Patent No. 4,719,127, especially column 2, line 16 to column 4, line 48, which is incorporated herein by reference.
Those skilled in the art can understand that the bottom surface 60 of the float glass ribbon placed directly on the molten tin (usually referred to as the "tin side") has tin diffused in the surface, and the tin absorption pattern provided on the tin side is different. On the opposite surface 21 that is not in contact with the molten tin (usually referred to as the "air side"). The PM coating of the present invention can be formed on the air side of the float glass ribbon by the CVD method as described above while it is carried on the tin, and after it leaves the tin bath, it can be formed on the float glass by the CVD or spray pyrolysis method. The air side of the ribbon is formed, and/or is formed on the tin side of the float glass ribbon by a CVD method after it leaves the tin bath.
As an alternative to introducing oxygen in the atmosphere of the tin bath to form an oxide coating, the precursor composition may itself include one or more organic oxygen sources. The organic oxygen may be, for example, an ester or a carboxylic acid ester, such as an alkyl ester in which the alkyl group has β-hydrogen. Suitable esters may be alkyl esters with C2-C10 alkyl groups. Exemplary esters useful in the present invention are described in WO 00/75087, which is incorporated herein by reference.
For MSVD, U.S. Patent Nos. 4,379,040; 4,861,669; 4,900,633; 4,920,006; 4,938,857; 5,328,768; and 5,492,750 (herein incorporated by reference) describe the sputter coating of metal oxide films onto substrates (including glass substrates) ) On the MSVD device and method. The MSVD process is generally not suitable for providing a PM coating on the float glass ribbon during the manufacturing process, because among other reasons, the MSVD process requires pressure reduction during the sputtering operation, which makes it difficult to form a reduction on the continuously moving float glass ribbon. Pressure. However, the MSVD method can be used to deposit the PM coating 24 onto a substrate 22, such as a glass sheet. The substrate 22 can be heated to a temperature of 400°C (752°F) to 500°C (932°F), so that the MSVD sputter coating on the substrate crystallizes during the deposition process, which eliminates subsequent heating operations. Heating the substrate during the sputtering process is generally not a preferred method because the additional heating operation during the sputtering process can reduce throughput. Alternatively, the sputtered coating can be directly crystallized in the MSVD coating device without the need for post-heat treatment by using high-energy plasma, but again due to its tendency to reduce the throughput of the MSVD coater, this is not a preferred method.
An exemplary method using the MSVD method to provide PM coatings (especially PM coatings of 300 angstroms or less and having an RMS surface roughness of 2 nm or less) is to sputter the dopant-containing coating onto the substrate , Remove the coated substrate from the MSVD coater, and then heat-treat the coated substrate to crystallize the sputtered coating. For example, but not limiting the present invention, doped with at least one selected from chromium (Cr), vanadium (V), manganese (Mn), copper (Cu), iron (Fe), magnesium (Mg), scandium (Sc) , Yttrium (Y), niobium (Nb), molybdenum (Mo), ruthenium (Ru), tungsten (W), silver (Ag), lead (Pb), nickel (Ni), rhenium (Re), and/or The metal titanium target of the light absorption band moving material of the mixture or combination can be sputtered on the substrate 22 in an argon/oxygen atmosphere with 5-50% oxygen, such as 20% oxygen, at a pressure of 5-10 mTorr. Sputtering deposits a doped titanium dioxide coating with the desired thickness. The deposited coating did not crystallize. The coated substrate is removed from the coater and heated to a temperature of 400°C (752°F)-600°C (1112°F) for a sufficient time to promote the formation of a crystalline form of titanium dioxide to generate photoactivity. In one embodiment, the substrate is heated at a temperature of 400°C (752°F) to 600°C (1112°F) for at least 1 hour. If the substrate 22 is a glass sheet cut from a float glass ribbon, the PM coating 24 may be sputter deposited on the air side and/or the tin side.
The substrate 22 with the PM coating 24 deposited by CVD, spray pyrolysis, or MSVD methods may subsequently be subjected to one or more post-coating annealing operations. It can be understood that the annealing time and temperature can be affected by several factors, including the composition of the substrate 22, the composition of the PM coating 24, the thickness of the PM coating 24, and whether the PM coating 24 is in direct contact with the substrate 22 or Whether it is one layer of the multilayer laminate on the substrate 22.
Regardless of whether the PM coating 24 is provided by a CVD process, a spray pyrolysis process, or an MSVD process, where the substrate 22 includes sodium ions that can migrate from the substrate 22 to the PM coating 24 deposited on the substrate 22, the sodium ions can pass through Form inert compounds while consuming titanium, for example, by forming sodium titanate or by causing photo-excited charge recombination to inhibit or destroy the photoactivity of the PE coating 24, for example, photocatalytic activity and/or photoactive hydrophilicity . Therefore, a sodium ion diffusion barrier (SIDB) layer may be deposited on the substrate before the PM coating 24 is deposited. Suitable SIDB layers are discussed in detail in U.S. Patent No. 6,027,766, which is incorporated herein by reference. By post-coating heating, a sodium barrier layer can be used for sodium-containing substrates, such as soda lime glass. For the application of the PM coating 24 of the present invention in a molten metal bath, a sodium barrier layer is optional.
The SIDB layer may include, but is not limited to, various types of cobalt oxide, chromium oxide and iron oxide, tin oxide, silicon oxide, titanium oxide, zirconium oxide, fluorine-doped tin oxide, aluminum oxide, magnesium oxide, zinc oxide, and mixtures thereof Amorphous or crystalline metal oxides are formed. Mixtures include, but are not limited to, magnesium/aluminum oxide and zinc/tin oxide. Those skilled in the art can understand that metal oxides may include metal oxides, super-oxides or suboxides. Although the thickness of the SIDB layer required to prevent the sodium ion poisoning of the PM coating varies with several factors, including the time the substrate is held at a temperature higher than the temperature at which sodium ion migration occurs, the rate of sodium ion migration from the substrate, The rate of sodium ion migration through the SIDB layer, the thickness of the PM coating, and the degree of photocatalytic activity required for most occasions on a given occasion, the thickness of the SIDB layer should be at least about 100 angstroms, such as at least about 250 angstroms, for example, At least about 500 angstroms thick to prevent sodium ion poisoning of the PM coating. The SIDB layer can be deposited on the substrate 22 by any conventional method, such as but not limited to CVD, spray pyrolysis, or MSVD method. If a spray pyrolysis or CVD method is used, the substrate 22 can be maintained at a temperature of at least about 400°C (752°F) to ensure that the metal-containing precursor decomposes to form the SIDB layer. The SIDB layer can be formed by other methods including a sol-gel method, and the sol-gel method as described above is generally not suitable for the manufacture of glass float tape.
The tin oxide SIDB layer, such as fluorine-doped tin oxide SIDB, can be deposited on the substrate by spray pyrolysis, including the formation of an aqueous suspension of dibutyltin difluoride (C4H9) 2SnF2 and water and the water by spray pyrolysis The suspension is applied to the substrate. Generally speaking, aqueous suspensions usually contain 100-400 grams of dibutyltin difluoride per liter of water. Wetting agents can be used as suspension enhancers. In the process of preparing the aqueous suspension, the dibutyltin difluoride particles can be ground to an average particle size of 1-10 microns. The aqueous suspension can be stirred vigorously to provide a uniform distribution of particles in the suspension. The aqueous suspension is delivered by spray pyrolysis to the surface of the substrate at a temperature of at least about 400°C (752°F), such as about 500°C-700°C (932°F-1292°F), so that the aqueous suspension is formed by pyrolysis Tin oxide SIDB layer. It can be understood that the thickness of the SIDB layer formed by this process can be controlled by the coating line speed, the concentration of dibutyltin difluoride in the aqueous suspension and the spray rate, and other parameters.
Alternatively, the tin oxide SIDB layer may be formed on the substrate by a CVD method using a metal-containing precursor such as monobutyltin trichloride vapor (hereinafter "MBTTCL") in an air carrier gas mixed with water vapor. MBTTCL vapor may be present at a concentration of at least about 0.5% in the air carrier gas applied to the substrate while the substrate is at a temperature sufficient to deposit the tin-containing layer, such as at least about 400°C (952°F), such as about 500°C -800°C (932°F-1472°F) to form a tin oxide SIDB layer. It can be understood that the thickness of the SIDB layer formed by this process can be controlled by the coating line speed, the concentration of MBTTCL vapor in the air carrier gas, the carrier gas flow rate, and other parameters.
The SIDB layer formed by the MSVD process is described in US Patent Application Serial No. 08/597,543 (filed on February 1, 1996, entitled "Alkali Metal Diffusion Barrier Layer (alkali metal diffusion barrier layer)", which is incorporated herein by reference. Invention), which discloses the formation of an alkali metal diffusion barrier layer. The barrier layer disclosed therein is generally effective at a thickness of about 20 angstroms to about 180 angstroms, and the effectiveness increases as the density of the barrier layer increases.
The PM coating 24 of the present invention can be photoactive when exposed to the ultraviolet range of the electromagnetic spectrum, such as 300nm-400nm, and/or the visible range (400nm-800nm), such as photocatalytic and/or photoactive. water. Ultraviolet radiation sources include natural sources, such as solar radiation, and artificial sources such as black light or ultraviolet light sources such as UVA-340 light sources available from Q-Panal Company (Cleverand, Ohio).
As shown in FIG. 1, in addition to the PM coating 24 of the present invention, one or more functional coatings 46 may be deposited on the substrate 22. For example, the functional coating 46 may be deposited on the major surface 60 of the substrate 22 opposite to the surface 21. The term "functional coating" as used herein refers to a coating that changes one or more of the physical properties of the substrate on which it is deposited, such as optical, thermal, chemical or mechanical properties, and is not intended to be used during subsequent processing. Remove from the substrate. The functional coating 46 may have one or more functional coating films with the same or different compositions or functions. The term "layer" or "film" as used herein refers to a coating area having a desired or selected coating composition. The film can be uniform, non-uniform, or have a gradient composition change. If the outer surface or part (that is, the surface or part furthest from the substrate), the inner surface or part (that is, the surface or part closest to the substrate) and the part between the outer and inner surfaces have substantially the same composition, The film is "uniform". When moving from the inner surface to the outer surface, the film is "graded" if it has one or more components in substantially increasing fractions and one or more other components in substantially decreasing fractions, and vice versa Of course. If the film is not uniform or graded, then the film is "non-uniform." The "coating" is composed of one or more "films".
The functional coating 46 may be a conductive coating, such as, for example, the conductive heating window coating disclosed in U.S. Patent Nos. 5,653,903 and 5,028,759, or a single-film or multi-film coating that can be used as an antenna. Likewise, the functional coating 46 may be a solar control coating, for example, a visible, infrared or ultraviolet energy reflecting or absorbing coating. Examples of suitable solar control coatings are, for example, in U.S. Patent Nos. 4,898,789; 5,821,001; 4,716,086; 4,610,771; 4,902,580; 4,716,086; 4,806,220; 4,898,790; 4,834,857; 4,948,677; 5,059,295; Found in. Similarly, the functional coating 46 may be a low emissivity coating. "Low-emissivity coating" refers to visible wavelength energy, for example, 400nm to about 800nm (eg, to about 780nm) can transmit through the coating but reflect longer wavelength solar infrared energy and/or thermal infrared energy and is generally used Improve the thermal insulation performance of architectural glass windows. "Low emissivity" means that the emissivity is lower than 0.4, such as lower than 0.3, such as lower than 0.2. Examples of low-emissivity coatings are found, for example, in U.S. Patent Nos. 4,952,423 and 4,504,109 and British document GB2,302,102. The functional coating 46 may be a single-layer or multi-layer coating and may contain one or more metals, non-metals, semi-metals, semiconductors, and/or alloys, compounds, composites, combinations, or blends thereof. For example, the functional coating 46 may be a single-layer metal oxide coating, a multi-layer metal oxide coating, a non-metal oxide coating, or a multi-layer coating.
Examples of functional coatings suitable for the present invention may be SUNGATE(R) and SOLARBAN(R) series coatings (available from PPG Industries, Inc. (Pittsburgh, Pennsylvania)). These functional coatings generally include one or more anti-reflective coating films containing dielectric or anti-reflective materials, such as metal oxides or metal alloy oxides, which are preferably transparent or substantially transparent to visible light. The functional coating 46 may also include an infrared reflective film containing a reflective metal, such as a precious metal such as gold, copper or silver, or a combination or alloy thereof, and may further include a base film or a base film on and/or under the metal reflective layer. Barrier films, such as titanium, are known in the art.
The functional coating 46 can be deposited in any conventional manner, such as but not limited to magnetron sputter vapor deposition (MSVD), chemical vapor deposition (CVD), spray pyrolysis (ie, pyrolytic deposition), atmospheric pressure CVD (APCVD) ), low pressure CVD (LPCVD), plasma enhanced CVD (PEVCD), plasma assisted CVD (PACVD), thermal or electron beam evaporation, cathodic arc deposition, plasma spray deposition, and wet chemical deposition (eg, sol-gel , Silver mirror method, etc.). For example, U.S. Patent Nos. 4,584,206, 4,900,110, and 5,714,199 (herein incorporated by reference in the present invention) disclose a method and apparatus for depositing a metal-containing film on the bottom surface of a glass ribbon by chemical vapor deposition. This known device can be located downstream of the molten tin bath in the float glass process, so that a functional coating is provided under the glass ribbon, that is, on the side opposite to the PM coating of the present invention. Alternatively, one or more other CVD coaters may be located in the tin bath to deposit the functional coating on or under the PM coating 24 on the float glass ribbon. If the functional coating is applied to the PM coating side of the substrate, the functional coating can be applied in a tin bath before the PM coating. If the functional coating is on the side 60 opposite to the PM coating, the functional coating can be applied to the tin side of the substrate 22 after the tin bath in the float process as described above, for example, by CVD or MSVD. In another embodiment, the PM coating 24 can be deposited on all or a portion of the surface 60 and the functional coating 46 can be deposited on all or a portion of the surface 21.
An exemplary article of the present invention is given in the form of an insulating glass (IG) unit 30 in FIG. 3. The insulating glass unit has a first pane 32 that is isolated from a second pane 34 by an isolation component (not shown) and fixed in place by a sealant system, forming a cavity between the two panes 32, 34. The first pane 32 has a first surface 36 (No. 1 surface) and a second surface 38 (No. 2 surface). The second pane 34 has a first surface 40 (No. 3 surface) and a second surface 42 (No. 4 surface). The first surface 36 may be the outer surface of the IG unit, that is, the surface exposed to the environment, and the second surface 42 may be the inner surface, that is, the surface that forms the interior of the structure. Examples of IG units are disclosed in U.S. Patent Nos. 4,193,236; 4,464,874; 5,088,258; and 5,106,663, which are incorporated herein by reference. In one embodiment shown in Figure 3, the PM coating 24 may be located on the No. 1 or No. 4 surface, such as the No. 1 surface. The PM coating 24 reduces fogging and makes the IG unit 30 easier to clean and maintain. In this embodiment, one or more optional functional coatings 46 as described above can be deposited on at least a portion of the No. 2, No. 3, or No. 4 surface.
The advantages of the present invention relative to the ion implantation and sol-gel methods for forming self-cleaning coatings include the method of forming a thin, dense, PM film on the substrate, which is different from the general methods obtained by ion implantation and sol-gel coating methods. Thicker, porous self-cleaning coating. Another advantage is that the method of providing PM coating according to the present invention avoids the need to reheat the substrate after applying the coating or coating precursor, which is used in conventional ion implantation and sol-gel methods of. This not only makes the method cheaper and more effective, such as lower equipment cost, lower energy cost, and lower production time, but also significantly reduces the possibility of sodium ion migration and therefore the effect of the present invention on the PM coating 24 The sodium ions are poisoned. In addition, the method of the present invention is easily applicable to forming a PM coating on a continuously moving substrate, such as a glass float belt.
Those skilled in the art can understand that the present invention can be improved without departing from the basic principles disclosed in the above description. Therefore, the specific embodiments described in detail herein are only illustrative and do not limit the scope of the present invention, while the latter is entirely given by the appended claims and any and all equivalents thereof.
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| US6054227A | United States of America | A | |
| PL335736A1 | Poland | A1 | |
| BR9808337A | Brazil | A | |
| CN1260767A | China | A | |
| HU0001814A2 | Hungary | A2 | |
| HUP0001814A2 | Hungary | A2 | |
| JP2000513695A | Japan | A | |
| TR199902245T2 | Türkiye | T2 | |
| SK119299A3 | Slovakia | A3 | |
| KR20000076278A | Republic of Korea | A | |
| HK1028014A1 | Hong Kong, China | A1 | |
| IL131767D0 | Israel | D0 | |
| AU732526B2 | Australia | B2 | |
| AU737164B2 | Australia | B2 | |
| AU5428401A | Australia | A | |
| JP2001524165A | Japan | A | |
| US6413581B1 | United States of America | B1 | |
| US2002114945A1 | United States of America | A1 | |
| US2002155299A1 | United States of America | A1 | |
| CA2434560A1 | Canada | A1 | |
| WO02085809A2 | World Intellectual Property Organization (WIPO) | A2 | |
| WO02085809A3 | World Intellectual Property Organization (WIPO) | A3 | |
| CA2452637A1 | Canada | A1 | |
| WO03006393A1 | World Intellectual Property Organization (WIPO) | A1 | |
| CA2452723A1 | Canada | A1 | |
| WO03009061A2 | World Intellectual Property Organization (WIPO) | A2 | |
| US2003027000A1 | United States of America | A1 | |
| EP0966409B1 | European Patent Office (EPO) | B1 | |
| US2003039843A1 | United States of America | A1 | |
| AT233230T | Austria | T | |
| ATE233230T1 | Austria | T1 | |
| DE69811640D1 | Germany | D1 | |
| WO02085809A8 | World Intellectual Property Organization (WIPO) | A8 | |
| DK0966409T3 | Denmark | T3 | |
| PT966409E | Portugal | E | |
| EP0968143B1 | European Patent Office (EPO) | B1 | |
| AT246155T | Austria | T | |
| ATE246155T1 | Austria | T1 | |
| DE69816792D1 | Germany | D1 | |
| AU765169B2 | Australia | B2 | |
| DE69811640T2 | Germany | T2 | |
| KR20030082943A | Republic of Korea | A | |
| WO03009061A3 | World Intellectual Property Organization (WIPO) | A3 | |
| DK0968143T3 | Denmark | T3 | |
| AR032859A1 | Argentina | A1 | |
| PT968143E | Portugal | E | |
| ES2195323T3 | Spain | T3 | |
| EP1366000A2 | European Patent Office (EPO) | A2 | |
| MXPA03007287A | Mexico | A | |
| CN1131183C | China | C | |
| US2003235695A1 | United States of America | A1 | |
| EP1375444A1 | European Patent Office (EPO) | A1 | |
| KR20040024582A | Republic of Korea | A | |
| EP1406847A1 | European Patent Office (EPO) | A1 | |
| DE69816792T2 | Germany | T2 | |
| US6722159B2 | United States of America | B2 | |
| ES2205457T3 | Spain | T3 | |
| CN1493539A | China | A | |
| EP1417158A2 | European Patent Office (EPO) | A2 | |
| CN1501895A | China | A | |
| TR200400058T2 | Türkiye | T2 | |
| TR200401194T2 | Türkiye | T2 | |
| CN1541196AThis record | China | A | |
| TR200401195T2 | Türkiye | T2 | |
| JP2004535922A | Japan | A | |
| JP2005500230A | Japan | A | |
| CN1596229A | China | A | |
| HK1066524A1 | Hong Kong, China | A1 | |
| JP2005507974A | Japan | A | |
| JP2005095894A | Japan | A | |
| AU2002316028B2 | Australia | B2 | |
| KR100499549B1 | Republic of Korea | B1 | |
| JP3676824B2 | Japan | B2 | |
| CA2283583C | Canada | C | |
| CA2283222C | Canada | C | |
| HU0001814A3 | Hungary | A3 | |
| HUP0001814A3 | Hungary | A3 | |
| AU2002320488B2 | Australia | B2 | |
| NZ530479A | New Zealand | A | |
| AU2002318321B2 | Australia | B2 | |
| US7049002B2 | United States of America | B2 | |
| CN1263695C | China | C | |
| US7096692B2 | United States of America | B2 | |
| US2006263610A1 | United States of America | A1 | |
| IL131767A | Israel | A | |
| EP1417158B1 | European Patent Office (EPO) | B1 | |
| AT361901T | Austria | T | |
| ATE361901T1 | Austria | T1 |
4 legal events, as the office reported them to INPADOC
Over the term
Point at a mark for the eventEvents
| Event | Code | |
|---|---|---|
| Termination of patent right or utility modelEXPY | EXPY | |
| Grant of patent or utility modelGrantedC14 | C14 | |
| Entry into substantive examinationC10 | C10 | |
| PublicationC06 | C06 |
Numbers
- Publication
- 1541196
- Publication, DOCDB
- 1541196
- Publication, EPODOC
- CN1541196
- Application
- 28158822
- Application, DOCDB
- 02815882
- Application, EPODOC
- CN20028015882
Titles3
- Chinese
- 可见光-响应光活性涂层,涂覆制品,及其制备方法
- English
- Visible light-responsive photoactive coating, coated product, and preparation method thereof
- Chinese
- 可见光-响应光活性涂层,涂覆制品,及其制备方法
Classification
- CPC, 22
- C03C17/2456
- C03C17/245
- C03C17/25
- C03C17/256
- C03C17/3417
- C03C17/3435
- C03C17/3441
- C03C2217/212
- C03C2217/24
- C03C2217/71
- C03C2218/112
- C03C2218/152
- C03C2218/154
- C03C2218/155
- C03C2218/156
- C03C2218/32
- C03C2218/365
- C23C16/40
- Y10T428/265
- Y10T428/315
- Y10T428/31678
- Y02T50/60
- IPC, 11
- B32B9 00
- B01J35 00
- B01J37 02
- B01J37 34
- C03B18 14
- C03C17 00
- C03C17 245
- C03C17 25
- C03C17 34
- C23C14 48
- C23C16 40