# Patent

## Title
Multi-layer coatings with an inorganic oxide network containing layer and methods for their application

## Abstract

Multi-layer coatings are disclosed that include (1) a first layer comprising an inorganic oxide network, and (2) a second layer applied over at least a portion of the first layer, wherein the second layer is deposited from at least one liquid composition that is hydrophilic and includes an essentially completely hydrolyzed organosilicate. Also disclosed are substrates coated with such multi-layer coatings, methods of applying such multi-layer coatings to a substrate and methods for improving the anti-fouling, self-cleaning, easy-to-clean, and/or anti-fogging properties of an article.

## Background
CROSS-REFERENCE TO RELATED APPLICATIONS
This application claims the benefit of U.S. Provisional Patent Application Ser. No. 60/575,438, filed May 28, 2004.


FIELD OF THE INVENTION
The present invention relates to multi-layer coatings that comprise a first layer and a second layer. The coatings are hydrophilic and durable, and may exhibit, for example, advantageous easy-to-clean, self-cleaning, anti-fouling, anti-fogging, anti-static and/or anti-bacterial properties. The coatings can, in certain embodiments, be rendered super-hydrophilic upon photoexcitation of a photocatalytic material.
BACKGROUND OF THE INVENTION
Hydrophilic coatings are advantageous for certain coating applications, such as where coated surfaces exhibiting anti-fouling, easy-to-clean, self-cleaning, and/or anti-fogging properties are desired. Such coatings can be particularly useful, by way of example, for application to surfaces exposed to the outdoor environment. Building structures as well as other articles that are exposed to the outdoors are likely to come in contact with various contaminants, such as dirt, oil, dust, clay, among others. Rainfall, for example, can be laden with such contaminants. A surface with a hydrophilic coating deposited thereon may be anti-fouling by preventing contaminants in rainwater from adhering to the surface when the rainwater flows down along the coated surface. Moreover, during fair weather air-born contaminants may come in contact with and adhere to surfaces. A surface with a hydrophilic coating deposited thereon may be self-cleaning and/or easy-to-clean because the coating has the ability to wash those contaminants away when the surface comes in contact with water, such as during a rainfall.
Coatings having self-cleaning, easy-to-clean, and/or anti-fouling properties may also be advantageous for application to surfaces that are exposed to indoor contaminants, such as, for example, kitchen contaminants, such as oil and/or fat. An article with a hydrophilic coating deposited thereon can be soaked in, wetted with, or rinsed by water to release contaminants from the coating and remove them from the surface of the article without use of a detergent.
Coatings having anti-fogging properties can be particularly useful in many applications as well. For example, articles containing surfaces where visibility is important, such as windshields, windowpanes, eyeglass lenses, mirrors, and, other similar articles can benefit from a coating with anti-fogging properties because they contain surfaces that can often be fogged by steam or moisture condensate or blurred by water droplets adhering to the surface thereof. It is known that the fogging of a surface of an article results when the surface is held at a temperature lower than the dew point of the ambient atmosphere, thereby causing condensation moisture in the ambient air to occur and form moisture condensate at the surface of the article. If the condensate particles are sufficiently small, so that the diameter thereof is about one half of the wavelength of the visible light, the particles can cause scattering of light, whereby the surface becomes apparently opaque, causing a loss of visibility.
A surface with a hydrophilic coating deposited thereon may be anti-fogging because such a coating can transform condensate particles to a relatively uniform film of water, without forming discrete water droplets. Similarly, a surface with a hydrophilic coating deposited thereon can prevent rainfall or water splashes from forming discrete water droplets on the surface, thereby improving visibility through windows, mirrors, and/or eyewear.
In view of these and other advantages, various hydrophilic coating compositions have been proposed. Some of these coatings achieve their hydrophilicity through the action of a photocatalytic material that is dispersed in a silicon-containing binder. For example, U.S. Pat. No. 5,755,867 (“the '867 patent”) discloses a particulate photocatalyst dispersed in a coat-forming element. The photocatalyst preferably consists of titanium dioxide particles having a mean particle size of 0.1 micron or less, where the titanium dioxide may be used in either the anatase or rutile form. The coat-forming element is capable of forming a coating of silicone resin when cured and is comprised of an organopolysiloxane formed by partial hydrolysis of hydrolyzable silanes followed by polycondensation. In the '867 patent, the silicone coat-forming element in itself is considerably hydrophobic, but upon excitation of the dispersed photocatalyst, a high degree of water affinity, i.e., hydrophilicity, can be imparted to the coating.
Japanese Patent Application JP-8-164334A discloses a coating film-forming composition comprising titanium oxide having an average particle diameter of 1 to 500 nanometers, a hydrolyzate of a hydrolyzable silicon compound, and a solvent. The hydrolyzable silicon compound is an alkyl silicate condensate expressed by the formula SinOn-1(OR)2n+2 (where n is 2 to 6, and R is a C1-C4 alkyl group). The hydrolyzate results from hydrolyzing the alkyl silicate condensate at a hydrolysis percentage of 50 to 1500%. The hydrolyzate itself, however, is not believed to be hydrophilic.
U.S. Pat. Nos. 6,013,372 and 6,090,489 disclose photocatalytic coating compositions wherein particles of photocatalyst are dispersed in a film-forming element of uncured or partially cured silicone (organopolysiloxane) or a precursor thereof. The photocatalyst may include particles of a metal oxide, such as the anatase and rutile forms of titanium dioxide. According to these patents, the coating compositions ate applied on the surface of a substrate and the film-forming element is then subjected to curing. Then, upon photoexcitation of the photocatalyst, the organic groups bonded to the silicon atoms of the silicone molecules of the film-forming element are substituted with hydroxyl groups under the photocatalytic action of the photocatalyst. The surface of the photocatalytic coating is thereby “superhydrophilified,” i.e., the surface is rendered highly hydrophilic to the degree that the contact angle with water becomes less than about 10. In these patents, however, the film-forming element in itself is considerably hydrophobic, i.e., the initial contact angle with water is greater than 50°. As a result, the coating is initially hydrophobic, and it is only upon excitation of the dispersed photocatalyst that hydrophilicity is imparted to the coating.
U.S. Pat. No. 6,165,256 discloses compositions that can hydrophilify the surface of a member to impart anti-fogging properties to the surface of the member. The compositions disclosed in this patent comprise (a) photocatalytic particles of a metallic oxide, (b) a precursor capable of forming a silicone resin film or a precursor capable of forming a silica film, and (c) a solvent, such as water, organic solvents, and mixtures thereof. The solvent is added in an amount such that the total content of the photocatalytic particle and the solid matter of the precursor in the composition is 0.01 to 5% by weight. As in the previous examples, however, hydrophilification of the coating formed from such a composition takes place upon photoexcitation of the photocatalyst, while the film forming material in itself is not hydrophilic. Therefore, the coating is not believed to be hydrophilic prior to excitation of the photocatalyst.
The prior art hydrophilic coatings that achieve their hydrophilicity through the action of a photocatalytic material that is dispersed in a silicon-containing binder suffer, however, from some drawbacks. One notable drawback is that these coatings do not exhibit hydrophilicity until photoexcitation of the photocatalyst. In addition, these compositions typically require a forced cure, i.e., they cannot be efficiently cured at room temperatures.
U.S. Pat. No. 6,303,229 (“the '229 patent”) discloses another composition that may include a photocatalytic material. The coating disclosed in the '229 patent is formed from applying a coating composition that contains a silicone resin, which acts as the binder and which is obtained by hydrolyzing and condensation-polymerizing certain tetra-functional alkoxysilanes. The coating compositions may also include colloidal silica. Evidently, the coated film formed from the composition disclosed in the '229 patent can be initially hydrophilic. This initial hydrophilicity, however, is believed to result from the presence of colloidal silica in the composition rather than the silicone resin itself. It is believed that the silicone resin disclosed in the '229 patent is not itself hydrophilic because the desired pH of the resin is 3.8 to 6.0, which indicates that Si—OR groups exist in the resin in an amount to prevent gellation and hydrophilicity.
It would be advantageous to provide multi-layer coatings that include a coating layer comprising an inorganic oxide network and a coating layer deposited from a liquid composition that is hydrophilic and comprises an essentially completely hydrolyzed organosilicate.



DESCRIPTION OF THE DRAWINGS
FIG. 1 is a chart reflecting a Fourier Transform Infrared. Spectroscopy (“FTIR”) analysis of a dry film formed from a binder material used in accordance with certain non-limiting embodiments of the present invention;
FIG. 2 is a schematic cross-sectional view in an enlarged scale of certain non-limiting embodiments of the second layer of the multi-layer coatings of the present invention; and
FIG. 3 is a Field Emission Scanning Electron Microscope Secondary Electron Micrograph (magnification 40,000×) depicting certain non-limiting embodiments of the second layer of the multi-layer coatings of the present invention.
FIG. 4 is a chart illustrating the results of the durability testing conducted as described in Example 2.



SUMMARY OF THE INVENTION
In one respect, the present invention is directed to multi-layer coatings comprising (1) a first layer comprising an inorganic oxide network, and (2) a second layer applied over at least a portion of the first layer, wherein the second layer is deposited from at least one liquid composition that is hydrophilic and comprises an essentially completely hydrolyzed organosilicate.
In another respect, the present invention is directed multi-layer coatings comprising (1) a first layer comprising an inorganic oxide network, and (2) a second layer applied over at least a portion of the first layer, wherein the second layer is deposited from at least one liquid composition that comprises (a) a photocatalytic material, and (b) a binder that is hydrophilic and comprises an essentially completely hydrolyzed organosilicate.
In still another respect, the present invention is directed to substrates coated with a multi-layer coating of the present invention.
In yet another respect, the present invention is directed to methods of applying a multi-layer coating to a substrate comprising the steps of (1) applying to a substrate a first layer comprising an inorganic oxide network; (2): applying onto at least a portion of the first layer a liquid composition from which a second layer is deposited, wherein the composition of the second layer is, hydrophilic and comprises an essentially completely hydrolyzed organosilicate; and (3) curing the second layer.
The present invention is also directed to methods of applying a multi-layer coating to a substrate comprising the steps of (1) applying to a substrate a first layer comprising an inorganic oxide network; (2) applying onto at least a portion of the first layer a liquid composition from which a second layer is deposited over the first layer, wherein the liquid composition of the second layer comprises (a) a photocatalytic material, and (b) a binder that is hydrophilic and comprises an essentially completely hydrolyzed organosilicate; and (3) curing the second layer.
The present invention is also directed to methods for improving the anti-fouling, self-cleaning, easy-to-clean, and/or anti-fogging properties of an article, wherein the article comprises a surface having a coating comprising a inorganic oxide network deposited thereon, the method comprising: (1) applying to at least a portion of the surface a liquid composition comprising an essentially completely hydrolyzed organosilicate; and (2) curing the liquid composition applied in step (1).
DETAILED DESCRIPTION OF EMBODIMENTS OF THE INVENTION
For purposes of the following detailed description, it is to be understood that the invention may assume various alternative variations and step sequences, except where expressly specified to the contrary. Moreover, other than in any operating examples, or where otherwise indicated, all numbers expressing, for example, quantities of ingredients used in the specification and claims are to be understood as being modified in all instances by the term “about”. Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and attached claims are approximations that may vary depending upon the desired properties to be obtained by the present invention. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.
Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the invention are approximations, the numerical values set forth in the specific examples are reported as precisely as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard variation found in their respective testing measurements.
In this application, the use of the singular includes the plural and plural encompasses singular, unless specifically stated otherwise. For example, and without limitation, this application refers to liquid compositions that comprise “a photocatalytic material”. Such references to “a photocatalytic material” is meant to encompass compositions comprising one photocatalytic material as well as compositions that comprise more than one photocatalytic material, such as compositions that comprise two different photocatalytic materials. In addition, in this application, the use of “or” means “and/or” unless specifically stated otherwise, even though “and/or” may be explicitly used in certain instances.
Also, it should be understood that any numerical range recited herein is intended to include all sub-ranges subsumed therein. For example, a range of “1 to 10” is intended to include all sub-ranges between (and including) the recited minimum value of 1 and the recited maximum value of 10, that is, having a minimum value equal to or greater than 1 and a maximum value of equal to or less than 10.
In one respect, the present invention is directed to multi-layer coatings comprising (1) a first layer comprising an inorganic oxide network, and (2) a second layer applied over at least a portion of the first layer, wherein the second layer is deposited from at least one liquid composition that is hydrophilic and comprises an essentially completely hydrolyzed organosilicate.
The multi-layer coatings of the present invention comprise a first layer that comprises an inorganic oxide network. As used herein, the term “network” refers to an interconnected chain or group of molecules.
In certain embodiments, the first layer of the multi-layer coatings of the present invention is deposited from a composition comprising a sol containing a network-forming metal alkoxide, such as an alkoxysilane and/or an alkoxide of another metal, such as zirconium, titanium and aluminum. The alkoxysilane, if used, may be an organoalkoxysilane, such as an alkylalkoxysilane or organofunctional alkoxysilane. The alkoxide may contain alkyl or aryl groups and may be in dimer or higher condensed form so long as hydrolysable alkoxide groups remain.
In certain embodiments, the network-forming metal alkoxide is an alkoxysilane of the general formula RxSi(OR′)4−x wherein R is an organic radical, R′ is selected from the group consisting of low molecular weight alkyl radicals, such as methyl, ethyl, propyl, and butyl radicals, and x is an integer and is at least one and is less than 4. The organic radical of R may, for example, be alkyl, vinyl, methoxyethyl, phenyl, γ-glycidoxypropyl, or γ-methacryloxypropyl, among others, including mixtures thereof. The alkoxide hydrolyzes according to the general reaction set forth below, where R, R′ and x are as described above and y is less than 4.

RxSi(OR′)4-x+yH2O→RxSi(OR')4-x-y(OH)y+yR—'OH

Condensation of the hydrolyzed alkoxide proceeds according to the general reactions





Further hydrolysis and condensation follow.

In certain embodiments, the first layer of the multi-layer coatings of the present invention may comprise other components, such as ultraviolet radiation absorbers, organic film-forming polymers, and components to improve flow properties, abrasion resistance and/or durability. Non-limiting examples of compositions from which the first layer of the multi-layer, coatings of the present invention may be formed, and methods for their production, are described in U.S. Pat. Nos. 4,753,827, 4,754,012, 4,799,963, 5,035,745, 5,199,979, 6,042,737 and 6,106,605, which are incorporated herein by reference.
In certain embodiments, the first layer of the multi-layer coatings of the present invention is transparent. As used herein, the term “transparent” is intended to mean that the cured coating does not substantially change the percentage of visible light transmitted through a transparent polymeric substrate to which it may be applied. The tintability of a coating is a function of the amount of dye that the coating acquires under certain defined conditions which is expressed quantitatively by the percentage of light transmitted through the dyed coating. The tintability of a coating can be measured as described in U.S. Pat. No. 6,042,737 at col. 4, line 57 to col. 5, line 8, which is incorporated herein by reference.
Examples of commercially available compositions that are suitable for use in depositing the first layer of the multi-layer coatings of the present invention, are the Hi-GardTM and SolGard® coating solutions available from PPG Industries, Inc., the Crizol® products available from Essilor International, S.A. and the CrystalCoatTM products available from SDC Technologies, Inc., among others.
The multi-layer coatings of the present invention comprise a second layer applied over at least a portion of the first layer, wherein the second layer is deposited from at least one liquid: composition that comprises an essentially completely hydrolyzed organosilicate. As used herein, the term “organosilicate” refers to a compound containing organic groups bonded to a silicon atom through an oxygen atom. Suitable organosilicates include, without limitation, organoxysilanes containing four organic groups bonded to a silicon atom through an oxygen atom and organoxysiloxanes having a siloxane main chain ((Si—O)n) constituted by silicon atoms.
The organic groups bonded to the silicon atom through an oxygen atom in the organosilicates are not limited and may include, for example, linear, branched or cyclicalkyl groups. Specific examples of the organic groups that may be bonded to the silicon atom through an oxygen atom in the organosilicates include, without limitation, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-pentyl, i-pentyl, neopentyl, hexyl, octyl or the like. Of these alkyl groups, C1 to C4 alkyl groups are often used. Examples of other suitable organic groups may include aryl, xylyl, naphthyl or the like. The organosilicate may contain two or more different kinds of organic groups.
Specific non-limiting examples of suitable organoxysilanes are tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, tetraisobutoxysilane, tetra-sec-, butoxysilane, tetra-t-butoxysilane, tetraphenoxysilane, and dimethoxydiethoxysilene. These organosilicates may be used alone or in combination of any two or more thereof. Among these organosilicates, tetramethoxysilane and/or partially hydrolyzed condensates thereof show a high reactivity for hydrolysis and, therefore, can readily produce silanol groups.
Specific non-limiting examples of suitable organoxysiloxanes are condensates of the above organoxysilanes. The condensation degree of the oganoxysiloxanes is not particularly restricted. In certain embodiments, the condensation degree lies within the range represented by the following formula:

SiOx(OR)y 

wherein x is 0 to 1.2, and y is: 1.4 to 4 with the proviso that (2x+y) is 4; and R is an organic group, such as C1 to C4 alkyl.

The factor or subscript x represents the condensation degree of the siloxane. When the siloxane shows; a molecular weight distribution, the factor x means an average condensation degree. Compounds represented by the above formula wherein x=0, are organoxysilanes as a monomer, and compounds represented by the above formula wherein 0<x<2, are oligomers corresponding to condensates obtained by partial hydrolysis condensation. Also, compounds represented by the above formula wherein x=2, corresponds to SiO2 (silica). In certain embodiments, the condensation degree x of the organosilicate used in the present invention is in the range of 0 to 1.2, such as 0 to 1.0. The siloxane main chain may have a linear, branched or cyclic structure or a mixture thereof. The above formula: SiOx(OR)y may be determined by Si—NMR as described in U.S. Pat. No. 6,599,976 at col. 5, lines 10 to 41, incorporated herein by reference.
As mentioned earlier, the organosilicate of the liquid composition from which the second layer is deposited is essentially completely hydrolyzed. As used herein, the term “essentially completely hydrolyzed organosilicate” refers to a material wherein the organoxy groups of the organosilicate are substantially replaced by silanol groups to an extent that the material is rendered hydrophilic. As used herein, the term “hydrophilic” means that the material has an affinity for water. One way to assess the hydrophilicity of a material is to measure the contact angle of water with a dry film formed from the material: In certain embodiments of the present invention, the composition from which the second layer is deposited comprises a hydrolyzed organosilicate that can form a dry film exhibits a water contact angle of no more than 20°, or, in other embodiments, no more than 15°, or, in yet other embodiments, no more than 10°. This hydrolysis may produce a network polymer, as illustrated below:




where m and n are positive numbers and m is no more than n. In certain embodiments of the present invention, the essentially completely hydrolyzed organosilicate is substantially free of —OR groups as determined by FTIR or other suitable analytical technique.

As a result, in certain embodiments of the present invention, the multi-layer coating exhibits an initial water contact angle of no more than 20° or, in some embodiments, no more than 15°, or, in yet other embodiments, no more than 10°, prior to photoexcitation of any photocatalytic material that may be present in the liquid composition from which the second layer is deposited, as described below. The water contact angles reported herein are a measure of the angle between a tangent to the drop shape at the contact point and the surface of the substrate as measured through the drop and may be measured by the sessile drop method using a modified captive bubble indicator:manufactured by Lord Manufacturing, Inc., equipped with Gaertner Scientific goniometer optics. The surface to be measured is placed in a horizontal position, facing upward, in front of a light source. A sessile drop of water is placed on top of the surface in front of the light source so that the profile of the sessile drop can be viewed and the contact angle measured in degrees through the goniometer telescope which is equipped with circular protractor graduations.
Referring now to FIG. 1, there is seen a chart reflecting an FTIR analysis of a dry film formed from such a hydrophilic material. As is apparent, significant peaks are observed at the Si—OH bond wavenumber, which is 920-950, and the Si—O—Si bond wavenumber, which is 1050-1100. On the other hand, it is apparent that the film is substantially free of —OR groups, where R represents C1 to C4 alkyl groups, as evidenced by the absence of any substantial peak at the Si—OR wavenumber, which is 2900-3000.
In certain embodiments, the essentially completely hydrolyzed organosilicate included in the composition from which the second layer of the multi-layer coating of the present invention is deposited is the product of the hydrolysis of an organosilicate with a large amount of water in the presence of an acid hydrolysis catalyst. The hydrolysis may be conducted with water present in an amount considerably greater than the stoichiometric amount capable of hydrolyzing organoxy groups of the organosilicate. It is believed that the addition of such an excessive amount of water allows silanol groups produced by hydrolysis of the organosilicate to coexist with a large amount of water, thereby preventing the condensation reaction of the silanol groups.
The hydrolysis of the organosilicate may be conducted in the presence of one or more acid hydrolysis catalysts. Specific examples of suitable catalysts include, without limitation, inorganic acids, such as hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid, among others; organic acids, such as acetic acid, benzenesulfonic acid, toluenesulfonic acid, xylenesulfonic acid, ethylbenzenesulfonic acid, benzoic acid, phthalic acid, maleic acid, formic acid, citric acid, and oxalic acid, among others; alkali catalysts, such as sodium hydroxide, potassium hydroxide, calcium hydroxide, ammonia; and organic amine compounds, organometallic compounds or metal alkoxide compounds other than the organosilicates, e.g., organotin compounds, such as dibutyl tin dilaurate, dibutyl tin dioctdate and dibutyl tin diacetate, organoaluminum: compounds, such as aluminum tris(acetylacetonate), aluminum monoacetylacetonate bis(ethylacetoacetate), aluminum tris(ethylacetoacetate) and ethylacetoacetate aluminum diisopropionate, organotitanium compounds, such as titanium tetrakis(acetylacetonate), titanium bis(butoxy)-bis(acetylacetonate) and titanium tetra-n-butoxide, and organozirconium compounds, such as zirconium tetrakis(acetylacetonate), zirconium bis(butoxy)-bis(acetylacetonate), zirconium (isopropoxy)-bis(acetylacetonate)and zirconium tetra-n-butoxide, and boron compounds, such as boron tri-n-butoxide and boric acid; or the like.
In certain embodiments, the liquid composition from which the second layer of the multi-layer coatings of the present invention is deposited may also comprise, in addition to water, an organic solvent, such as alcohols, glycol derivatives, hydrocarbons, esters, ketones, ethers or the like. These solvents may be used alone or in the form of a mixture of any two or more thereof.
Specific examples of alcohols that may be used include, without limitation, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, acetylacetone alcohol or the like. Specific examples of glycol derivatives that may be used include, without limitation, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate or the like. Specific examples of hydrocarbons that may be used include, without limitation, benzene, toluene, xylene, kerosene, n-hexane or the like. Specific examples of esters that may be used include, without limitation, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl acetoacetate, ethyl acetoacetate, butyl acetoacetate or the like. Specific examples of the ketones that may be used include acetone, methyl ethyl ketone, methyl isobutyl ketone, acetyl acetone or the like. Specific examples of ethers that may be used include, without limitation, ethyl ether butyl ether, methoxy ethanol, ethoxy ethanol, dioxane, furan, tetrahydrofuran or the like.
Materials suitable for use in the liquid compositions from which the second layer of the multi-layer coatings of the present invention is deposited and methods for their production are described in U.S. Pat. No. 6,599,976 at col. 3, line 57. to col. 10, line 58, incorporated herein by reference. Non-limiting examples of commercially available materials that are essentially completely hydrolyzed organosilicates, and which are suitable for use in the compositions from which the second layer of the multi-layer coatings of the present invention is deposited, are MSH-200, MSH-400, and MSH 500 silicates, available from Mitsubishi Chemical Corporation, Tokyo, Japan, and Shinsui Flow MS-1200 silicate, available from Dainippon Shikizai, Tokyo, Japan.
In certain embodiments, the binder is prepared in a multi-stage process wherein, in a first stage, an organoxysilane, such as any of those mentioned earlier, is reacted with water in the presence of an acid hydrolysis catalyst, such as any of those mentioned earlier, wherein the water is present in an amount that is less than the stoichiometric amount capable of hydrolyzing the organoxy groups of the organoxysilane. In certain embodiments, the acid hydrolysis catalyst comprises an organic acid. In certain embodiments, the water is present during the first stage in a stoichiometric amount capable of hydrolyzing 50 percent of the organoxy groups of the organoxysilane. The result of the first stage is a partial hydrolysis polycondensation reaction product.
In certain embodiments, the first stage of the multi-stage binder preparation process is conducted at conditions that limit the degree of condensation of Si—OH groups formed as a result of the hydrolysis reaction. Such conditions can include, for example, controlling the reaction exotherm by, for example, external cooling, controlling the rate of addition of the acid catalyst, and/or conducting the first stage hydrolysis in the substantial absence (or complete absence) of any organic cosolvent.
In a second stage, the partial hydrolysis polycondensation reaction product is then contacted with a large amount of water, often in the absence of an acid hydrolysis catalyst. The amount of water used in the second stage is considerably greater (by “considerably greater” it is meant that the resulting solution contains no more than 2% solids) than the stoichiometric amount capable of hydrolyzing organoxy groups of the organoxysilane.
In yet other embodiments, the binder is prepared by starting with a tetraalkoxysilane oligomer, such as those commercially available from Mitsubishi. Chemical Corp under the tradenames MKC Silicate MS-51, MKC Silicate MS-56 and MKC Silicate, MS-60 (all trademarks; products of Mitsubishi Chemical Corp.). Such an oligomer is reacted with water in the presence of an organic acid hydrolysis catalyst (such as, for example, acetic acid) and/or an organic solvent, wherein the water is present in an amount that is considerably greater than the stoichiometric amount capable of hydrolyzing organoxy groups of the tetralkoxysilane.
In certain embodiments, the amount of organosilicate that is present in the liquid composition from which the second layer of the multi-layer coating is deposited ranges from 0.1 to 2 percent by weight calculated as SiO2 in the organosilicate, such as 0.2 to 0.90 percent by weight based on the total weight of the composition. In these embodiments, the amount of the organosilicate that may be present in the liquid composition from which the second layer is deposited can range between any combination of the recited values, inclusive of the recited values. It will be understood by those skilled in the art that the amount of the organosilicate present in the liquid composition from which the second layer of the multi-layer coating is deposited is determined by the properties desired to be incorporated into the composition.
In certain embodiments, the multi-layer coatings of the present invention comprise a second layer applied over at least a portion of the first layer, wherein the second layer is deposited from at least one liquid composition comprising a (a) a photocatalytic material, and (b) a binder. In these embodiments, the binder is hydrophilic and comprises an essentially completely hydrolyzed organosilicate, such as those discussed above. As used herein, the term “binder” refers to a continuous material in which particles of the photocatalytic material are dispersed.
In these embodiments, the second layer is deposited from a liquid composition that comprises a photocatalytic material in addition to the hydrophilic binder. As used herein, the term “photocatalytic material” refers to a material that is photoexcitable upon exposure to, and absorption of, radiation, such as ultraviolet or visible radiation. A photocatalytic material is a material that, when exposed to light having higher energy than the energy gap between the conduction band and the valence band of the crystal, causes excitation of electrons in the valence band to produce a conduction electron and leaving a hole behind on the particular valence band. In certain embodiments, the photocatalytic material comprises a metal oxide, such as zinc oxide, tin oxide, ferric oxide, dibismuth trioxide, tungsten trioxide, strontium titanate, titanium dioxide, or mixtures thereof.
In certain embodiments, at least a portion of the photocatalytic material is present in the liquid composition from which the second layer is deposited in the form of particles having an average crystalline diameter of 1 to 100 nanometers, such as 3 to 35 nanometers, or, in yet other embodiments, 7 to 20 nanometers. In these embodiments, the average crystalline diameter of the particles can range between any combination of the recited values, inclusive of the recited values. It will be understood by those skilled in the art that the average crystalline diameter of the particles may be selected based upon the properties desired to be incorporated into the second layer. In some embodiments, substantially all of the photocatalytic material is present in the composition from which the second layer is deposited in the form of such particles. The average crystalline diameter of the photocatalytic metallic oxide particles may be determined by scanning electron microscope or transmission electro-microscope and the crystal phase of such particles may be determined by X-ray diffraction, as known by those skilled in the art.
As mentioned above, certain materials may be photocatalytic upon exposure to, and absorption of, for example, ultraviolet (“UV”), and/or visible radiation. In certain embodiments, the photocatalytic materials that are present comprise materials that are photoexcitable by one or more of these mechanisms. Examples of materials that may be used as part of the liquid composition from which the second layer of the multi-layer coatings of the present invention is deposited, and which are photocatalytic upon exposure to UV radiation include, without limitation, tin oxide, zinc oxide, and the brookite, anatase and rutile forms of titanium dioxide. Examples of materials that may be used as part of the liquid composition from which the second layer of the multi-layer coatings of the present invention are deposited, and which are photocatalytic upon exposure to visible radiation include, without limitation, the brookite form of titanium oxide, titanium dioxide chemically modified via flame pyrolysis of titanium metal, nitrogen doped titanium dioxide, and plasma treated titanium dioxide.
In certain embodiments, the photocatalytic material is provided in the form of a sol comprising particles of photocatalytic material dispersed in water, such as a titania sol. Such sols are readily available in the marketplace. Examples of such materials, which are suitable for use as part of the liquid composition from which the second layer of the multi-layer coatings of the present invention is deposited, include, without limitation, S5-300A and S5-33B available from Millenium Chemicals, STS-01, STS-02, and STS-21 available from Ishihara Sangyo Corporation, and NTB-1, NTB-13 and NTB-200 available from Showa Denko Corporation.
In certain embodiments, the photocatalytic material is present in the form of a sol comprising brookite-type titanium oxide particles or a mixture of brookite-type with anatase-type and/or rutile-type titanium oxide particles dispersed in water. Such sols can be prepared by hydrolysis of titanium tetrachloride under certain conditions, such as is taught by U.S. Pat. No. 6,479,031, which is incorporated herein by reference. Sols of this type which are suitable for use in the present invention include, without limitation. NTB-1 and NTB-13 titania sols available from Showa Denko Corporation.
In certain embodiments, the photocatalytic material comprises chemically modified titanium dioxide. Examples of such materials include titanium dioxide chemically modified by flame pyrolysis as described by Khan et al., Efficient Photochemical Water Splitting by a Chemically Modified n-TiO2, Science Reprint, Volume 297, pp. 2243-2245 (2002), which is incorporated herein by reference, nitrogen-doped titanium oxide:manufactured as described in U.S. Patent Application Publication 2002/0169076A1l at, for example, paragraphs [0152] to [0203], which is incorporated herein by reference and/or plasma treated titanium dioxide as described in U.S. Pat. No. 6,306,343 at col. 2, line 49 to col. 7, line 17, which is incorporated herein by reference.
In certain embodiments, the amount of the photocatalytic material that is present in the liquid composition from which the second layer of the multi-layer coating is deposited ranges from 0.05 to 5 percent solids by weight, such as 0.1 to 0.75 percent solids by weight, with percent solids by weight being based on the total solution weight of the composition. In these embodiments, the amount of photocatalytic material that may be present can range between any combination of the recited values, inclusive of the recited values. It will be understood by those skilled in the art that the amount of photocatalytic material present in the liquid composition from which the second layer of the multi-layer coating is deposited is determined by the properties desired to be incorporated into that layer.
In certain embodiments, the photocatalytic material and the essentially completely hydrolyzed organosilicate are present in the liquid composition from which the second layer is deposited at a ratio of 0.05:0.95 to 5:0.3 by weight, or, in other embodiments 0.10:0.90 to 3.0:0.5 by weight, or, in yet other embodiments, 0.2:0.6 by weight. In these embodiments, the ratio of the photocatalytic material to the organosilicate can range between any combination of the recited values, inclusive of the recited values. It will be understood by those skilled in the art that the ratio of photocatalytic material and organosilicate in the composition of the second layer is determined by the properties desired to be incorporated into that layer, such as the refractive index desired for the composition which may be determined with reference to the substrate upon which the composition is to be applied.
In certain embodiments, the liquid composition from which the second layer of the multi-layer coating of the present invention is deposited comprises a binder that exhibits anti-static properties, i.e., the binder can form a dry film that has the ability to dissipate electrostatic charges. As will be appreciated by those skilled in the art, one way to assess the anti-static capability of a material is to measure the surface resistivity of the material. In certain embodiments, the binder of the composition of the second layer comprises a material that can form a dry film that exhibits a surface resistivity of from 7.5×109 to 1.5×1012 ohms/cm2, or, in other embodiments, no more than 10×1010 ohms/cm2. The surface resistivities reported herein can be determined with an ACL Statitide Model 800 Megohmeter using either (1) large extension probes placed 5 millimeters apart at several locations on the sample, or (2) the meter's onboard probes spaced 23⁄4 inches apart at several locations on the sample. As a result, the present invention is also directed to multi-layer coating having a second layer having such anti-static properties.
In certain embodiments, the liquid composition from which the second layer of the multi-layer coatings of the present invention is deposited can further include inorganic particles, for example, silica, alumina, including treated alumina (e.g. silica-treated alumina known as alpha aluminum oxide), silicon carbide, diamond dust, cubic boron nitride, and boron carbide. Such inorganic particles may, for example, be substantially colorless, such as silica, for example, colloidal silica. Such materials may provide enhanced mar and scratch resistance. Such particles can have an average particle size ranging from sub-micron size (e.g. nanosized particles) up to 10 microns depending upon the end use application of the composition and the desired effect.
In certain embodiments, such particles comprise inorganic particles that have an average particle, size ranging from 1to 10 microns, or from 1 to 5 microns prior to incorporation into the liquid composition. In other embodiments, the particles may have an average particle size ranging from 1 to less than 1000 nanometers, such as 1 to 100 nanometers, or, in certain embodiments, 5 to 50 nanometers, prior to incorporation into the liquid composition. In some embodiments, inorganic particles have an average particle size ranging from 5 to 50, or 5 to 25 nanometers prior to incorporation into the liquid composition. The particle size may range between any combination of these values inclusive of the recited values.
In certain embodiments, the particles can be present in the liquid composition from which the second layer of the multi-layer coating is deposited in an amount ranging from:up to 5.0 percent by weight, or from 0.1 to 1.0 weight percent; or from 0.1 to 0.5 weight percent based on total weight of the composition. The amount of particles present in the liquid composition can range between any combination of these values inclusive of the recited values.
In certain embodiments, the liquid composition from which the second layer of the multi-layer coating is deposited also comprises an antimicrobial enhancing material, such as, for example, metals; such as silver, copper, gold, zinc, a compound thereof, or a mixture thereof; quaternary ammonium compounds, such as benzalkonium chlorides, dialkyldimethyl-ammonium chlorides, cetyltrimethyl-ammonium bromide, cetylpyridinium chloride, and 3-(trimethoxysilyl)-propyldimethyl-octadecyl-ammonium chloride; phenolics, such as 2-benzyl4-chlorophenol, o-phenylphenol, sodium o-phenylphenate, pentachlorophenol, 2(2′,4′-dichlorophenoxy)-5-chlorophenol, and 4-chloro-3-methylphenol; halogen compounds, such as trichloroisocyanurate, sodium dichloroisocyanurte, potassium dichloroisocyanurate monotrichloroisocyanurate, potassium dichloro-isocyanurate, 1:4 dichlorodimethylhydantoin, bromochlorodimethylhydantoin, 2,2′-dibromo-3-nitrilopropionamide, bis(1,4-bromoacetoxy)-2-butene, 1,2-dibromo-2,4-dicyarobutane, 2-bromo-2-nitropropane-1,3-diol, and benzyl bromoacetate; organometallics, such as 10,10′-bxybisphenoxi-arsine, tributyltin oxide, tributyltin fluoride, copper 8-quinolinolate, copper naphthenate, chromated copper arsenate, ammoniacal copper arsenate, and cuprous oxide; organosulfur compounds, such as methylenebisthiocyanate (MBT), vinylenebisthiocyanate, chloroethylenebisthiio-cyanate, sodium dimethyldithiocarbamate, disodium ethylenebisdithiocarbamate, zinc dimethyldithiocarbamate, and bis(trichloromethyl) sulfone; heterocyclics, such as tetrahydro-3,5-dimethyl-2H-1,3,5-thiadiazine-2-thione (DMTT), sodium pyridinethione, zinc pyridinethione, 1,2-benzisothiazoline-3-one, 2-(n-octyl)-4-isothiazolin-3-one, 2-(4-thiazolyl)benzimidazole, N-(trichloromethylthio)-4-cyclohexene-1,2-dicarboximide, N-(trichloromethylthio)-phthalimide, and 5-chloro-2-methyl-4-isothiazolin-3-one 2-methyl-4-isothiazolin-3-one; and nitrogen compounds, such as N-cocotrimethylenediamine, N-[α-(1-nitroethyl)benzyl]-ethylenediamine, 2-(hydroxymethyl)amino-ethanol, 2-(hydroxymethyl)amino-2-methylpropanol, 2-hydroxymethyl-2-nitro-1,3-propanediol, hexahydro-1,3,5-tris-(2-hydroxyethyl)-s-triazine, hexahydro-1,3,5-triethyl-s-triazine, 4-(2-nitrobutyl)morpholine +4,4′-(2-ethyl-2-nitro-trimethylene)-dimorpholine, glutaraldehyde, 1,3-dimethylol-5,5-dimethyl-hydantoin, and imidazolidinyl urea, and mixtures thereof.
The liquid composition from which the second layer is deposited may, in certain embodiments, include a quantity of antimicrobial agent sufficient to exhibit an efficacy against microbes and particularly various species of fungi. More specifically, in certain embodiments, the second layer of the multi-layer coatings of the present invention may be deposited from a liquid composition that contains a quantity of antimicrobial agent sufficient to inhibit microbial growth on a substrate tested in accordance with MTCC (American Association of Chemists & Colorists) Test Method 30, Part III. Those skilled in the art are familiar with this test method and its parameters. In certain embodiments, the amount of antimicrobial enhancing material that is present in the liquid composition from which the second layer is deposited ranges from 0.01 to 1.0 percent by weight, such as 0.1 to 1.0 percent by weight, or, in other embodiments, 0.1 to 0.5 percent by weight based on the total weight of the composition. In these embodiments, the amount of the antimicrobial enhancing material that may be present in the liquid composition can range between any combination of the recited values, inclusive of the recited values.
In certain embodiments, the liquid composition from which the second layer of the multi-layer coatings of the present invention is deposited may comprise an optical activity enhancer, such as platinum, gold, palladium, iron, nickel, or, soluble salts thereof. The addition of these materials to compositions comprising a photocatalytic material is known to enhance the redox activity of the photocatalyst, promoting decomposition of contaminants adhering to the coating surface. In certain embodiments, the amount of optical activity enhancer present in the liquid composition from which the second layer of the multi-layer coating is deposited ranges from 0.01 to 1.0 percent by weight, such as 0.1 to 1.0 percent by weight, or, in other embodiments, 0.1 to 0.5 percent by weight based on the total weight of the compositions. In these embodiments, the amount of optical activity enhancer that may be present can range between any combination of the recited values, inclusive of the recited values. In certain embodiments, the liquid composition from which the second layer of the multi-layer coatings of the present invention is deposited may comprise a coupling agent, which may, for example, improve the adhesion of the second layer to the first layer. Examples of coupling agents suitable for this purpose include, without limitation, the materials described in U.S. Pat. No. 6,165,256 at col. 8, line 27 to col. 9, line 8, incorporated herein by reference.
In certain embodiments, the amount of coupling agent that is present in the liquid composition from which the second layer of the multi-layer coating is deposited ranges from 0.01 to 1 percent by weight, such as 0.01 to 0.5 percent by weight based on the total weight of the composition. In these embodiments, the amount of coupling agent that may be present in the liquid, composition can range between any combination of the recited values, inclusive of the recited values.
In certain embodiments, the liquid composition from which the second layer of the multi-layer coatings of the present invention is deposited may comprise a surface active agent, which may, for example, aid in improving the wetting properties of the composition when that composition is applied over the first layer. Examples of surface active agents suitable for use in the present invention include, without limitation, the materials identified in U.S. Pat. No. 6,610,777 at col. 37, line 22 to col. 38, line 60 and U.S. Pat. No. 6,657,001 at col. 38, line 46 to col. 40, line 39, which are both incorporated herein by reference.
In certain embodiments, the amount of surface active agent that is present in the liquid composition from which the second layer of the multi-layer coating is deposited ranges from 0.01 to 3 percent by weight, such as 0.01 to 2 percent by weight, or, in other embodiments, 0.1 to 1 percent by weight based on the total weight of solids in the composition. In these embodiments, the amount of surface active agent that may be present in the liquid composition can range between any combination of the recited values, inclusive of the recited values.
In certain embodiments, the liquid composition from which the second layer of the multi-layer coating is applied also comprises a cleaning composition. Suitable cleaning compositions includes those materials that comprise a surfactant, a solvent system, water, and a pH adjusting agent, such as acetic acid or ammonia. A suitable cleaning composition is disclosed in U.S. Pat. No. 3,463,735, which discloses a cleaning composition comprising a solvent system comprising a low boiling solvent such as isopropanol, and a moderately high boiling solvent, such as a C1 to C4 alkylene glycol alkyl ether having a total of 3 to 8 carbon atoms. Suitable commercially available cleaning compositions include WINDEX®, commercially available from SC Johnson and Son, Inc. As a result, certain embodiments of the present invention are directed to liquid compositions that are hydrophilic and comprise (a) an essentially completely hydrolyzed organosilicate, and (b) a cleaning composition. Certain embodiments of such compositions also comprise a photocatalytic material.
In certain embodiments, the cleaning composition is present in such liquid compositions in an amount of at least 10 weight percent, such as at least 20 weight percent, or, in some cases at least 25 weight percent, with weight percent being based on the total weight of the liquid composition.
If desired, the liquid composition from which the second layer of the multi-layer coatings of the present invention is deposited can comprise other optional coatings materials well known to those skilled in the coatings art.
The liquid composition from which certain embodiments of the second layer of the multi-layer coatings of the present invention is deposited can be made by a variety of methods. In certain cases, the composition is prepared by (i) providing a hydrophilic material comprising an essentially completely hydrolyzed organosilicate, wherein the pH of the hydrophilic material is no more than 3.5; (ii) providing a sol or paste comprising a photocatalytic material dispersed in a diluent, wherein the pH of the sol is no more than 3.5; and (iii) mixing the hydrophilic material provided in (i) with the sol or paste provided in (ii) to disperse the photocatalytic material in the hydrophilic material. It has been found that liquid compositions made by this method can be stable for over 12 months with little or no agglomeration or precipitation. The pH values reported herein can be determined using an ACCUMET pH meter commercially available from Fisher Scientific.
In certain cases, the liquid composition from which the second layer of the multi-layer coatings of the present invention is deposited is produced by providing a hydrophilic material comprising an essentially completely hydrolyzed organosilicate, wherein the pH of the hydrophilic material is no more than 3.5 or, in some cases, from 1.3 to 3.5 or, in yet other cases, 3.0 to 3.5. In certain embodiments, such a hydrophilic material is obtained by first providing an essentially completely hydrolyzed organosilicate wherein the pH of the hydrophilic material is greater than the desired pH and then adding acid to the hydrophilic material until the pH of the hydrophilic material is no more than 3.5 or, in some cases from 1.3 to 3.5 or, in yet other cases, 3.0 to 3.5. For example, as mentioned earlier, the hydrophilic material may comprise the MSH-200 and/or Shinsul. Flow MS-1200 silicates, which are typically provided by the supplier at a pH of 3.5 to 4.5.
In certain embodiments, the hydrophilic material may be diluted with a diluent, such as water or an organic solvent, before the addition of acid to, for example, reduce the solids content of the hydrophilic material, thereby allowing for the formation of thinner films.
Acids that may be added to the hydrophilic material to adjust the pH thereof include both inorganic and organic acids. Suitable inorganic acids include, without limitation, hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid, among others. Suitable organic acids include acetic acid, dichloroacetic acid, trifluoroacetic acid, benzenesulfonic acid, toluenesulfonic acid, xylenesulfonicacid, ethylbenzenesulfonic acid, benzoic acid, phthalic acid, maleic acid, formic acid and oxalic acid, among others.
In certain cases, the liquid composition from which the second layer of the multi-layer coating is deposited is produced by providing a sol or paste comprising a photocatalytic material dispersed in a diluent, wherein the pH of the sol or paste is no more than 3.5 or, in some cases, from 1.3 to 3.5 or, in yet other cases 3.0 to 3.5. In certain embodiments, the pH of the sol or paste is substantially the same as that of the hydrophilic material. In certain embodiments, such a sol or paste is obtained by first providing such a sol or paste wherein the pH thereof is greater than the desired pH and then adding acid to the sol or paste until the pH of the sol or paste is no more than 3.5 or in some cases from 1.3 to 3.5 or, in yet other cases, 3.0 to 3.5. For example, as mentioned earlier, the photocatalytic material used in certain embodiments of the liquid compositions from which the second layer of the multi-layer coatings of the present invention is deposited may comprise a sol of titanium dioxide available from Showa Denko Corporation under the names NTB-1 and/or NTB-13, wherein the sol comprises brookite-type titanium oxide particles or a mixture of brookite-type with anatase-type and/or rutile-type titanium oxide particles dispersed in water. NTB-1 and NTB-13 are typically provided by the supplier at a pH of 2 to 4.
Acids that may be added to the sol or paste comprising the photocatalytic material to adjust the pH thereof include both the inorganic and organic acids described earlier, among others. In certain embodiments, the acid that is added to the sol or paste comprising the photocatalytic material is the same acid that is added to the hydrophilic material as described earlier.
The liquid compositions from which the second layer of the multi-layer coatings of the present invention are deposited can be made by mixing the hydrophilic material provided as described above with the sol or paste provided as described above to disperse the photocatalytic material in the hydrophilic material. The mixing step is not particularly limited and may be accomplished by any conventional mixing technique known to those of skill in the art so long as the mixing results, in a dispersion of the photocatalytic material in the hydrophilic material. As a result, certain embodiments of the present invention are directed to multi-layer coatings, wherein the second layer is deposited from a liquid composition having a pH of no more than 3.5, such as 1.3 to 3.5, or, in some cases, 3.0 to 3.5.
In other cases, the liquid composition from which the second layer of the multi-layer coatings of the present invention is deposited is prepared by (i) providing a hydrophilic material comprising an essentially completely hydrolyzed organosilicate, wherein the pH of the hydrophilic material is from 7.0 to 8.5; (ii) providing a sol or paste comprising a photocatalytic material dispersed in a diluent, wherein the pH of the sol or paste is from 7.0 to 8.5; and (iii) mixing the hydrophilic material provided in (i) with the sol or paste provided in (ii) to disperse the photocatalytic material in the hydrophilic material.
In certain cases, the compositions from which the second layer of the multi-layer coatings of the present invention is deposited is produced by providing a hydrophilic material that comprises an essentially completely hydrolyzed organosilicate, wherein the pH of the hydrophilic material is from 7.0 to 8.5, such as 7.0 to 8.0 or, in some cases, 7.5 to 8.0. In certain embodiments, such a hydrophilic material is obtained by first providing an essentially completely hydrolyzed organosilicate wherein the pH of the hydrophilic material is less than the desired pH and then adding a base to the hydrophilic material until the pH of the hydrophilic material is from 7.0 to 8.5, such as 7.0 to 8.0 or, in some cases, 7.5 to 8.0.
In certain embodiments; the hydrophilic material may be diluted with a diluent, such as water or an organic solvent, before the addition of the base to, for example, reduce the solids content of the hydrophilic material thereby allowing for the formation of thinner films.
Materials that may be added to the hydrophilic material to adjust the pH thereof include both organic bases and inorganic bases. Specific examples of bases which may be used to raise the pH of the hydrophilic material include, without limitation, alkali metal hydroxides, such as sodium hydroxide, potassium hydroxide and lithium hydroxide; ammonium hydroxide; quaternary ammonium hydroxides, such as tetraethyl ammonium hydroxide and tetraethanol ammonium hydroxide; ammonia; amines such as, triethylamine and 3-(diethylamino)-propan-1-ol; tertiary sulfonium hydroxides, such as trimethyl sulfonium hydroxide and triethyl sulfonium hydroxide; quaternary phosphonium hydroxides such as, tetramethyl phosphonium hydroxide and tetraethyl phosphonium hydroxide; organosilanolates, such as tripotassium γ-aminopropylsilantriolate, tripotassium N-(β-aminoethyl)-γ-aminopropylsilantriolate, dipotassium dimethylsilandiolate, potassium trimethylsilanolate, bis-tetramethylammonium dimethylsilandiolate, bis-tetraethylammonium dimethylsilandiolate, and tetraethylammonium trimethylsilanolate; sodium acetate; sodium silicate; ammonium bicarbonate; and mixtures thereof.
In certain cases, the liquid composition from which the second layer of the multi-layer coatings of the present invention is deposited is prepared by providing a sol or paste that comprises a photocatalytic material dispersed in, a diluent, wherein the pH of the sol or paste is from 7.0 to. 8.5,such as 7.0 to 8.0 or, in some embodiments, from 7.5 to 8.0. In certain embodiments, the pH of the sol or paste is substantially the same as that of the hydrophilic material. In certain embodiments, such a sol or paste is obtained by first providing such a sol or paste wherein the pH thereof is less than the desired pH and then adding an alkali material to the sol or paste until the pH thereof is from 7.0 to 8.5, such as 7.0 to 8.0 or, in some cases from 7.5 to 8.0.
Bases that may be added to the sol or paste comprising the photocatalytic material to adjust the pH thereof include the inorganic and organic bases described earlier, among others. In certain embodiments, the base that is added to the sol or paste comprising the photocatalytic material is the same base that is added to the hydrophilic material.
The liquid compositions from which the second layer of the multi-layer coatings of the present invention is deposited can be made by mixing the hydrophilic material as described above with the sol or paste provided as described above to disperse the photocatalytic material in the hydrophilic material. The mixing step is not particularly limited and may be accomplished by any conventional mixing technique known to those:of skill in the art, so long as the mixing results in a dispersion of the photocatalytic material in the hydrophilic material. As a result, certain embodiments of the present invention are directed to multi-layer coatings, wherein the second layer is deposited from a liquid composition having a pH of 7.0 to 8.5, such as 7.0 to 8.0, or, in some cases, 7.5 to 8.0.
Referring now to FIGS. 2 and 3, there is seen (i) a schematic cross-sectional view in an enlarged scale of certain embodiments of the second layer of a multi-layer coating of the present invention, and (ii) a micrograph illustrating an embodiment of a second layer of a multi-layer coating of the present invention, respectively. As is apparent from FIGS. 2 and 3, in certain embodiments, the second layer of the multi-layer coatings of the present invention are deposited from a liquid composition wherein the photocatalytic material is dispersed throughout the hydrophilic binder. In these embodiments, the second layer of the multi-layer coating comprises a photocatalytic material in the form of nano-sized photocatalytic particles 10 (in these particular examples, the particles have an average crystalline diameter no more than 20 nanometers), which are relatively uniformly dispersed throughout the hydrophilic binder 20. In particular, as shown in FIG. 3, the particles 10 are non-agglomerated, i.e., all-or nearly all of the particles are encapsulated by, and separated by, the binder rather than being combined to each other. While not being limited by any theory it is believed that, by controlling the pH of the hydrophilic material and the sol or paste of photocatalytic material prior to their combination, the photocatalytic particles can be well dispersed in the hydrophilic material, such that agglomeration is prevented, which results in a liquid composition of low turbidity. Thus, in certain embodiments of the present invention, the second layer of the multi-layer coating is deposited from a liquid composition having low turbidity.
One advantage of the liquid compositions from which the second layer of the multi-layer coatings of the present invention is deposited, and/or the methods of their production, is that they may form stable one-package liquid compositions. Therefore, in certain embodiments, the second layer of the multi-layer coating of the present invention is deposited from a one-pack liquid composition. As used herein, the term “one-pack liquid composition” refers to a liquid composition wherein the components comprising the liquid composition are stored together in a single container.
The one-pack liquid compositions that may be used to form the second layer in the multi-layer coatings of the present invention comprise at least two components, including the previously discussed photocatalytic materials and hydrophilic binders. In addition, such one-pack liquid compositions have a shelf-life of at least 3 months. As used herein, the term “shelf-life” refers to the amount of time between when the components are combined in a single container and the occurrence of precipitation or agglomeration to an extent that the turbidity of the composition increases such that the composition can no longer form a low haze film. In certain embodiments, the one-pack liquid compositions have a shelf-life of at least 3 months or, in certain other embodiments, at least 6 months, or, in some cases, at least 12 months.
In certain embodiments, the liquid composition from which the, second layer of the multi-layer coatings of the present invention is deposited has a turbidity of no more than 600 NTU or, in some cases, not more than 400 NTU (Nephelometric Turbidity Units) after 3 months, 6 months, or, in some cases, 12 months. The turbidity values reported herein can be determined by a Turbidimeter, Model DRT-100D, manufactured by Shaban Manufacturing Inc, H. F. Instruments Division using a sample cuvette of 28 mm diameter by 91 mm in length with a flat bottom. Moreover, in certain embodiments, the second layer of the multi-layer coatings of the present invention have low haze. As used herein, “low haze” means that the film has a haze of no more than 0.3%. The haze values reported herein can be determined with a haze meter, such as a Hazegard® Model No. XL-211, available from Pacific Scientific Company, Silver Spring, Md.
The present invention is also directed to methods of applying a multi-layer coating to a substrate comprising the steps of (1) applying to a substrate a first layer comprising an inorganic oxide network; (2) applying onto at least a portion of the first layer a liquid composition from which a second layer is deposited, wherein the composition of the second layer is hydrophilic and comprises an essentially completely hydrolyzed organosilicate; and (3) curing the second layer.
In these methods, the first layer comprises an inorganic oxide network and the composition from which such a layer is deposited may be applied to the substrate by any of the methods used in coating technology such as, for example, spray coating, roll coating, dipping, spin coating, flow coating, brushing, and wiping, among others. After application, such a composition may be cured. For example, the composition from which the first layer of the multi-layer coating is deposited may be applied to the substrate as a solution of solids in an appropriate solvent, such as water, an organic solvent, or a mixture thereof. The solvent may then be evaporated and the coating cured by heating to elevated temperatures, such as 80° to 130° C. for 1 to 16 hours.
In these methods of the present invention, the liquid composition from which the second layer is deposited may be applied to the substrate by any of the methods used in coating technology such as those mentioned earlier.
In these methods of the present invention, the second layer is cured, i.e., dried, after it is applied onto the first layer. Though not being bound by any theory, it is believed that, upon cure, some of the silanol groups of the essentially completely hydrolyzed binder are condensed so that Si—O—Ti bonds are formed within the composition. It is believed that the presence of these groups enhance the durability of the second layer in the multi-layer coatings of the present invention, as described in more detail below.
The liquid composition from which the second layer of the multi-layer coatings of the present invention is deposited may be self-curing, such that the composition may cure without the aid of any cure catalyst. Moreover, the liquid composition from which the second layer of the multi-layer coating of the present invention is deposited may, for example, be cured at ambient temperatures. In other words, curing of the liquid composition of the second layer may be accomplished by allowing the composition to stand in air, i.e., air drying. According to certain embodiments of the present invention, the liquid composition is cured by exposing it to air for 2 to 3 hours at 25° C. to achieve superhydrophilicity and 16 hours to achieve long-term durability. Such liquid compositions may also be cured by heat drying. For example, according to certain embodiments of the present invention, the second layer is cured by exposing it to air for 3 to 5 minutes and then force drying it at 80° C. to 100° C. for at least 3 seconds.
The multi-layer coatings of the present invention may be applied to polymeric, ceramic, concrete, cement, glass, wood, paper, or metal substrates, composite materials thereof, or other materials, including painted substrates. In certain particular embodiments, the multi-layer coatings of the present invention are applied to a polymeric substrate. In certain embodiments, such polymeric substrates may comprise a solid transparent or optically clear solid material, such as is disclosed in U.S. Pat. No. 6,042,737at col. 6, line 66 to col. 8, lines 34, which is incorporated herein by reference. In certain embodiments, such polymeric substrates may comprise a photochromic material, such as is disclosed in U.S. Pat. No. 6,042,737 at col. 8, line 35 to col. 10, line 19, which is incorporated herein by reference.
Specific examples of articles upon which the multi-layer coatings of the present invention may be applied include, without limitation, windows; windshields on automobiles aircraft, watercraft and the like; indoor and outdoor mirrors; lenses, ;eyeglasses or other optical instruments; protective sports goggles; masks; helmet shields; glass slides of frozen food display containers; glass covers; buildings walls; building roofs; exterior tiles on buildings; building stone; painted steel plates; aluminum panels; window sashes; screen doors; gate doors; sun parlors; handrails; greenhouses; traffic signs; transparent soundproof walls; signboards; billboards; guardrails; road reflectors; decorative panels; solar cells; painted surfaces on automobiles watercraft, aircraft, and the like; painted surfaces on lamps; fixtures, and other articles; air handling systems and purifiers; kitchen and bathroom interior furnishings and appliances; ceramic tiles; air filtration units; store showcases; computer displays; air conditioner heat exchangers; high-voltage cables; exterior and interior members of buildings; window panes; dinnerware; walls in living spaces, bathrooms, kitchens, hospital rooms, factory spaces, office spaces, and the like; sanitary ware, such as basins, bathtubs, closet bowls, urinals, sinks, and the like; and electronic equipment, such as computer displays.
In certain embodiments, the liquid composition from which the second layer of the multi-layer coatings of the present invention is deposited can have a very low solids content, approximately 1 percent by weight total solids based on the total weight of the composition. Consequently, such a liquid composition can be applied at extremely small film thicknesses. In particular, according to certain embodiments of the present invention; the liquid composition is applied onto at least a portion of the first layer in the form of a thin film that has a dry film thickness of no more than 200 nanometers (0.2 micrometers) or, in some embodiments, 10 to 100 nanometers (0.01 to 0.1 micrometers), in yet other embodiments of the present invention, 20 to 60 nanometers (0.02 to 0.06 micrometers). Application of the second layer of the multi-layer coatings of the present invention at such low film thickness can be particularly advantageous in providing an optical thin film without necessarily matching the refractive index of the composition to that of the first layer.
As mentioned previously, the liquid composition from which the second layer of the multi-layer coatings of the present invention is deposited is initially hydrophilic, that is, upon application, and prior to excitation of any photocatalyst that may be present in the composition of the second layer, the second layer exhibits an affinity to water. This initial hydrophilicity can be illustrated by an initial water contact angle of no more than 20° or, in some embodiments, no more than 15°, or, in yet other embodiments, no more than 10°. Upon excitation of the photocatalytic material, if any, the second layer of the multi-layer coatings of the present invention can be rendered “super-hydrophilic,” that is, following excitation of the photocatalyst, the second layer of the multi-layer coatings of the present invention can exhibit a water contact angle of less than 5°, even as little as 0°.
The means that may be used for exciting the photocatalyst, if any is present in the liquid composition from which the second layer is deposited, depends on the photocatalytic material used in the composition. For example, materials that are photoexcited upon exposure to visible light, such as the brookite form of titanium dioxide, as well as nitrogen or carbon doped titanium dioxide, may be exposed to any visible light source including any radiation of a wavelength of at least 400 nanometers. On the other hand, the anatase and rutile forms of titanium dioxide, tin oxide, and zinc oxide can be photoexcited by exposure UV radiation of a wavelength of less than 387 nanometers, 413 nanometers, 344 nanometers, and 387 nanometers, respectively. Suitable UV radiation sources for photoexciting such photocatalysts include, without limitation, a UV lamp, such as that sold under the tradename UVA-340 by the Q-Panel Company of Cleveland, Ohio, having an intensity of 28 watts per square meter (W/m2) at the coating surface.
In certain embodiments, the multi-layer coatings of the present invention exhibit a photoactivity of at least 0.5 cm−1min−1, such as, at least 1.0 cm−1min−1. Photoactivity can be evaluated as described in U.S. Pat. No. 6,027,766 at col. 11, line 1 to col, 12, line 55, which is incorporated herein by reference.
In certain embodiments, the multi-layer coatings of the present invention are rendered superhydrophilic upon exposure to sunlight for a period of 1to 2 hours. Alternatively, the multi-layer coatings of the present invention may be rendered superhydrophilic upon exposure to UV radiation of an intensity of 28 W/m2 for 1 hour.
As discussed previously, the multi-layer coatings of the present invention can exhibit very favorable hydrophilic, anti-static and/or anti-bacterial properties, among others. Because they are hydrophilic, the multi-layer coatings of the present invention may exhibit advantageous self-cleaning, anti-fouling, and/or anti-fogging properties. The present invention, therefore, is also directed to methods for improving the anti-fouling, self-cleaning, easy-to-clean, and/or anti-fogging properties of an article, wherein the article comprises a surface having a coating layer comprising an inorganic oxide network deposited thereon, the method comprising: (1) applying to at least a portion of the surface a liquid composition comprising an essentially completely hydrolyzed organosilicate; and (2) curing the composition applied in step (1).
Another feature of the multi-layer coatings of the present invention is that they may result in a second layer that is particularly durable. The surprising durability of such coatings can be measured in terms of the ability of the film surface to maintain a contact angle over time under accelerated weather conditions. The lower the degree of contact angle that can be maintained by the sample tested over time or number of wiping cycles, the more durable the film. Simulating weathering of the film can be obtained via weathering chambers, which include the Cleveland Condensing Cabinet (CCC) and QUV Tester (products of The Q-Panel Company, Cleveland, Ohio).
In certain embodiments, the photocatalytic material is present in the liquid composition from which the second layer of the multi-layer coatings of the present invention is deposited in an amount sufficient to produce a multi-layer coating that maintains:a contact angle of less than 10 degrees, such as less than 5 degrees and/or a photoactivity of 3 cm−1min−1 after exposure to a CCC chamber for 4000 hours, where the CCC chamber is operated at a vapor temperature of 140° F. (60° C.) in an indoor ambient environment which results in constant water condensation on the test surface. Indeed, as illustrated by the Examples herein, it was discovered that the inclusion of a photocatalytic material in certain embodiments of such compositions produced coatings exhibiting dramatically improved durability as compared to compositions containing a hydrophilic binder of the type described herein but no photocatalytic material. As illustrated by FIG. 4, in certain embodiments, the photocatalytic material can be included in the composition from which the second layer of the multi-layer coatings of the present invention is deposited in an amount sufficient to yield a multi-layer coating that maintains its initial water contact angle (i.e., the water contact angle is within 4 degrees of the initial water contact angle, wherein “initial water contact angle” refers to the water contact angle observed after exposure to UV light for 2 hours as described in the Examples but before exposure to the CCC chamber) even after exposure of the coating to a CCC chamber for 4000 hours as described above, whereas the absence of a photocatalytic material yielded a coating that could not maintain its initial water contact angle after approximately 2000 to 3000 hours of such exposure. Indeed, the Examples illustrate that in the absence of a photocatalytic material the contact angle of the surface increased to nearly three times the initial contact angle a exposure in a CCC for,3500 hours. Without being bound by any theory the inventors believe that this surprising result can be attributed to a partial crosslinking of the photocatalytic material with the organosilicate which yields Si—O—Ti bonds in the coating. The inventors believe that some photocatalytic material takes part in such crosslinking, while some photocatalytic material remains available for photocatalytic activation even after 4000 hours of CCC exposure.
In certain embodiments, the multi-layer coatings of the present invention may maintain a contact angle of 5 to 6 degrees after exposure to 650 hours in a QUV Tester equipped with fluorescent tubes (B313 nanometers) at black panel temperature of 65 to 70° C. and 4 hours condensing humidity at 50° C.
Illustrating the invention are the following examples, which, however, are not to be considered as limiting the invention to their details. Unless otherwise indicated, all parts and percentages in the following examples, as well as throughout the specification, are by weight.
EXAMPLES
Example 1 
Preparation of a Hydrolyzed Organosilicate Binder
An acid hydrolysis catalyst solution, referred to herein as solution “A”, was prepared by adding 7,000 grams of deionized water to a clean, dry 2 gallon container. With stirring 1.0 gram of 70% nitric acid was added and set aside.
15.5 grams ( ̃0.10 moles) of 98% TMOS (tetramethoxysilane) representing  ̃6 grams of SiO2 was added to a clean, dry 1 liter glass beaker. 3.6 grams of solution A ( ̃0.20 moles of H2O) was slowly added to the TMOS, controlling the exotherm by using an ice bath to maintain the temperature below 25° C. Upon the completion of the addition of solution A, this partially hydrolyzed silane solution was held for one hour at  ̃25° C. In a separate clean, dry beaker, 290.5 grams of ethanol and 290.5 grams of deionized water were mixed and then added to the partial hydrolyzate with stirring, after the one hour hold time. Then the pH of the diluted silane solution (pH ̃5) was adjusted to pH ̃3.9 by adding 0.80 grams of glacial acetic acid with stirring. The resultant 1% SiO2 binder solution was allowed to fully hydrolyze overnight with stirring.
Application on test panels with above solution show good wetting with no optical flaws and passes 50 flood/dry cycles maintaining good hydrophilicity.
Example 2 
Preparation of a Hydrolyzed Organosilicate Binder
15.5 grams ( ̃0.10 moles) of 98% TMOS representing  ̃6 grams of SiO2 and 3.6 grams of anhydrous methanol (cosolvent) were added to a clean, dry 1 liter glass beaker. 3.6 grams of solution A ( ̃0.20 moles of H2O) was slowly added to the TMOS solution, controlling the exotherm by the rate of addition of solution A. The peak temperature attained during the addition was 33° C. Upon the completion of the addition of solution A, this partially hydrolyzed silane solution was held for one hour at  ̃25° C. In a separate clean, dry beaker, 287 grams of ethanol and 290.5 grams of deionized water was mixed and then added to the partial hydrolyzate with stirring, after the one hour hold time. Then, the pH of the diluted silane solution. (pH ̃5) was adjusted to pH ̃3.9 by adding 0.80 grams of glacial acetic acid with stirring. The resulting. 1% SiO2 binder solution was allowed to fully hydrolyze overnight with stirring.
Application on test panels with above solution show dewetting problems with mottling. The test results suggest that the inclusion of cosolvent provided for a more efficient hydrolysis and corresponding condensation to form higher molecular weight oligomers which demonstrated the observed behavior upon application.
Example 3 
Preparation of a Hydrolyzed Organosilicate Binder
15.5 grams ( ̃0.10 moles) of 98% TMOS (tetramethoxysilane) representing  ̃6 grams of SiO2 was added to a clean, dry 1 liter glass beaker. 3.6 grams of solution A ( ̃20 moles of H2O) was slowly added to the TMOS, controlling the exotherm by the rate of addition of solution A. The peak temperature attained during the addition was 40° C. Upon the completion of the addition of solution A, this partially hydrolyzed silane solution was held for one hour at  ̃25° C. In a separate clean, dry beaker, 290.5 grams of ethanol and 290.5 grams of deionized water were mixed and then added to the partial hydrolyzate with stirring, after the one hour hold time. Then, the pH of the diluted silane solution (pH ̃5) was adjusted to pH ̃3.9 by adding 0.80 grams of glacial acetic acid with stirring. The 1% SiO2 binder solution was allowed to fully hydrolyze overnight with stirring.
Application on test panels with above solution show dewetting problems with mottling. The test results suggest that by not controlling the exotherm and allowing the temperature of the hydrolysis to reach  ̃40° C., resulted in a much higher degree of condensation to form higher molecular weight oligomers which demonstrated the observed behavior upon application.
Example 4 
Preparation of a Hydrolyzed Organosilicate Binder
Methanol and deionized water were mixed at 1:1 (w:w) ratio under stirring, The mixture was cooled to room temperature. 10.0 g of MS-51 silicate solution (Mitsubishi Chemical Corporation, Tokyo, Japan) was charged into a glass reactor, followed by addition of 504.8 g of the pre-mixed methanol/water solvent mixture as one portion. The solution was stirred at 20-22° C. for 15 minutes. Then, 5.2 g of glacial acetic acid was added into the reactor under agitation. The solution mixture was kept stirred at ambient for additional 24 hours. The final SiO2 content of the solution was 1% with a pH of 3.5.
Example 5 
Preparation of a Hydrolyzed Organosilicate Binder
1-propanol and deionized water were mixed at 1:1 (w:w) ratio under stirring. The mixture was cooled to room temperature. In a separate, container, acetic acid solution was prepared by diluting 10.0 g of glacial acetic acid with 90.0 g of 1-propanol/water solvent mixture. 5.0 g of MS-51 silicate solution was charged into a glass reactor, followed by addition of 253.7 g of the pre-mixed 1-propanol/water solvent mixture as one portion. The solution was stirred at 20-22° C. for 15 minutes. Then 1.4 g of pre-prepared acetic acid solution was added into the reactor under agitation. The solution mixture was kept stirred at ambient for additional 24 hours. The final SiO2 content of the solution was 1% with a pH of 4.1.
Example 6 
Preparation of Liquid Compositions
Liquid compositions A through G in Table 1 were prepared as follows. Charge I was prepared in a one liter glass vessel equipped with a magnetic stirrer. Charge I was prepared by adding the binder material to the vessel and then adding deionized water to the vessel under agitation. The pH of the mixture was adjusted to 1.8 by adding 2N hydrochloric acid under agitation until the desired pH was achieved.
Charge II was prepared in a 4 oz. glass container equipped with a magnetic stirrer. Titania sol was added to this vessel and the pH was adjusted to 1.8 by adding 2N hydrochloric acid under agitation until the desired pH was achieved. Charge II was then added under agitation to Charge I to produce the hydrophilic compositions A through G.












TABLE 1






Silicate/TiO2



Titania


Composition
Weight Ratio
Binder1
DI Water
Titania Sol2
Sol3







A
0.5/0.3
500 g
 480 g
  20 g
—


B
0.5/0.3
500 g
 480 g
  20 g
—


C
0.4/0.24
 40 g
58.4 g
 1.6 g
—


D
0.31/0.19
 31 g
67.7 g
1.27 g
—


E
0.25/0.25
 25 g
73.3 g
1.67 g
—


F
0.9/0.1
 47 g
 2.3 g
0.33 g
—


G
0.5/0.3
 25 g
24.5 g
—
0.5 g





1MSH-200 hydrolyzed organosilicate (1% solids) commercially available from Mitsubishi Chemical Corporation, Tokyo, Japan.


2NTB-1 titania sol commercially available from Showa Denko K.K., Tokyo, Japan.


3STS-01 titania sol commercially available from Ishihara Sangyo Kaisha Ltd.






Example 7 
Float Glass Test Substrates
The surface of 9′′×12′′ float glass test substrates were prepared by cleaning the substrate with a diluted Dart 210 solution (commercially available from. Madison Chemical Co., Inc.) prepared by diluting concentrated Dart 210 with deionized water so that the solution had a concentration of 5% to 10% Dart 210. The substrate was then rinsed with hot tap water and then deionized water. The test substrate was sprayed with Windex® and wiped dry with a paper towel (Kaydry® commercially available from Kimberly-Clark Corp.).
The liquid compositions of Example 6 were each applied to a test substrate by wipe application using a BLOODBLOC Protective Pad, commercially available from Fisher Scientific. The pad was wrapped around the foam applicator. Then, 1.5 grams of the hydrophilic composition was applied to the pad using an eye dropper or plastic bottle with a dropper top. The compositions were then applied by contacting the wet pad with the glass test substrate with straight, slightly overlapping strokes. After application, the substrate was allowed to dry at room temperature for at least 2 prior to testing. Results are summarized in Table 2











TABLE 2






Ti
PCA
Surface Resistivity



Composition
(μg/cm2)1
(cm−1min−1)2
(ohms/cm2)3
Haze4







A
1.2
3.9
3.84 × 109
0.1%


B
2.3
8.1
6.25 × 108
0.2%


C
0.7
2.1
—
—


D
0.5
1.3
—
—


E
0.7
2.6
—
—


F
0.4
0.6
—
—


G
1.9
5.5
—
—





1Sample analyzed using X-ray fluorescence analysis.


2Photocatalytic activity was evaluated as described in U.S. Pat. No. 6,027,766 at col. 11, line 1 to col, 12, line 55.


3Surface resistivity was evaluated with an ACL Statitide Model 800 Megohmeter using either (1) large extension probes placed 5 millimeters apart at several locations on the sample, or (2) the meter's onboard probes spaced 23⁄4 inches apart at several locations on the sample.


4Haze was evaluated with a Hazegard ® Model No. XL-211 haze meter, available from Pacific Scientific Company, Silver Spring, Md.






Durability Testing-Test 1 
Test substrates coated with liquid compositions A and B were placed in a Cleveland Condensation Chamber operating at 140° F. (60° C.). Each test substrate was removed from the chamber weekly and tested to determine the water contact angle. The photoactivity of the composition was determined by measuring the water contact angle difference before and after exposure of the substrate to UV light. The exposure interval was 2 hours to a UVA-340 lamp supplied by the Q-Panel Company of Cleveland, Ohio or direct sunlight. The water contact angles reported were measured by the sessile drop method using a modified captive bubble indicator manufactured by Lord Manufacturing, Inc., equipped with Gartner Scientific goniometer optics. The surface to be measured was placed in a horizontal position, facing upward, in front of a light source. A sessile drop of water was placed on top of the surface in front of the light source so that the profile of the sessile drop could be viewed and the contact angle, measured in degrees through the goniometer telescope which is equipped with circular protractor graduations. Results are summarized in Table 3.










TABLE 3









Composition A












Contact

Composition B












Angle
Contact
Contact Angle
Contact Angle


Hours in
Before
Angle After
Before
After


CCC
Exposure
Exposure
Exposure
Exposure














0
20
3
12
3


498
14
3
12
3


1062
38
3
37
3


1535
32
3
27
3


2221
18
4
9
3


2573
30
3
26
3


2975
30
5
33
4


3565
—
—
30
5


4040
—
—
19
4









Durability Testing-Test 2 
The durability of test substrates coated with liquid compositions A through G was tested by measuring the water contact angle after exposure to UV light as described above but prior to placement in the Cleveland Condensation Chamber The same substrates were then placed in the CCC as described above-for at least 4000 hours and then removed. The substrates were then exposed to UV light as described above and tested by measuring the water contact angle. Results are summarized in Table 4.









TABLE 4






Contact Angle




Before CCC
Contact Angle After


Composition
Exposure
4000 Hours CCC







A
3
5


B
3
4


C
5
4


D
5
3


E
6
2


F
5
9


G
3
3









Durability Testing-Test 3 
The durability of test substrates coated with compositions of the present invention was also compared to substrates coated with compositions comprising hydrophilic organosilicate binder but no the photocatalytic material. Hydrophilic compositions B and F of Example 6 as well as a similar composition having a binder to titanium dioxide ratio of 95/0.5 (composition J) were placed in the Cleveland Condensation Chamber as described above a periodically removed and exposed to UV light as described above. Comparative composition A was Shinsui Flow MS-1200, available from Dainippon Shikizai, Tokyo, Japan and comparative composition B was MSH-200, available from Mitsubishi Chemical Corporation, Tokyo, Japan. The test substrates were tested for water contact angle as described above. Results are illustrated in FIG. 4.
Example 8 
Preparation of Liquid Compositions
Liquid compositions H and I were prepared in the manner described in Example 6 except that WINDEX was included in the composition in the amount identified in Table 5 and the Binder/TiO2Weight Ratio was as adjusted as set forth in Table 5. The durability of these compositions was then analyzed in the manner described in Durability Testing-Test 1. Results are set forth in Table 6.












TABLE 5








Silicate/TiO2
Amount of
Amount of



Composition
Weight Ratio
Binder/TiO21
WINDEX









H
0.35/0.25
30 g
8.91 g



I
0.35/0.25
30 g
6.26 g




















TABLE 6









Composition H
Composition I












Contact
Contact
Contact
Contact


Hours in
Angle Before
Angle After
Angle Before
Angle After


CCC
Exposure
Exposure
Exposure
Exposure














0
4
4
5
4


330
27
2
21
2


834
19
2
31
2


2390
26
3
23
5


3374
18
3
16
3


4022
38
4
32
11









Example 9 
Turbidity of Liquid Compositions
Liquid compositions K, L, M, and O were prepared in the manner described in Example 6 except that the pH was adjusted to the value set forth in Table 7 and the Binder/TiO2Weight Ratio was as adjusted, as set forth in Table 7. Liquid compositions N, P, and Q were prepared in a manner similar to Example 6, except that the pH of Charge I was not adjusted, and Charge II was a mixture of the titania sol and deionized water in an amount sufficient to dilute the titania sol from 15% solids to 2% solids with deionized water. The pH of Charge II was not adjusted and Charge II was added to Charge I to make the liquid composition. The turbidity of these compositions, was then analyzed over time by a Turbidimeter, Model DRT-100D, manufactured by Shaban Manufacturing Inc, H. F. Instruments Division using a sample cuvette of 28 mm diameter by 91 mm in length with a flat bottom. Results are set forth in Table 7.









TABLE 7









Turbidity (NTU)














Silicate/TiO2


1
3



Composition
Weight Ratio
pH
Initial
month
months
6 months
















K
0.5/0.3
1.96
490
558
569
652


L
0.5/0.3
1.57
438
552
567
653


M
0.35/0.2 
1.8
321
383
393
442


N
0.35/0.2 
3.25
454
412
385
425


O
 0.4/0.25
1.8
415
488
511
573


P
0.5/0.1
3.1
145
143
145
153


Q
0.9/0.1
3.11
149
143
145
162









Example 10 
Fogging Resistance on a Plastic Lens
This example is intended to illustrate the anti-fogging properties of the present invention. Thermoplastic polycarbonate lenses that were previously coated by the supplier with a non-tintable hardcoat (Gentex® PDQ®, commercially available from Gentex Optics, Inc.) were surface treated by washing with soap and water, rinsing with deionized water and isopropyl alcohol, and air drying. The lenses were then plasma treated. For example, 10A no additional coating was applied to the lens. For example 10B, the plasma-surface treated lens was coated with MSH-200 hydrolyzed organosilicate (1% solids) commercially available from Mitsubishi Chemical Corporation, Tokyo, Japan. For Example 10C, the plasma-surface treated lens was coated with a composition of the type described in Example 6, composition E by dip coating at an extraction rate of 230 mm/min.
Fogging property was evaluated by placing the lens over a cup filled with hot water. The lens of Example 10A fogged over the entire area thereof. The lens of Example 10B fogged over 50-60% of the area thereof. The lens of Example 10C has not fogging on the surface thereof.
Example 11 
Resistance to Fouling by Automotive Break Dust
This Example is intended to illustrate the anti-fouling properties of the present invention. Two aluminum alloy wheels purchased from DaimlerChrysler were divided into five even areas using masking tape. The wheels were installed on a 1996 model Chrysler Jeep Cherokee with one wheel (wheel #1) being installed on the front passenger side, and the other wheel (wheel #2) being installed on the front driver's side. Prior to installation, the five areas of each of wheel #1 and wheel #2 were treated as follows.
Wheel #1 Preparation
Prior to installation on the vehicle, the five areas of wheel #1 were treated as follows. No coating was applied to Area 1. Area 2 was coated with Hi-GardTM 1080 (an organosilane-containing coating solution available from PPG Industries, Inc.) by curtain coating using a wash bottle, air drying for 5 minutes, and the baking at 240° F. (116° C.) for 3 hours. Area 3 was coated with Hi-Gard 1080 as described above for Area #2. After baking, Area,3 was then coated with MSH-200 hydrolyzed organosilicate (1% solids) commercially available from Mitsubishi Chemical Corporation, Tokyo, Japan by wipe on application with a soaked sponge. The MSH-200 was then allowed to air dry and self-condense. Area 4 was coated with Hi-Gard 1080 as described above for Area 2. After baking, Area 4 was coated with a composition of the type described in Example 6, composition E and a mixture of deionized water: and ethanol (50/50 weight ratio) by wipe-on application using a soaked sponge. Area 5 was coated with a composition of the type described in Example 6, composition E.
The vehicle was driven for one Week. Areas 1 through 5 of Wheel #1 showed no significant difference in cleanliness prior to a water rinse. After being rinsed with water from a garden hose, the cleanliness of Areas 1 to 5 of wheel #1 was measured on a scale of 1 to 10 with higher number reflecting a cleaner surface. The results are summarized in Table 8.










TABLE 8







Area
Cleanliness



















1
2



2
6



3
8



4
10



5
10










Wheel #2 Preparation 
Prior to installation on the vehicle, the five areas of wheel #2 were treated as follows. No coating was, applied to Area 1. Area 2 was coated with SolGard® 330 coating (an organosilane-containing coating solution available from PPG Industries, Inc.) by curtain coating using a wash bottle, air drying for 5 minutes, and the baking at 240° F. (116° C.) for 3 hours. Area 3 was coated with Hi-Gard 1080 as described above for Area.2. After baking, Area 3 was then coated with MSH-200 hydrolyzed organosilicate (1% solids) commercially available from Mitsubishi Chemical Corporation, Tokyo, Japan by wipe on application with a soaked sponge. The MSH-200 was then allowed to air dry and self-condense. Area 4 was coated with Hi-Gard 1080 as described above for Area 2. After baking, Area 4 was coated with a composition of the type described in Example 6, composition E and a mixture of deionized water and ethanol (50/50 weight ratio) by wipe-on application using a soaked sponge. Area 5 was coated with a composition of the type described in Example 6, composition E.
The vehicle was driven for one week. Areas 1 through 5 of wheel #1 showed no significant difference in cleanliness prior to a Water rinse. After being rinsed with water from a garden hose, the cleanliness of Areas 1 to 5 of wheel #1 was measured on a scale of 1 to 10 with higher number reflecting a cleaner surface. The results are summarized in Table 9.










TABLE 9







Area
Cleanliness



















1
2



2
8



3
10



4
10



5
10










It will be readily appreciated by those skilled in the art that modifications may be made to the invention without departing from the concepts disclosed in the foregoing description. Such modifications are to be considered as included within the following claims unless the claims, by their language, expressly state otherwise. Accordingly, the embodiments described in detail herein are illustrative only and are not limiting to the scope of the invention, which is to be given the full breadth of the appended claims and any and all equivalents thereof.

## Claims

1. A method for improving the anti-fouling, self-cleaning, easy-to-clean, and/or anti-fogging properties of an article, wherein the article comprises a surface having a coating layer comprising an inorganic oxide network deposited thereon, the method comprising:
(1) applying a liquid composition comprising a hydrophilic ungelled essentially completely hydrolyzed organosilicate directly to at least a portion of the coating layer comprising an inorganic oxide network; and
(2) curing the composition applied in step (1) to provide a coating layer that:
(i) has a dry film thickness of no more than 200 nanometers, and
(ii) is substantially free of Si—OR groups, where R represents C1 to C4 alkyl groups; wherein the pH of the liquid composition is no more than 3.5 or from 7.0 to 8.5.

2. The method of claim 1, wherein the liquid composition further comprises a photocatalytic material.

3. The method of claim 2, wherein the photocatalytic material is in the form of particles having an average crystalline diameter of 3 to 35 nanometers.

4. The method of claim 2, wherein the photocatalytic material is present in the liquid composition in an amount ranging from 0.1 to 0.75 percent by weight based on the total weight of the composition.

5. The method of claim 1, wherein the organosilicate is present in the liquid composition in an amount ranging from 0.1 to 2 percent by weight calculated as SiO2, based on the total weight of the composition.

6. The method of claim 1, wherein the dry film thickness is 20 to 60 nanometers.

7. The method of claim 1, further comprising preparing the hydrophilic ungelled essentially completely hydrolyzed organosilicate by a process selected from:
(a) a multi-stage process comprising a first stage wherein a partial hydrolysis polycondensation reaction product is formed by reacting an organosilicate in water in the presence of an acid hydrolysis catalyst, wherein the water is present in an amount that is less than the stoichiometric amount capable of hydrolyzing the organoxy groups of the organosilicate, and a second stage wherein the partial hydrolysis polycondensation reaction product is contacted with water to form a hydrophilic ungelled essentially completely hydrolyzed organosilicate, and
(b) reacting a tetraalkoxysilane oligomer with water in the presence of an organic acid hydrolysis catalyst and/or an organic solvent, wherein the water is present in an amount that is greater than the stoichiometric amount capable of hydrolyzing organoxy groups of the alkoxysilane to form a hydrophilic ungelled essentially completely hydrolyzed organosilicate.