Methods of obtaining photoactive coatings and/or anatase crystalline phase of titanium oxides and articles made thereby

【0001】<u style="single">Reference related application</u>This application claims the rights of US Provisional Patent Application Serial No. 60 / 229,449 filed on August 31, 2000, incorporated herein by reference in its entirety.

【0002】

(Technical Field) The present invention relates to a method for changing or obtaining a phase of a material phase with respect to a photoactive coating, for example, a method for obtaining an anatase crystal phase of titanium oxide from an amorphous phase of titanium oxide or a titanium metal. With respect to methods and / or articles made thereby to obtain hydrophilic and / or photocatalytic coatings by crystallization.

【0003】

(Background Technology) For many substances, such as glass substrates such as building windows, automotive transparency, and aircraft windows, the surface of the substrate can produce surface contaminants such as common organic and inorganic surface contaminants. It is desirable to have virtually no for a long period of time. By convention, this has often meant cleaning these surfaces. This cleaning operation is typically performed by hand wiping the surface with or without a chemical cleaning solution. This method is laborious, time consuming and / or costly. Therefore, there is a need for a glass substrate cleaning method that reduces the frequency and / or need for such manual cleaning operations.

【0004】

Certain semiconductor metal oxides are known to provide a photoactive (hereafter referred to as "PA") coating. The term "photoactive" or "photoactively" refers to the generation of hall-electron pairs when irradiated with electromagnetic waves of a specific frequency, typically ultraviolet light (UV). These PA coatings are typically photocatalytic (hereafter referred to as "PC") when they are thicker than a minimum thickness. "Photocatalytic" means a coating that, when exposed to certain electromagnetic waves such as UV, interacts with organic pollutants on the coating surface and degrades or decomposes those organic pollutants. With sufficient PC activity, these PC coatings are also self-cleaning. "Self-cleaning" means having sufficient PC activity to decompose organic pollutants quickly enough that they do not need to be wiped by hand to remove the contaminants. In addition, the PC coating is typically also hydrophilic. "Hydrophilic" generally means getting wet with water with a contact angle with water less than 20 °. The hydrophilicity of the PC coating helps reduce fogging, the accumulation of water droplets on the coating that reduces visible light transmission and visibility through the coating substrate.

【0005】

Titanium dioxide (TiO₂) Coatings are known to be hydrophilic and / or self-cleaning. However, not all titanium dioxide phases are acceptable as providing a self-cleaning and / or hydrophilic coating. Currently, it is preferable to use the anatase crystal phase rather than the amorphous phase or rutile crystal phase of titanium dioxide to form the PC coating.

【0006】

For example, sputter coating of titanium dioxide has been used as a protective surface coating and is described in US Pat. No. 4,716,086. The limitation of conventional sputter deposition of titanium dioxide is the inability to obtain anatase crystal phases. Another limitation is that sputter-deposited metal films are more efficient than vapor-deposited metal oxide films. If a metal oxide film is desired, it is an effective method to sputter-deposit the metal film on the substrate, and then heat the vapor-deposited metal film in the air. In the case of a titanium metal film vapor-deposited with a spatter, the oxide film formed after heating is usually a rutile phase of titanium dioxide rather than an anatase phase. Publications relating to the formation of titanium dioxide coatings on glass substrates include US Pat. Nos. 5,595,813 and 6,027,766, and J. Mater. Res., Vol. 10, No. 11 by Paz et al. , pp. 2842-48, November (1995), "Photooxidative Self-cleaning Transparent Titanium Dioxide Films on Glass" is included.

【0007】

For example, a method of producing a sputter-deposited hydrophilic and / or photocatalytic coating by heating sputter-deposited titanium metal films and converting them into titanium dioxide films that are at least partially anatase-phased. It will be acknowledged that it would be advantageous to give.

【0008】

(Disclosure of the Invention) The present invention relates to a method for changing or obtaining a phase of a material, and includes the deposition of a film that facilitates the phase change or preferable deposition. As one aspect of the present invention, a titanium oxide film is deposited on a cubic or orthorhombic phase zirconium oxide film. As one aspect of the present invention, the deposited titanium oxide film is in the anatase phase. In another embodiment, a titanium metal film is deposited on a cubic or orthorhombic phase zirconium oxide film and the titanium metal film is heated in the presence of oxygen to obtain at least titanium oxide, eg, titanium dioxide film. Partially given as anatase phase.

【0009】

As another aspect of the invention is provided a method of producing a photoactive, eg, photoactively hydrophilic and / or photocatalytic coating. One method of producing a photoactive coating is to cover at least a portion of the substrate to deposit a first coating layer of zirconium oxide and cover at least a portion of the first coating layer to cover a photoactive material such as titanium dioxide. Includes depositing a second coating layer consisting of and providing a coated substrate. In one embodiment, the method comprises heating at least one substrate and / or the first coating layer and / or the second coating layer to produce a photoactive article.

【0010】

The present invention relates to articles, such as windows for residential and commercial use, windows for land, air, sea, space and underwater vehicles, manufactured using the coating substrate of the present invention. In one embodiment, the article comprises a substrate, a zirconium oxide layer having a thickness of 10 Å to 200 Å deposited over at least a portion of the substrate, and a titanium oxide layer deposited over the zirconium oxide layer. In another embodiment, the article has a first layer comprising a first material of a cubic or orthorhombic crystalline phase deposited over at least a portion of the substrate. A second layer with at least one photoactive material is deposited over , for example, on the first layer .

【0011】

(Detailed description of the invention) "inner", "outer", "above", "below", "top" used here. Spatial or directional terms such as "," bottom ", etc. relate to the present invention as shown in the drawings. However, it will be understood that the present invention can also take a variety of different orientations and therefore such terms should not be considered as limiting. Furthermore, all numbers used in the present specification and claims to express size, physical characteristics, processing parameters, component amounts, reaction conditions, etc. are modified by the term "about" in any case. It should be understood as possible. Therefore, unless the opposite is instructed, the numbers given in the following specification and claims are approximate and depend on the desired nature required to be obtained by the present invention. It can be changed. At a minimum, any number should be considered to have been given by referring to at least a large number of reported significant numbers and applying the usual rounding method, which is the doctrine of equivalents for the scope of claims. Is not intended to limit the application of. Moreover, it should be understood that many of the ranges described herein include the beginning and ending values, and any small range contained therein is included. For example, the range "1-10" should be considered to include any small range (including those numbers) that falls between the lowest value of 1 and the highest value of 10. .. That is, a small range starting with a minimum value of 1 or more and ending with a maximum value of 10 or less, for example 5. The entire range, such as 5-10, is included. Furthermore, the term "deposited over" or "provided over" as used herein is used above, but not necessarily in contact with the surface. It also means being there. For example, a "covered" coating of a substrate does not preclude the presence of one or more other coating films of the same or different composition located between the deposited coating and the substrate. .. In addition, all% listed herein are by "weight" unless otherwise indicated. The photocatalytic activity values discussed herein have been determined by the conventional stearic acid test described in US Pat. No. 6,027,766, which is cited herein by reference in its entirety.

【0012】

With respect to FIG. 1, an article 20 having the features of the present invention is shown. Article 20 has a substrate 22 having a first surface 24 and a second surface 26 on the opposite side. The substrate 22 is not limited to the invention and may be made of any desired material with any desired properties, such as an opaque, translucent, transparent, or substantially transparent substrate. By "substantially transparent" is meant having a visible light transmittance of 60% or more. By "translucent" is meant having a visible light transmittance greater than 0% and less than 60%. "Opaque" means that the visible light transmittance is 0%. Further, the substrate 22 may have any desired shape, such as flat or curved. Examples of suitable substrates include, but are limited to, plastic substrates [eg, polyacrylates, polycarbonates, and polyethylene terephthalates (PETs); metal substrates; ceramic substrates; glass substrates; or mixtures or combinations thereof; It's not something. For example, the substrate may be conventional uncolored soda, lime, silica glass, i.e. "transparent glass", or tinted or separately colored glass, borosilicate glass, lead glass, and / or tempered, untempered, It may be annealed or heat-strengthened glass. The glass can be of any kind, such as conventional float glass, flat glass, or float glass strip (ribbon), with any optical properties, eg, any value of visible light transmittance. , UV transmittance, infrared transmittance, and / or total solar energy transmittance, or any composition having them. Suitable types of glass for practicing the present invention are, for example, US Pat. Nos. 4,746,347, 4,792,536, 5,240,886, 5,385,872, and 5,393, It is described in Specification 593, but should not be considered limited to them. For example, the substrate 22 may be a glass plate of a building window, a light window, a single glass plate of an insulating glass unit, or a laminate for conventional automobile windshield, side or rear windows, to name a few. , Sunroof, or transparent aircraft.

【0013】

The substrate 22 has a coated laminate or coating 28 of the invention that covers all or at least a portion of the substrate 22, eg, covers all or part of the surface 24, and is a substantially transparent article, substantially. Consists of a translucent article or a substantially opaque article. The term "coating" or "coating laminate" used herein has one or more coating layers or films. The term "layer" or "film" refers to a region of the coating having the desired or selected coating composition. The coating 28 can be photocatalytic, photoactively hydrophilic, or both. By "photoactively hydrophilic" is meant a coating in which the contact angle of water droplets on the coating decreases over time as a result of exposing the coating to electromagnetic waves within the light absorption band of the coating. If photoactively hydrophilic, the coating 28 does not necessarily have to be photocatalytic.

【0014】

The example of the coating 28 of the present invention shown in FIG. 1 covers at least a part of the surface 24 of the substrate 22, eg, the first film 30 deposited on it, and at least a part of the first film 30, eg, on top. It has a deposited second film 32. In the coating 28 of this example, the first and second films 30, 32 are separate coating layers, that is, the coating 28 is not a mixture of the materials of the first and second films 30, 32. In one embodiment, the first film 30 comprises a material that significantly increases the photoactivity of the second film 32, such as photoactive hydrophilicity and / or photocatalytic activity, as compared to the case of the second film 32 alone. There is. In another aspect, the first film 30 comprises a material that promotes or enhances the growth of a special crystalline phase of the second film 32. The first film 30 can be of the same film (ie, of the same material), to achieve both of these objectives, or to use different materials. Good.

【0015】

The first film 30 may contain any material and may have any thickness that gives one or more of the results described above. For example, the first film 30 can contain at least one type of metal oxide. The term "metal oxide" as used herein includes metal oxides, super-oxides, or sub-oxides. For example, the terms "zirconium oxide", "titanium oxide", etc. used herein refer to dioxides, suboxides, and peroxides, and combinations of these with other materials, such as hafnium oxide zirconium and / or oxynitride. It should be understood to include objects, such as combinations with titanium oxynitride. As an example, the first film 30 is zirconium oxide (ZrO).₂ ). The zirconium oxide film should be thick enough to achieve one or more of the above objectives. In one embodiment, the zirconium oxide primary film 30 can have a thickness greater than 0 Å, eg equal to or greater than 15 Å, eg equal to or greater than 25 Å, eg in the range 25 Å to 500 Å. is there. For example, the zirconium oxide film 30 can have thicknesses in the range of 25 Å to 150 Å; 40 Å to 80 Å; and / or 60 Å to 70 Å. In another embodiment, the zirconium oxide film 30 can have a thickness equal to or greater than 100 Å, for example in the range of 100 Å to 500 Å, for example 120 Å to 200 Å, for example 140 Å to 160 Å.

【0016】

The second film 32 contains a photoactive material. The photoactive material includes, but is not limited to, at least one type of metal oxide, for example, one or more types of metal oxides or semiconductor metal oxides. Suitable metal oxides include titanium oxides, silicon oxides, iron oxides, tungsten oxides, zinc oxides, tin oxides, zinc / tin oxides, calcium titanium oxides, to name a few. Includes molybdenum oxides, niobium oxides, and mixtures thereof. The second film 32 is crystalline or can be at least partially crystalline. However, crystallinity is not always required to achieve photoactive hydrophilicity.

【0017】

As an example of the coating 28 of the present invention, the photoactive coating material of the second film 32 is titanium dioxide (TiO).₂). Titanium dioxide may exist as an amorphous form or as one of three crystalline forms, namely anatase, rutile, and brookite crystalline forms. Anatase phase titanium dioxide is particularly useful. This is because it exhibits strong photoactivity while having excellent resistance to chemical erosion and excellent physical durability. The second film 32 may have any desired thickness. As an example, the titanium dioxide secondary film has a thickness equal to or greater than 100 Å, eg, equal to or greater than 200 Å, eg, in the range of 100 Å to 500 Å, eg, 300 Å to 400 Å. Has.

【0018】

The first and second films 30 and 32 of the coating 28 should be thick enough to provide acceptable levels of photoactivity, eg, photocatalytic activity and / or photoactive hydrophilicity for the desired purpose. Is. There is no absolute value that makes coating 28 "acceptable" or "unacceptable". This is because whether the coating 28 has an acceptable level of photoactivity depends largely on the purpose and conditions of using the coated article and the performance criteria selected to meet that purpose. .. However, the thickness of the coating 28 to achieve photoactive hydrophilicity can be much thinner than the thickness required to achieve commercially acceptable levels of coating catalytic activity. For example, the zirconium oxide / titanium oxide coating described above may have any desired thickness. However, for most automotive applications, the coating 28 should not be thick enough to be invisible through it. For example, the coating 28 can have a total thickness of 50 Å to 5000 Å. As the coating thickness decreases in the range of 50 Å to 3000 Å, for example 100 Å to 1000 Å, for example 200 Å to 600 Å, for example 200 Å to 300 Å, the photocatalytic activity becomes very low and by conventional stearic acid tests. Can even be unmeasurable, but photoactive hydrophilicity can still be present in the presence of electromagnetic waves within the light absorption band of the photoactive material.

【0019】

The coating 28 may be the outer or outermost coating of the multilayer laminate of coatings present on the substrate 22, or the coating 28 is one of the coatings other than the outermost coating in such a multilayer. It may be embedded as. For example, as shown in FIG. 1, it is possible to cover all or part of the coating 28 and optionally apply a primary or removable protective material or film. The protective film 36 is organic such that the protective film 36 is photocatalytically removed from the surface of the coating 28 when the coating substrate 22 is exposed to electromagnetic energy in the light absorption band of the photoactive material of the second film 32, for example. Materials can be included. The protective film 36 can be applied to form the desired pattern on the coating 28 and may be transparent, translucent or opaque.

【0020】

The coating 28 may be deposited directly on, i.e., in contact with, the surface 24 of the substrate 22. Alternatively, one or more functional coatings 38 may optionally be interposed between the coating 28 and the substrate 22. As used herein, the term "functional coating" is a coating that modifies one or more physical properties of the substrate on which it is deposited, such as optical, thermal, chemical, or mechanical properties, and is a post-treatment. Refers to a coating that is unlikely to be removed from the substrate. The functional coating 38 may have one or more functional coating films of the same or different composition or functionality. The functional coating 38 can be, for example, an electrically conductive coating such as a window coating that is electrically heated as described in US Pat. Nos. 5,653,903 and 5,028,759, or a single film or multiple films. It may be a coating. Similarly, the functional coating 38 may be a solar controlled coating, eg, a coating that reflects or absorbs visible, infrared, or UV energy. Examples of suitable solar control coatings are, for example, U.S. Pat. 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, It is found in No. 4,948,677, No. 5,059,295, and No. 5,028,759, and in US Patent Application No. 09 / 058,440. Similarly, the functional coating 38 can be a low emissivity coating. A "low emissivity coating" allows visible wavelength energies, such as 400 nm to about 800 nm (eg, up to about 780 nm), to pass through the coating, but with longer wavelengths of solar infrared energy and / or. Thermal infrared energy is reflected and is typically aimed at improving the thermal insulation of building-embedded window glass. "Low emissivity" means an emissivity lower than 0.4, preferably lower than 0.3, and even more preferably lower than 0.2. Examples of low emissivity coatings are, for example, U.S. Pat. No. 4,952, Found in 423 and 4,504,109 and the British literature, GB2,302,102. The functional coating 38 may be a single layer or multilayer coating from one or more metals, non-metals, metalloids, semiconductors and / or alloys, compounds, composites, combinations thereof, or mixtures thereof. It may be. For example, the functional coating 38 may be a single layer metal oxide coating, a multilayer metal oxide coating, a non-metal oxide coating, or a multilayer coating. The functional coating 38 contains one or more transparent conductive oxides (eg, indium tin oxide or tin oxide), or doped metal oxides (eg, fluorine or antimony-doped tin oxide). May be. In addition, the functional coating 38 contains one or more types of nitrides (eg, titanium nitride, silicon nitride, or zirconium nitride), borides (eg, titanium diboronized), or carbides (eg, titanium carbide). be able to. Further, or otherwise, another functional coating 40 can optionally be deposited on all or part of the second surface 26. Found in 102. The functional coating 38 may be a single layer or multilayer coating from one or more metals, non-metals, metalloids, semiconductors and / or alloys, compounds, composites, combinations thereof, or mixtures thereof. It may be. For example, the functional coating 38 may be a single layer metal oxide coating, a multilayer metal oxide coating, a non-metal oxide coating, or a multilayer coating. The functional coating 38 contains one or more transparent conductive oxides (eg, indium tin oxide or tin oxide), or doped metal oxides (eg, fluorine or antimony-doped tin oxide). May be. In addition, the functional coating 38 contains one or more types of nitrides (eg, titanium nitride, silicon nitride, or zirconium nitride), borides (eg, titanium diboronized), or carbides (eg, titanium carbide). be able to. Further, or otherwise, another functional coating 40 can optionally be deposited on all or part of the second surface 26. Found in 102. The functional coating 38 may be a single layer or multilayer coating from one or more metals, non-metals, metalloids, semiconductors and / or alloys, compounds, composites, combinations thereof, or mixtures thereof. It may be. For example, the functional coating 38 may be a single layer metal oxide coating, a multilayer metal oxide coating, a non-metal oxide coating, or a multilayer coating. The functional coating 38 contains one or more transparent conductive oxides (eg, indium tin oxide or tin oxide), or doped metal oxides (eg, fluorine or antimony-doped tin oxide). May be. In addition, the functional coating 38 contains one or more types of nitrides (eg, titanium nitride, silicon nitride, or zirconium nitride), borides (eg, titanium diboronized), or carbides (eg, titanium carbide). be able to. Further, or otherwise, another functional coating 40 can optionally be deposited on all or part of the second surface 26.

【0021】

Examples of suitable functional coatings used in the present invention are from PPG Industries, Inc. of Pittsburgh, PA, SUNGATE (registered trademark) and SOLARBAN (registered trademark). It is commercially available as a system coating. Such functional coatings typically include one or more anti-reflective coating films containing dielectrics or anti-reflective materials such as metal oxides or oxides of metal alloys. It is preferably transparent or substantially transparent to visible light. Functional coatings (s) may include reflective films consisting of reflective metals such as precious metals such as gold, copper or silver, or combinations or alloys thereof, and further in the art. As is known, it may have a base film or barrier film such as titanium that covers and / or underlies the metal reflective layer.

【0022】

An example of a manufactured article of the present invention is shown in FIG. 2 in the form of an insulating glass (IG) unit 42. The insulating glass unit has a first glass plate 44 located away from the second glass plate 46 by a spacer assembly (not shown), forming a chamber between the two glass plates 44 and 46. It is held in place by a sealing material system so that it does. The first glass plate 44 has a first surface 48 (surface number 1) and a second surface 50 (surface number 2). The second glass plate 46 has a first surface 52 (surface number 3) and a second surface 54 (surface number 4). The first surface 48 can be the outer surface of the IG unit 42, i.e. the surface exposed to the environment, and the second surface 54 can be the inner surface, i.e. the surface forming the inside of the structure. Examples of IG units are described in US Pat. Nos. 4,193,236, 4,464,874, 5,088,258, and 5,106,663 (cited here for reference). The coating 28 of the present invention can be deposited over one or more of those surfaces (one or more of surface numbers 1 to 4). In the non-limiting aspect shown in FIG. 2, the coating 28 is deposited on the first surface 48. The coating 28 reduces fogging and makes it easier to keep the IG unit 42 clean. As mentioned above, optionally one or more functional coatings 62 are deposited over one or more of their surfaces (numbers 1 to 4), eg, the surfaces of numbers 2, 3, or 4. You may.

【0023】

One or both of the films 30 and 32 of the coating 28 of the present invention may be placed on the substrate 22 by any conventional method, for example, by spray pyrolysis, chemical vapor deposition (CVD), or magnetron sputter vacuum deposition (MSVD). It can be formed, but is not limited to them. For example, both films 30 and 32 may be deposited in the same way, or one film may be deposited in one way and one or more of the other films in coating 28 may be deposited in one or more other ways. May be deposited with. Each of these methods has advantages and restrictions, depending on the desired properties of the coating 28 and the type of glass manufacturing method. For example, in the case of the glass manufacturing method by the conventional float method, the CVD and spray pyrolysis methods are preferable to the MSVD method. This is because they are even better compatible with coating continuous substrates such as float glass strips at elevated temperatures. Examples of CVD and spray pyrolysis coating methods are US Pat. Nos. 4,344,986, 4,393,095, 4,400,412, 4,719,126, 4,853,257, 5,536,718, 5,464,657, 5,714,199, 5,599,387, and It is described in No. 4,971,843 (these patents are cited herein for reference).

【0024】

U.S. Pat. Nos. 4,379,040, 4,861,669, 4,900,633, 4,920,006, 4,938,857, 5,328,768, and 5,492,750 (cited here for reference) include substrates including glass substrates. MSVD equipment and methods for sputter coating metal oxide films are described above. The MSVD method can be used to deposit one or more of the coated films 30, 32 on a substrate 22, eg, a glass sheet. In one embodiment, the substrate 22 is heated and then one or more of the coated films, such as the films 30 and / or 32, are deposited. Alternatively or additionally, the substrate 22 may be heated during the sputtering process itself.

【0025】

In one embodiment, the coating 28 may be sputter-deposited on the first surface 24 of the substrate 22 and the functional coating 40 may be deposited on the second surface 26 with the same coating machine. WO 00/37377, cited and described herein for reference, describes a sputtering method suitable for this embodiment. Since the sputtering is performed in vacuum, the substrate 22 is oriented in any orientation during the sputtering process of this embodiment of the present invention as long as targets for depositing the coating 28 and the functional coating 40 are present on both sides of the substrate 22. It may be.

【0026】

Next, an example of a method of applying the coating 28 by the MSVD method will be described. A substrate 22 such as a glass substrate can be preheated prior to depositing the coating 28. For example, before depositing the coating 28, the substrate should be heated to a temperature equal to or higher than 38 ° C (100 ° F), eg, in the range of about 38 ° C to 537 ° C (100 ° F to 1000 ° F). , For example, equal to or higher than 65 ° C (150 ° F), 93 ° C to 260 ° C (200 ° F to 500 ° F), for example, 149 ° C to 204 ° C (300 ° F to It can be heated to temperatures in the range of 400 ° F) (ie, the temperature of the substrate at the beginning of the coating process is within one of these temperature ranges). The heated substrate then has an argon / oxygen atmosphere, such as 5% by volume to 100% by volume of oxygen, such as 5% to 50% by volume of oxygen, such as 20% by volume of oxygen, and 5 to Place in a conventional MSVD coating device with an atmosphere of 10 millitorol pressure. To deposit the zirconium oxide primary film 30, the zirconium-containing target is sputtered in a conventional manner to form the zirconium oxide primary film 30 of the desired thickness. The zirconium-containing target preferably contains 50% by weight or more of zirconium, for example, 80% by weight or more of zirconium. However, zirconium targets may include one or more other metals or dopants such as molybdenum, strontium, titanium, lead, barium, silicon, calcium, hafnium, lantern, chromium, vanadium, manganese, copper, iron, magnesium, scandium, etc. It may contain yttrium, niobium, molybdenum, ruthenium, tantalum, tungsten, silver, nickel, renium, aluminum, or a mixture thereof, or the zirconium target may be a zirconium oxide target.

【0027】

The titanium oxide (eg, titanium dioxide) second film 32 can then be formed over the zirconium oxide first film 30 using a titanium-containing target. If the coating is not crystallized, the coated substrate may be removed from the coating machine and heated to a temperature sufficient to form a crystalline coating. For example, the coated substrate is evaporated to a temperature in the range of 100 ° C (212 ° F) to 650 ° C (1200 ° F), for example 400 ° C (752 ° F) to 650 ° C (1200 ° F). It can be heated for a time sufficient to promote the formation of titanium crystal forms. In general, temperatures in the range of 100 ° C (212 ° F) to 600 ° C (1112 ° F) are sufficient for less than one hour. When the substrate 22 is a glass sheet cut from a float glass strip, the coating 28 can be sputter-deposited on the air side and / or the tin side of the glass. Alternatively, the substrate 22 may be coated without preheating the substrate 22 prior to coating.

【0028】

The substrate 22 with the coating 28 deposited by CVD, spray pyrolysis, or MSVD method can then be subjected to one or more post-coating heating operations such as annealing or strengthening. The time and temperature of post-heating depends on several factors, including the composition of the substrate 22, the composition of the coating 28, the thickness of the coating 28, and whether the coating 28 is in direct contact with the substrate 22 or on the substrate 22. It will be appreciated that it is affected by whether or not it is one layer of the multi-layer laminate. Alternatively, a photoactive hydrophilic coating 28 is formed by practicing the present invention as an example of aspects of the invention discussed below under the heading FEATURE 2 below, without the need for any post-heating steps. Can be done.

【0029】

In the embodiment described immediately above, the coating films 30 and 32 are sputtered in an oxygen-containing atmosphere to form a metal oxide-containing coating 28. However, first and / or second films 30 and 32 are cited here in a non-reactive atmosphere or in US Pat. No. 5,830,252 and US Patent Application No. 09 / 156,730 (both for reference). It will be appreciated that it can be sputtered as a metal film in an active atmosphere below the material turning point as defined in) and the metal film can be oxidized to a metal oxide film.

【0030】

The coating 28 of the present invention is photoactive, eg, photocatalytic and / or light when exposed to radiation in the ultraviolet range of the electromagnetic spectrum, eg, 300 nm to 400 nm and / or visible range, eg, 400 nm to 700 nm. It is preferably active hydrophilic. UV sources include natural sources, such as solar radiation, and artificial sources, such as black, such as the UVA-340 light source commercially available from Q-Panel Co. in Cleveland, Ohio. A light, i.e. an ultraviolet light source, is included.

【0031】

The present invention provides some features that are advantageous for use in various industrial fields. Four of these characteristics (crystal phase selection, hydrophilicity, chemical durability, and photocatalytic activity) will be discussed next.

【0032】<u style="single">Feature 1 (Crystal phase selection)</u>In one aspect, the invention relates to a technique or method of altering or changing the phase of a film. The term "phase" is used to describe the crystalline or non-crystalline nature of a film. For example, the term "amorphous phase" is the count of diffraction peaks for an amorphous phase, as measured by conventional X-ray diffraction (XRD), that is, the film is completely or substantially amorphous. It means that it does not show measurable and detectable intensity. The term "rutile phase" means that the film or coating has a completely or substantially rutile crystal structure (ie, a detectable intensity as measured by XRD and measured by the count of diffraction peaks for the rutile phase. The term "antase phase" means that the film or coating has a complete or substantially anatase crystal structure (ie, the number of diffraction peak counts for the anatase phase as measured by XRD). (Indicates the strength that can be detected by measuring with). Yet another feature of the present invention is to change the phase of the titanium oxide film, eg, change the phase (s) of the sputter-deposited film from the amorphous phase to the anatase and / or rutile phase (s). Regarding changing to a film that includes. This feature of the present invention will be recognized from the following studies.

【0033】

In the next review, the following conditions apply unless it is shown to be contrary. The substrate was a piece of glass about 2.3 mm (0.088 inches) thick, 30 cm (12 inches) square, or 15 cm x 30 cm (6 inches x 12 inches) manufactured by the float method. The air side of these glass pieces was coated. The air side of the glass produced by the float method is the side opposite to the side where the glass strip floats on the molten metal bath as it moves through the molding chamber. For a discussion of forming float glass strips, see US Pat. Nos. 6,027,766 and 4,091, See specification 156. Those pieces of glass were cut from a glass sheet cut from the glass strip. The composition, type, shape, and size of the substrate are not limited to the present invention, and some types of materials that can be used with any type of substrate include, for example, colored glass, plastic, metal, and the like. It will be appreciated that it can also be used in ceramics and wood. Each piece of glass was sputter coated with an Airco ILS1600 magnetron sputter vacuum coater. It will be acknowledged that the present invention is not limited to the type or apparatus of sputter used. For example, any type of sputtering method can be used. The titanium metal film was sputter-deposited on a glass piece, that is, a substrate, by exciting a titanium metal target placed in a room having a 100% argon gas atmosphere. The zirconium metal film was deposited on a piece of glass, a substrate, by exciting a zirconium metal target placed in a room with a 100% argon gas atmosphere. The titanium oxide film was deposited on a glass piece, that is, a substrate, by exciting a titanium target placed in a room having an atmosphere of about 50% oxygen and 50% argon gas. As used herein, the term "titanium oxide" includes films having titanium dioxide and / or titanium suboxides and / or peroxides when referring to the anatase phase, rutile phase, and amorphous phase. The zirconium oxide film was deposited on a piece of glass, a substrate, by exciting a zirconium metal target placed in a room with an atmosphere of about 50% oxygen and 50% argon gas. The percentage of oxygen and argon in the room when sputter-depositing titanium oxide and zirconium oxide films is based on the combined flow of oxygen and argon gas entering the room. The titanium nitride film was deposited on a glass piece, that is, a substrate, by exciting a titanium metal target placed in a room having an atmosphere of about 100% nitrogen gas. Operate for all atmospheres The gas pressure was 4μ. Pump the room before filling the room with the desired atmosphere, i.e. about 5-9 × 10 atmosphere from the room^-6The pressure was reduced to a value within the range of Thor.

【0034】

Table I below shows the power in KW and shows the number of times the sample passed at a linear velocity of 304.8 cm (120 inches) per minute. The spatter-coated substrate was cut into 10.2 cm (4 inch) square pieces and heated in a furnace. The pieces were moved into a furnace set at a temperature of about 704.4 ° C (1300 ° F) and heated for about 2-1 / 2 minutes. The temperature of the furnace was calculated using uncoated glass pieces of the same size as the coated pieces. The temperature was measured using a thermocouple in contact with the surface of the calculated piece. The measured temperature was about 657.8 ° C (1216 ° F) after about 2-1 / 2 minutes. After heating, the glass pieces were removed and placed in a furnace heated to about 135 ° C (275 ° F) for about 4 minutes and then removed. Glass pieces were placed in an oven to anneal them to prevent their breakage and facilitate cutting. The crystal phases of sputter-deposited titanium metal, titanium oxide, titanium nitride, titanium oxynitride, zirconium metal, and zirconium oxide were measured using X-ray diffraction (XRD). The sample measured was approximately 2.54 cm (1 inch) square cut from a 102 cm (4 inch) square piece. X-ray diffraction analysis is for diffraction data commercially available from the JCPDS International Center using the Philips X-Pert MPD and the glazing angle method. It was performed by comparing the peaks with the standard X-ray diffraction identification card (PDF card) of. The obtained image or curve has 2θ (°) on the x axis and the intensity according to the count number on the y axis. In the case of cubic phase zirconium oxide, the (111) plane has a peak at 2θ at about 30.484 ° (PDF # 27-0997). Orthorhombic zirconium oxide is 30. It has a peak at 2θ of 537 (PDF # 34-1084), but the peak observed in the present invention is considered to be cubic rather than orthorhombic zirconium oxide. However, orthorhombic zirconium oxide would also have been present. Alternatively, in another aspect, zirconium oxide can be of Baderei stone structure (PDF # 37-1484). For titanium oxide in the rutile phase, the (110) plane has a peak at 2θ at about 27.446 °, and for titanium oxide in the anatase phase, the (101) plane has a peak at 2θ at about 25.281 °. have. Amorphous titanium oxide and amorphous zirconium oxide do not show peaks when analyzed using X-ray diffraction. Intensity counts for peaks were determined using software that is part of the Philip device or by estimating the height of the peaks. The peak count indicates the presence of a phase, and the higher the count, the more prominent the presence of the phase. The count is performed every 10 seconds, that is, it corresponds to a 10-second count. The numbers given here are relative to each other unless otherwise indicated, as the device was not calculated using the standard prior to making the measurements. When estimating the peak, the count range was determined at the discretion of the operator. Specifically, the operator selects one point on the curve or image as the starting point, selects another point on the curve as the ending point of the peak, and interpolates the height from the curved part between the starting point and the ending point. .. Although operator judgment is involved, the purpose is to identify the presence and relative amounts of anatase crystal phases. For the purposes of understanding the present invention, X-ray diffraction is acceptable to determine the presence of different phases of zirconium oxide and titanium oxide. Acknowledging that using this method to determine the presence, type, and intensity of a phase present does not indicate that the oxide is amorphous, even in the absence of peaks. There must be. More sensitive techniques, such as electron diffraction, are required to determine the presence or absence of crystals. It has a peak at 2θ at 281 °. Amorphous titanium oxide and amorphous zirconium oxide do not show peaks when analyzed using X-ray diffraction. Intensity counts for peaks were determined using software that is part of the Philip device or by estimating the height of the peaks. The peak count indicates the presence of a phase, and the higher the count, the more prominent the presence of the phase. The count is performed every 10 seconds, that is, it corresponds to a 10-second count. The numbers given here are relative to each other unless otherwise indicated, as the device was not calculated using the standard prior to making the measurements. When estimating the peak, the count range was determined at the discretion of the operator. Specifically, the operator selects one point on the curve or image as the starting point, selects another point on the curve as the ending point of the peak, and interpolates the height from the curved part between the starting point and the ending point. .. Although operator judgment is involved, the purpose is to identify the presence and relative amounts of anatase crystal phases. For the purposes of understanding the present invention, X-ray diffraction is acceptable to determine the presence of different phases of zirconium oxide and titanium oxide. Acknowledging that using this method to determine the presence, type, and intensity of a phase present does not indicate that the oxide is amorphous, even in the absence of peaks. There must be. More sensitive techniques, such as electron diffraction, are required to determine the presence or absence of crystals.

【0035】

The area below the curve between the start and end points gives the size of the crystal in the calibrated device. In the case of the present invention, the area under the curve gives a relative magnitude. The key point of this study is to determine the presence of the anatase phase, so the height of the peak is of primary concern. Table I lists the peak heights by count for the samples whose X-ray diffraction images were analyzed using the software. The peak heights for the other samples were not determined using the software, but were estimated from the X-ray diffraction curves. The evaluation of these samples is given in the examination of those samples and is indicated in Table I by the check mark ν.

【0036】

Table I shows the target materials; indoor atmosphere (gas) during coating; power (KW); number of passes; thickness of sputter-deposited film after coating; thickness of sputter-deposited metal film after heating; and Peak heights shown in 10-second counts for each of the phases identified to be present; are listed, and if the peak height is determined by the operator, that value is considered for the sample. It is given in and is marked as "ν" in Table I. The values determined using the software are given numerically in Table I. Reported thicknesses of spatter-deposited films (excluding samples 19 and 25) and / or coatings were measured by conventional X-ray fluorescence and stylus roughening measurements. The thicknesses reported for samples 19 and 25 were estimated using curves developed by past coater performance.

【0037】

If no peaks are observed for zirconium oxide and titanium oxide film, a check mark "ν" is put in the amorphous column. If the presence of a peak is mentioned, it is the presence of a peak at a 2θ angle. Moreover, the samples were not tested in the order listed. The samples are practically arranged so that similar coatings can be compared.

【0038】<u style="single">Sample 1</u>A zirconium oxide film with a thickness of about 68 Å was deposited on a glass substrate. The X-ray diffraction image of the zirconium oxide film after heating showed a cubic phase. The height of the peak by counting was estimated to be in the range of about 250-350 counts.

【0039】<u style="single">Sample 2</u>A zirconium oxide film with a thickness of about 187 Å was deposited on a glass substrate. The X-ray diffraction image of zirconium oxide after heating showed a cubic phase. It was estimated that the height of the peak by counting was in the range of about 1000 to 1100 counts.

【0040】<u style="single">Sample 3</u>A zirconium metal film with a thickness of 177 Å was deposited on a glass substrate. The coated glass substrate was heated. The zirconium oxide film formed during heating had a thickness of approximately 256 Å. The X-ray diffraction image of the zirconium oxide film showed a cubic phase. It was estimated that the peak height by counting was in the range of about 250-350 counts. Yet another peak was observed at about 28.5 at 2θ °. The peak or its cause has not been clarified. However, the peak did not exist in the X-ray diffraction curve of Sample 2.

【0041】

Samples 1 to 3 were prepared and their films were analyzed to determine whether the zirconium metal and / or zirconium metal oxide had a peak at the same 2θ value as the anatase peak of titanium oxide. The zirconium oxide film did not show any peak at its 2θ value.

【0042】<u style="single">Sample 4</u>A titanium oxide film having a thickness of 218 Å was deposited on a glass substrate. After heating, the film was analyzed by X-ray diffraction. No peak was observed.

【0043】<u style="single">Sample 5</u>A titanium film having a thickness of 109 Å was deposited on a glass substrate and the coated substrate was heated. The film thickness after heating was 207 Å. The titanium oxide film was analyzed by X-ray diffraction. No peak was observed.

【0044】<u style="single">Sample 6</u>A zirconium oxide film having a thickness of 20 Å was deposited on a glass substrate, and a titanium oxide film having a thickness of 220 Å was deposited on the zirconium oxide film. The X-ray diffraction image did not show a peak for zirconium oxide film or titanium oxide film. The absence of peaks indicated that the zirconium oxide film and the titanium oxide film were amorphous.

【0045】<u style="single">Sample 7</u>Sample 7 was a repetition of Sample 6, and it was confirmed that neither the zirconium oxide film nor the titanium oxide film had a peak.

【0046】<u style="single">Sample 8</u>A zirconium oxide film having a thickness of 31 Å was deposited on a glass substrate, and a titanium oxide film having a thickness of 221 Å was deposited on the zirconium oxide film. After heating, the coated substrate was analyzed by X-ray diffraction. The zirconium oxide film did not have a peak indicating the presence of cubic zirconium. Titanium oxide had a rutile phase with a peak height of about 94 counts. No anatase was observed.

【0047】<u style="single">Sample 9</u>A zirconium oxide film having a thickness of 45 Å was deposited on a glass substrate, and a titanium oxide film having a thickness of 215 Å was deposited on the zirconium oxide film. After heating, the coated substrate was analyzed by X-ray diffraction. No cubic zirconium oxide peak was observed. Titanium oxide had a rutile peak as high as 171 counts and anatase peak as high as 310 counts.

【0048】<u style="single">Sample 10</u>A zirconium oxide film having a thickness of 45 Å was deposited on a glass substrate, and a titanium oxide film having a thickness of 215 Å was deposited on the zirconium oxide film. The X-ray diffraction image of the heated substrate did not have a cubic zirconium oxide peak. The image showed a titanium dioxide rutile peak with a peak as high as 235 counts and anatase peak as high as 475 counts. Samples 9 and 10 were similar, and the difference in peak count values was within the expected fluctuations.

【0049】<u style="single">Sample 11</u>A zirconium oxide film having a thickness of 65 Å was deposited on a glass substrate, and a titanium oxide film having a thickness of 215 Å was deposited on the zirconium oxide film. The X-ray diffraction image has a measurement peak with a height of 283 counts for cubic zirconium oxide, a measurement peak with a height of 158 counts for the rutile phase of titanium oxide, and a measurement peak with a height of 665 counts for the anatase phase. Had a peak.

【0050】<u style="single">Sample 12</u>A zirconium oxide film having a thickness of 91 Å was deposited on a glass substrate, and a titanium oxide film having a thickness of 217 Å was deposited on the zirconium oxide film. The X-ray diffraction image has a measurement peak with a height of 416 counts for cubic zirconium oxide, a measurement peak with a height of 210 counts for the rutile phase of titanium oxide, and a measurement peak with a height of 258 counts for the anatase phase of titanium oxide. It had a measurement peak.

【0051】<u style="single">Sample 13</u>A zirconium oxide film having a thickness of 105 Å was deposited on a glass substrate, and a titanium oxide film having a thickness of 221 Å was deposited on the titanium oxide film. The X-ray diffraction image has a measurement peak with a height of 548 counts for cubic zirconium oxide, a measurement peak with a height of 171 counts for the rutile phase of titanium oxide, and a measurement peak with a height of 62 counts for the anatase phase of titanium oxide. It had a measurement peak.

【0052】<u style="single">Sample 14</u>A zirconium oxide film having a thickness of 153 Å was deposited on a glass substrate, and a titanium oxide film having a thickness of 221 Å was deposited on the zirconium oxide film. The X-ray diffraction image had a measurement peak with a height of 555 counts for cubic zirconium oxide and a measurement peak with a height of 85 counts for rutile titanium oxide. No measurable anatase titanium oxide peak was observed.

【0053】<u style="single">Sample 15</u>A zirconium oxide film having a thickness of 190 Å was deposited on a glass substrate, and a titanium oxide film having a thickness of 215 Å was deposited on the zirconium oxide film. The X-ray diffraction image had a measurement peak with a height of 690 counts for cubic zirconium oxide and a measurement peak with a height of 19 counts for rutile titanium oxide. No measurable anatase titanium oxide peak was observed.

【0054】<u style="single">Sample 16</u>Sample 16 was a repetition of Sample 15. The measured peak height for the cubic zirconium oxide peak was 687 counts, and the measured peak height for rutile titanium oxide was 206 counts. No anatase titanium oxide peak was observed. There is a difference in the peak height counts for the titanium rutile oxides of samples 15 and 16, but the problem here is that no anatase peaks are observed in samples 15 and 16.

【0055】<u style="single">Sample 17</u>A zirconium oxide film with a thickness of 184 Å was deposited on a glass substrate, and a titanium metal film with a thickness of 106 Å was deposited on the zirconium oxide film. After heating, the titanium oxide film had a thickness of 205 Å. From the X-ray diffraction image, the cubic zirconium oxide was expected to have a peak height of 1000 to 1100 counts. No peaks were observed for rutile and anatase.

【0056】<u style="single">Sample 18</u>A zirconium metal film with a thickness of 64 Å was deposited on a glass substrate. Titanium oxide film was deposited on top of the zirconium metal film and had a thickness of 220 Å. After heating, zirconium oxide had a thickness of 93 Å. The X-ray diffraction image had a measurement peak with a height of 208 counts for cubic zirconium oxide and a measurement peak with a height of 146 counts for the rutile phase of titanium oxide. No measurable anatase titanium oxide peak was observed.

【0057】<u style="single">Sample 19</u>A zirconium metal film with a thickness of 148 Å was deposited on a glass substrate. A titanium oxide film with a thickness of 215 Å was deposited onto the zirconium metal film. After heating, the zirconium oxide film had a thickness of 264 Å. No peaks were observed on the X-ray diffraction curve for neither cubic zirconium oxide nor rutile or anatase titanium oxide.

【0058】<u style="single">Sample 20</u>A zirconium metal film with a thickness of 87 Å was deposited on a glass substrate. A titanium oxide film with a thickness of 225 Å was deposited onto the zirconium metal film. After heating, the zirconium oxide film had a thickness of 126 Å. The X-ray diffraction image has a measurement peak of 259 counts for cubic zirconium oxide, a measurement peak of 146 counts for rutile titanium oxide, and a measurement peak of 80 counts for anatase oxide. Was there.

【0059】<u style="single">Sample 21</u>A zirconium metal film having a thickness of 182 Å was deposited on a glass substrate, and a titanium metal film having a thickness of 113 Å was deposited on the zirconium metal film. After heating, the zirconium oxide film had a thickness of 263 Å and the titanium oxide film had a thickness of 214 Å. X-ray diffraction images did not show measurable peaks for cubic zirconium oxide and anatase titanium oxide. From the X-ray diffraction image, rutile titanium oxide was expected to have a peak height of 900-1000 counts.

【0060】<u style="single">Sample 22</u>A zirconium metal film with a thickness of 87 Å was deposited on a glass substrate and a titanium metal film with a thickness of 115 Å was deposited on the zirconium metal film. After heating, the zirconium oxide film had a thickness of 126 Å and the titanium oxide film had a thickness of 217 Å. X-ray diffraction images did not show measurable peaks for cubic zirconium oxide and rutile and anatase titanium oxide.

【0061】<u style="single">Sample 23</u>A titanium oxide film having a thickness of 218 Å was deposited on a glass substrate, and a titanium metal film having a thickness of 110 Å was deposited on the titanium oxide film. After heating, the titanium metal film had a thickness of 208 Å. X-ray diffraction images did not show measurable peaks for rutile and anatase titanium oxide.

【0062】<u style="single">Sample 24</u>A titanium metal film with a thickness of 58 Å was deposited on a glass substrate. After heating, the film was a titanium oxide film with a thickness of 110 Å. A titanium oxide film with a thickness of 223 Å was deposited on the titanium metal film. X-ray diffraction images did not show measurable peaks for rutile and anatase titanium oxide.

【0063】<u style="single">Sample 25</u>A titanium metal film with a thickness of 119 Å was deposited on a glass substrate. After heating, the film was a titanium oxide film with a thickness of 249 Å. A titanium oxide film with a thickness of 215 Å was deposited on the titanium metal film. X-ray diffraction images did not show measurable peaks for rutile and anatase titanium oxide.

【0064】<u style="single">Sample 26</u>A titanium nitride film having a thickness of 216 Å was deposited on a glass substrate. The film thickness after heating was 384 Å. The composition of the film was not analyzed. The film during heating was expected to be oxidized, but the extent was undecided. Therefore, the film may contain titanium nitride, titanium oxynitride, or titanium oxide. A titanium film with a thickness of 119 Å was deposited on the titanium nitride film. After heating, the titanium oxide film had a thickness of 223 Å. The X-ray diffraction image showed a rutile peak. It was not known whether the peaks were from heated titanium rutile film, heated titanium metal film, or a combination thereof. Rutile was expected to have a peak height of 100-250 counts. No anatase peak was observed.

【0065】<u style="single">Sample 27</u>A zirconium oxide film with a thickness of 190 Å was deposited on a glass substrate. A titanium nitride film of unknown thickness was deposited on the zirconium oxide film. The titanium nitride film after heating had a thickness of 364 Å. For the composition of the heated titanium nitride film, refer to the study in Sample 26. From the X-ray diffraction image, the cubic zirconium oxide was expected to have a peak height of 900 to 1000. It was expected that the heated titanium nitride film rutile had a peak height of 100-200 counts and the anatase had a peak height of 250-300 counts.

【0066】<u style="single">Sample 28</u>A 10.2 cm (4 inch) square piece of sample 2 was heated and a titanium oxide film with a thickness of 220 Å was deposited on the heated coating of sample 2. After depositing the titanium oxide film, the sample was not heated. As discussed in Sample 2, a peak of cubic zirconium oxide was observed. No peak was observed for rutile or anatase titanium oxide.

【0067】<u style="single">Sample 29</u>A 10.2 cm (4 inch) square piece of sample 1 was heated and a titanium oxide film with a thickness of 220 Å was deposited on the heated coating of sample 1. After coating, the coated sample piece was not heated. As discussed in Sample 1, a peak of cubic zirconium oxide was observed. No peak was observed for rutile or anatase titanium oxide.

【0068】<u style="single">Sample 30</u>Sample 30 was a repetition of Sample 28. However, after the titanium oxide film was deposited, the coated sample was subjected to a second heating. The X-ray diffraction image had a cubic zirconium oxide peak with a height of 1036 counts and a rutile titanium oxide peak with a height of 167 counts. No anatase peak was observed.

【0069】<u style="single">Sample 31</u>Sample 31 was a repetition of Sample 29. However, after the titanium oxide film was deposited, the coated glass was heated for the second time. The X-ray diffraction image had a cubic zirconium oxide peak with a height of 285 counts and a rutile titanium oxide peak with a height of 246 counts. No anatase peak was observed.

【0070】<u style="single">Sample 32</u>A zirconium oxide film with a thickness of 173 Å was deposited on a glass substrate. After heating the glass substrate, a titanium metal film having a thickness of 115 Å was deposited on the heated zirconium oxide coated glass substrate. Heating the coated glass substrate, the titanium oxide film had a thickness of 217 Å. The X-ray diffraction image had a cubic zirconium oxide peak as high as 932 counts. No rutile or anatase titanium oxide peaks were observed.

【0071】<u style="single">Sample 33</u>A zirconium oxide film having a thickness of 65 Å was deposited on a glass substrate, and a titanium metal having a thickness of 115 Å was deposited on the zirconium oxide. The glass substrate was heated. After heating, a titanium oxide film having a thickness of 217 Å was deposited on the heated zirconium oxide coated glass substrate. The X-ray diffraction image had a cubic zirconium oxide peak as high as 288 counts. No rutile or anatase titanium oxide peaks were observed.

【0072】

The studies of Samples 1-33 show that the peak heights of both the anatase titanium oxide phase and the rutile titanium oxide phase of Samples 6-16 are plotted as a function of the thickness of the zirconium oxide layer, which is almost a bell-shaped curve (figure). 3) is shown to be followed. Table II below shows the peak counts of the cubic zirconium oxide phase and the rutile and anatase titanium oxide phases for Samples 6-16. The first layer for each of Samples 6-16 is zirconium oxide, and the second layer for each of Samples 6-16 is titanium oxide. It should be noted that the thickness of the titanium oxide layer of samples 6 to 16 is the same. It was unexpected that the bell-shaped curve for the peak height was the result of the change in the thickness of the zirconium oxide layer, not the change in the thickness of the titanium oxide layer. Supporting this conclusion is the fact that the shape of the increase in peak height for the zirconium oxide phase is not bell-shaped.

【0073】<img file="JP2004513864A_D0001.tif" /> 【0074】<img file="JP2004513864A_D0002.tif" /> 【0075】<img file="JP2004513864A_D0003.tif" /> 【0076】<img file="JP2004513864A_D0004.tif" /> 【0077】<img file="JP2004513864A_D0005.tif" /> 【0078】

It should be further noted that the values for sample 16 are not plotted on the curve shown in FIG. This is because the peak count for the titanium oxide phase rutile was abnormally larger than the peak height for the rutile titanium oxide phase of sample 15 and did not follow the bell-shaped curve. The curves in Figure 3 and the data in Table II show an increase in the peak count for the anatase titanium oxide phase at a zirconium oxide thickness of approximately 65-75 Å, after which the peak height count for the anatase titanium oxide phase is It shows that it will decrease. The rutile titanium oxide phase has an increased peak height count with zirconium oxide up to a thickness in the range of about 51-102 Å, followed by a decreasing peak height count.

【0079】

In the following samples 34-37, the deposition parameters were controlled to deposit each coating with a zirconium oxide layer thickness of about 65-75 Å, which would give the anatase titanium oxide phase a count of maximum peak height ( See Table II). The deposition parameters for samples 34-45 are shown in Table III below. In the next sample 38, the thickness of the titanium oxide layer was similar to the thickness of titanium oxide of samples 34 to 37, and the thickness of the zirconium oxide layer was increased. In the following samples 39 to 43, the thickness of the zirconium oxide layer and the first layer of titanium oxide was kept constant, and the thickness of the second layer of titanium oxide was changed. In the following samples 44 and 45, the thickness of the zirconium oxide and titanium oxide layers was changed. Samples 38-45 were coated as discussed above. However, the samples 34 to 45 were heated, and after heating, the samples were taken out of the furnace instead of being placed in the furnace and cooled to room temperature.

【0080】<u style="single">Sample 34</u>A zirconium oxide film having a thickness of 71 Å was deposited on a glass substrate, and then a titanium oxide film having a thickness of 130 Å was deposited on the zirconium oxide film. The X-ray diffraction image had a measured peak with a height of 241 counts for the cubic zirconium oxide phase and a measured peak with a height of 164 counts for the rutile titanium oxide phase. No anatase titanium oxide peak was observed.

【0081】<u style="single">Sample 35</u>A zirconium oxide film having a thickness of 65 Å was deposited on a glass substrate, and then a titanium oxide film having a film thickness of 65 Å was deposited on the zirconium oxide film. The X-ray diffraction image had a measured peak as high as 267 counts for the cubic zirconium oxide phase. No rutile or anatase titanium oxide phase peak was observed.

【0082】

(Note: For samples 36 and 37, peak height counts were performed using a different X-ray tube than the one used for those samples. The peak counts were significantly higher and comparisons were made. Should be taken into account when doing so).

【0083】<u style="single">Sample 36</u>A zirconium oxide film having a thickness of 65 Å was deposited on a glass substrate, and then a titanium oxide film having a thickness of 177 Å was deposited onto the zirconium oxide film. The X-ray diffraction image had a measured peak at a height of 1136 for the cubic zirconium oxide phase and a measured peak at a height of 1169 for the rutile titanium oxide phase. Anatase titanium oxide peak was observed in trace amounts.

【0084】<u style="single">Sample 37</u>A zirconium oxide film having a thickness of 62 Å was deposited on a glass substrate, and then a titanium oxide film having a thickness of 192 Å was deposited onto the zirconium oxide film. The X-ray diffraction image has a measured peak at a height of 1315 for the cubic zirconium oxide phase, 845 for the rutile titanium oxide phase, and 2284 for the anatase titanium oxide phase. It was.

【0085】<u style="single">Sample 38</u>A zirconium oxide film with a thickness of 173 Å was deposited on a glass substrate. A titanium oxide film with a thickness of 114 Å was deposited on top of the zirconium oxide film. An X-ray diffraction image was obtained, but the peak height was not estimated or calculated. From the X-ray diffraction image, what seems to be a peak of the cubic zirconium oxide phase and a displaced peak of the rutile titanium oxide phase was observed. The zirconium oxide phase was even more pronounced than the rutile titanium oxide phase. No peak was observed for the anatase titanium oxide phase.

【0086】<u style="single">Sample 39</u>Sample 39 is the same as Sample 34. However, a titanium metal film having a thickness of 48 Å was further deposited on the titanium oxide film before heating the coated substrate having the zirconium oxide and the titanium oxide film. The coated substrate was heated and the heated titanium metal film was oxidized, and the obtained titanium oxide film had a thickness of 90 Å. The X-ray diffraction image showed a cubic zirconium oxide phase with a peak count of 240, a rutile titanium oxide phase with a peak count of 178, and anatase titanium oxide phase with a peak count of 187 counts.

【0087】<u style="single">Sample 40</u>Sample 40 is the same as Sample 35. However, a titanium metal film having a thickness of 80 Å was deposited on the titanium oxide film. The coated substrate was heated and the heated titanium metal film was oxidized, and the obtained titanium oxide film had a thickness of 151 Å. The X-ray diffraction image had a cubic zirconium oxide phase peak with a count of 241. No rutile or anatase titanium oxide peaks were observed.

【0088】<u style="single">Sample 41</u>Sample 41 is the same as Sample 35. However, a titanium metal having a thickness of 25 Å was deposited on the titanium oxide film. The coated substrate was heated and the heated titanium metal film was oxidized, and the obtained titanium oxide film had a thickness of 47 Å. An X-ray diffraction image was obtained, but the peak height was not estimated and was not obtained. From the X-ray diffraction image, a peak was observed for the cubic zirconium oxide phase, and no peak was observed for the rutile and anatase titanium oxide phases.

【0089】<u style="single">Sample 42</u>A zirconium oxide film with a thickness of 62 Å is deposited on a glass substrate, a titanium oxide film with a thickness of 98 Å is deposited on the zirconium oxide, and a titanium metal film with a thickness of 46 Å is deposited on the titanium oxide film. Vapor deposition on top. The coated substrate was heated and the thickness of titanium oxide due to the oxidation of the titanium metal was calculated to be 87 Å. An X-ray diffraction image was obtained, but the peak height was not estimated or calculated. From the X-ray diffraction image, peaks were observed for the zirconium oxide phase and the rutile titanium oxide phase. No peaks or trace amounts were observed for the anatase titanium oxide phase.

【0090】<u style="single">Sample 43</u>Sample 43 is the same as Sample 42. However, a titanium metal having a thickness of 61 Å was deposited on the titanium oxide film. The calculated thickness of the titanium oxide film due to the oxidation of the titanium metal film was 116 Å. An X-ray diffraction image was obtained, but the peak height was not estimated or calculated. From the X-ray diffraction image, peaks for the zirconium oxide phase and the rutile titanium oxide phase were observed. No peak was observed for the anatase titanium oxide phase.

【0091】<u style="single">Sample 44</u>A zirconium oxide film with a thickness of 57 Å is deposited on a glass substrate, a titanium metal with a thickness of 25 Å is deposited on the zirconium oxide film, and a titanium oxide film with a thickness of 65 Å is deposited on the titanium metal. Was vapor-deposited on. The coated glass was heated in air and the calculated thickness of the titanium oxide film by oxidation of the titanium metal film was 47 Å. An X-ray diffraction image was obtained, but the peak height was not estimated and was not obtained. From the X-ray diffraction image, a peak was observed for the cubic zirconium oxide phase. No peaks were observed for the rutile and anatase titanium oxide phases.

【0092】<u style="single">Sample 45</u>Sample 45 is the same as Sample 38. However, a titanium metal having a thickness of 48 Å was deposited on the titanium oxide film. The titanium oxide film after heating the titanium metal film had a calculated thickness of 91 Å. An X-ray diffraction image was obtained, but the peak height was neither estimated nor calculated. From the X-ray diffraction image, peaks were observed for what seems to be the displaced peaks of the cubic zirconium oxide and rutile titanium oxide phases. No peak was observed for the anatase titanium oxide phase.

【0093】

From the results of Samples 34-37, it is observed that the anatase titanium oxide phase developed in a titanium oxide film with a thickness of about 169 Å. It will be appreciated that the thickness at which anatase titanium oxide can develop is reduced. Sample 38 supports the conclusion from Table II that the thick first layer of zirconium oxide is insufficient to develop the anatase titanium oxide phase with the titanium dioxide phase within this thickness range of the curve in Figure 3. There is. This will depend on the thickness of the titanium dioxide film. From the results of Samples 37-45, it is concluded that the anatase titanium oxide phase can develop from the titanium metal film (see Sample 39). However, if the zirconium oxide film is increased, the effect of developing the anatase titanium oxide phase appears to be significantly reduced (see sample 45).

【0094】

The present invention allows the self-cleaning of anatase and / or rutile titanium oxide for residential and commercial windows, automotive transparency, such as side lites, rear windows, windshields, roof windows, oven doors, mirrors, etc. Can be done to give a film.

【0095】<img file="JP2004513864A_D0006.tif" /> 【0096】<img file="JP2004513864A_D0007.tif" /> 【0097】

Yet another glass substrate was coated with a coating of the present invention covering titanium oxide, zirconium oxide, and zirconium oxide with a titanium oxide coating deposited (Samples 54-68 shown in Table IV). The vapor deposition parameters and intensity measurements for these samples 54-68 are shown in Table IV.

【0098】

Samples 54 to 57 show the effect of the thickness of the zirconium oxide layer on the anatase peak of the titanium oxide layer. Its behavior is similar to that of the sample discussed above and shown in Figure 3. However, the samples 54 to 57 are post-heated at a lower temperature than the above samples 1 to 45.

【0099】

Samples 58-62 show the effect of the thickness (70 Å-166 Å) of the zirconium oxide layer with the titanium oxide layer thick (382 Å-441 Å). The thick zirconium oxide layer does not reduce the magnitude of the anatase peak (101) intensity.

【0100】

Samples 63 and 64 are comparative samples of titanium dioxide. Compared with Samples 58-62, Samples 58-62 of the present invention show significantly higher anatase peak (101) intensity.

【0101】

Samples 65-68 were zirconium oxide coated and showed peak intensities of zirconium oxide in the cubic phase (111), which clearly showed differences in peak positions in the anatase, rutile, and cubic phases in a thin film. Shown.

【0102】

Table IV also shows the presence of rutile, but the intensity is significantly lower.

【0103】<img file="JP2004513864A_D0008.tif" /> 【0104】<img file="JP2004513864A_D0009.tif" /> 【0105】<u style="single">Feature 2 (hydrophilic)</u>The coating of the present invention was compared with the conventional titanium dioxide coating under various conditions to determine the effect on the coating hydrophilicity of the present invention.

【0106】

A transparent glass substrate having a thickness of 2.3 nm was coated using a commercially available Airco ILS1600 magnetron sputter vacuum coating machine. Samples 46 to 49 were coated only with titania coating as a comparative example. Samples 50 to 53 were coated with the coating of the present invention in which a zirconium oxide film (first film) was vapor-deposited on a glass substrate and a titanium dioxide film (second film) was vapor-deposited on the zirconium oxide film. The vapor deposition parameters for samples 46-53 are shown in Table V below. As shown in Table V, the substrates of Samples 48, 49, 52, and 53 had a substrate of approximately 188 ° C (370 ° F) at the start of the coating operation in a furnace external to the vacuum coating machine. Preheated to have temperature. No further heating was done on the substrate during the coating process. After coating, the sample is evaluated at room temperature of 21 ° C (70 ° F) to temperatures of 243 ° C (470 ° F), 304 ° C (579 ° F), and 363 ° C (686 ° F). The effect of heat treatment after heating and coating on the hydrophilicity of the coating was evaluated.

【0107】

As mentioned in Feature 1 above, the phase peak count was also measured. The phase peak counts here can be compared directly within the given table, but we did not standardize the measurements for different sets of samples, so when comparing counts from different tables. Should admit that you should be careful. It should be noted that the post-heating temperatures of samples 46-53 were much lower than for the samples discussed in Feature 1, and samples 48, 49, 52, and 53 were preheated. Samples 46 and 47 (titanium dioxide, no preheating) were amorphous. In contrast, by preheating the substrate, the anatase (101) peak showed some XRD intensity at the highest preheating temperature (363 ° C) for samples 48 and 49. Coatings with a first layer of zirconium oxide (Samples 50 and 51) showed anatase (101) peaks at 363 ° C (Sample 50) and 304 ° C (Sample 51) at their temperatures. The temperature is lower than that of the sample described in Feature 1. In samples 48-51, no other peak intensities were present at these temperatures. This indicates that the first layer of zirconium oxide affects the presence of anatase.

【0108】

For titanium oxide with a first layer of zirconium oxide preheated to 188 ° C (370 ° F), sample 52 shows that its coating is amorphous and sample 53 appears to have small rutile and anatase peaks. That was totally unexpected. Most notably, there are peaks at about the same intensity over the range of room temperature to 363 ° C. Even in the case of sample 53, the rutile peak intensity seems to shift toward a larger 2θ value.

【0109】<img file="JP2004513864A_D0010.tif" /> 【0110】

24 W / m on the coated surface of the coated substrate²The UVA-340 light source was exposed to UV radiation and the contact angle of water droplets on the coating was measured over time. The results of this procedure are shown in FIGS. 4 to 11 for samples 46 to 53, respectively. In the figure, the numbers in the legend indicate the postheating temperature (° F) as described above.

【0111】

From FIGS. 4 to 11, in the case of non-preheating (Fig. 8) zirconium oxide (73 Å) / titanium oxide (164 Å) coating (Sample 50), the coating of the present invention is Titania (173 Å) coating (Sample 46) alone. It can be seen that the contact angle of water was significantly reduced by post-heating higher than 243 ° C (470 ° F) (Fig. 4). In the case of a similar coating (Sample 52) of the present invention preheated to 188 ° C (370 ° F), the contact angle is even higher without postheating compared to a similarly preheated titania coating alone (Sample 48). It becomes smaller (compare Figures 10 and 6).

【0112】

As shown in FIG. 9, the unpreheated zirconium oxide (155 Å) / titania (287 Å) coating (Sample 51) has a lower coating than the titanium dioxide (397 Å) coating alone (Sample 47). It showed a contact angle (Fig. 5), and the contact angle continued to decrease with postheating. For a similar coating (Sample 53) preheated to 188 ° C (370 ° F), the coating of the present invention showed good hydrophilicity without postheating. Significant time and energy savings by implementing the methods of the invention by not requiring post-heating to achieve hydrophilicity or superhydrophilicity (ie, contact angles equal to or less than 5 °). Can be achieved.

【0113】

Figures 12 and 13 illustrate the effects of preheating and postheating temperatures on the duplicate coating of the coating of sample 52. Figure 12 shows UV (24 W / on coated surface) for post-heating temperatures for substrates preheated to 121 ° C (250 ° F), 149 ° C (300 ° F), and 188 ° C (370 ° F). m²It is a graph of the contact angle when irradiating with 340 nm) having the intensity of 60 minutes. From FIG. 12, it can be seen that the contact angle decreases as the preheating temperature rises. It can be seen that preheating has a greater effect on the resulting contact angle than postheating to a postheating temperature of up to about 260 ° C (500 ° F). Figure 13 shows that preheating the substrate at postheating temperatures of 127 ° C (261 ° F), 198 ° C (388 ° F), and 257 ° C (495 ° F) has a better contact angle than postheating. It shows that it seems to have a greater impact on.

【0114】<u style="single">Feature 3 (Chemical durability)</u>A replica coating of samples 46-53 is applied to a conventional Cleveland Condensation Test (CCC) device [Condensation commercially available from Q-Panel, Cleveland, Ohio. Tester) QCT]. The degree of coating deterioration is determined by measuring the reflectivity of the coating [represented by the tristimulus value and Y or Y (R1) shown in the figure] using a commercially available BYK-Gardner TCS meter. did. The results are shown in Figures 14-21. Samples 46 and 47 (Titania alone, no preheating) showed poor CCC results, as shown in FIGS. 14 and 15. As used herein, "bad" means that the coating could not withstand a CCC test longer than 400 hours, as evidenced by the reduced observed reflectance indicating deterioration of the coating. Samples 48 and 49 (Titania alone, with preheating) in Figures 16 and 17 showed some good results. However, samples 50 and 51 (zirconia / titania, no preheating) in Figures 18 and 19 showed better CCC results than the titania coating without preheating. It was quite unexpected that samples 52 and 53 (zirconia / titania, preheated) in FIGS. 20 and 21 showed significantly improved CCC results over titania coating with preheated. For example, sample 53 (Fig. 21) has UV radiation (24 W / m at 340 nm) without postheating.²After exposure to (intensity) for 40 minutes, it not only gave a coating with photoactive hydrophilicity less than 10 °, but also gave good CCC results other than at all.

【0115】

Figures 22-25 show the duplicate coating of sample 52 after 127 ° C (261 ° F), 198 ° C (388 ° F), 257 ° C (495 ° F), 294 ° C (561 ° F). For heating temperature and room temperature, preheating temperature of 121 ° C (250 ° F) (Fig. 22), 149 ° C (300 ° F) (Fig. 23), and 188 ° C (370 ° F) (Fig. 24). CCC test results are shown. From these results, it seems that as the preheating temperature increases, the effect on the chemical durability of the postheating coating gradually decreases. Figure 25 shows that for this coating, if the substrate is heated to about 188 ° C (370 ° F), post-heating below about 294 ° C (561 ° F) has little or no effect on the chemical durability of the coating. Indicates that it does not appear to be.

【0116】<u style="single">Feature 4 (photocatalytic)</u>Some of the coatings of the present invention were measured for photocatalytic activity according to standard stearic acid tests. Table VI shows statistics R greater than 0.93 for these measurements.²The results with values are shown. Photocatalytic activity value is cm^-1Shown in / minute units.

【0117】<img file="JP2004513864A_D0011.tif" /> 【0118】

As can be seen from Table VI, the coatings tested show photocatalytic activity under the evaluated conditions. For other samples tested for photocatalytic activity, the result is R less than 0.93²It shows values and their results are statistically worthless and therefore these values are not listed.

【0119】

It will be readily appreciated by those skilled in the art that the present invention can be modified without departing from the concepts disclosed above. Accordingly, the special embodiments described in detail herein are merely exemplary and are not limited to the scope of the invention, the invention is provided by the scope of the claims and all equivalents. Should be done.

[Simple explanation of drawings]

[Figure 1]

FIG. 1 is a partial side sectional view (not full size) of a substrate having a coated laminate incorporating the features of the present invention.

[Figure 2]

FIG. 2 is a side sectional view (not the actual size) of the insulating glass unit having the coated laminate of the present invention.

[Fig. 3]

FIG. 3 is a graph showing the curve of film thickness vs. peak height count for the cubic zirconium oxide phase, the rutile titanium oxide phase, and the anatase titanium oxide phase.

[Fig. 4]

FIG. 4 is a graph showing the contact angle of water droplets with respect to the time (minutes) of exposure to ultraviolet rays for the titanium dioxide coating.

[Fig. 5]

FIG. 5 is a graph showing the contact angle of water droplets with respect to the time (minutes) of exposure to ultraviolet rays for the titanium dioxide coating.

[Fig. 6]

FIG. 6 is a graph showing the contact angle of water droplets with respect to the time (minutes) of exposure to ultraviolet rays for the titanium dioxide coating.

[Fig. 7]

FIG. 7 is a graph showing the contact angle of water droplets with respect to the time (minutes) of exposure to ultraviolet rays for the titanium dioxide coating.

[Fig. 8]

FIG. 8 is a graph showing the contact angle of water droplets with respect to the time (minutes) of exposure to ultraviolet light for various coatings incorporating the features of the present invention.

[Fig. 9]

FIG. 9 is a graph showing the contact angle of water droplets with respect to the time (minutes) of exposure to ultraviolet light for various coatings incorporating the features of the present invention.

[Fig. 10]

FIG. 10 is a graph showing the contact angle of water droplets with respect to the time (minutes) of exposure to ultraviolet rays for various coatings incorporating the features of the present invention.

[Fig. 11]

FIG. 11 is a graph showing the contact angle of water droplets with respect to the time (minutes) of exposure to ultraviolet light for various coatings incorporating the features of the present invention.

[Fig. 12]

FIG. 12 is a graph showing the contact angle vs. the post-heating temperature for a coating similar to that of FIG.

[Fig. 13]

FIG. 13 is a graph showing the contact angle vs. preheating temperature for a coating similar to that of FIG.

[Fig. 14]

FIG. 14 is a graph showing the results of a Cleveland condensation test for a coating similar to that of FIG.

[Fig. 15]

FIG. 15 is a graph showing the results of a Cleveland condensation test for a coating similar to that of FIG.

[Fig. 16]

FIG. 16 is a graph showing the results of a Cleveland condensation test for a coating similar to that of FIG.

[Fig. 17]

FIG. 17 is a graph showing the results of a Cleveland condensation test for a coating similar to that of FIG.

[Fig. 18]

FIG. 18 is a graph showing the results of a Cleveland condensation test for a coating similar to that of FIG.

[Fig. 19]

FIG. 19 is a graph showing the results of a Cleveland condensation test for a coating similar to that of FIG.

[Fig. 20]

FIG. 20 is a graph showing the results of a Cleveland condensation test for a coating similar to that of FIG.

[Fig. 21]

FIG. 21 is a graph showing the results of a Cleveland condensation test for a coating similar to that of FIG.

[Fig. 22]

FIG. 22 is a graph showing reflectance vs. Cleveland condensation test (CCC) exposure time for a coating similar to that of FIG. 10 at a preheating temperature of 121 ° C (250 ° F).

[Fig. 23]

FIG. 23 is a graph showing reflectance vs. Cleveland condensation test (CCC) exposure time for a coating similar to that of FIG. 10 at a preheating temperature of 149 ° C (300 ° F).

[Fig. 24]

FIG. 24 is a graph showing reflectance vs. Cleveland condensation test (CCC) exposure time for a coating similar to that of FIG. 10 at a preheating temperature of 188 ° C (370 ° F).

[Fig. 25]

FIG. 25 is a graph showing the CCC reflectance result vs. preheating temperature for a coating similar to that shown in FIG.