Process for the production of a photocatalytically active durable coated substrate, the photocatalytically active durable coated substrate and glass, articles made therefrom as well as process of their manufacture
41 claims: 13 independent, 28 dependent
- 1PATENTOVÉ NÁROKY 1. Způsob výroby trvanlivého fotokatalyticky aktivního skla s povlakem, při kterém se nanáší na povrch skleněného substrátu fotokatalyticky aktivní vrstva oxidu titanu, mající tlouštku menší než 40 nm, a to tím, že se s povrchem substrátu, který je na teplotě v rozmezí od 645°C do 720°C, uvádí do styku tekutá směs obsahující zdroj titanu.
- 2Způsob podle nároku 1, vyznačený tím, že substrát je na teplotě v rozmezí od 670°C do 720°C.
- 3Způsob podle nároku 1 neo 2, vyznačený tím, že tekutá směs je plynná směs obsahující tetraalkoxid titanu jako zdroj titanu.
- 4Způsob podle kteréhokoli z nároků 1 až 3, vyznačený tím, že tekutá směs je plynná směs obsahující tetraethoxid titanu jako zdroj titanu.
- 5Způsob podle kteréhokoli z nároků 1 až 4, vyznačený tím, že tekutá směs obsahuje chlorid titanu jako zdroj titanu a ester jiný než methylester.
- 6Způsob výroby fotokatalyticky povlakovaného substrátu, při kterém se nanáší na povrch substrátu povlak oxidu titanu, mající tloušťku menší než 40 nm, a to tím, že se s povrchem substrátu uvádí do styku tekutá směs obsahující chlorid titanu a ester jiný než methylester.
- 7Způsob podle nároku 6, vyznačený tím, že se sub-34• * ·· · · ·· ·· • · · ♦ · · · · * · • · · · · · · ·· · · • · · · · · · ·· ·· ···· · · ··· · strát uvádí do styku s tekutou směsí, když je na teplotě v rozmezí od 600°C do 750°C.
- 8Způsob podle kteréhokoli z nároků 5 až 7, vyznačený tím, že ester je alkylester mající alkylovou skupinu s β vodíkem.
- 9Způsob podle kteréhokoli z nároků 5 až 8, vyznačený tím, že ester je karboxylátový ester.
- 10Způsob podle kteréhokoli z nároků 5 až 9, vyznačený tím, že ester je alkylester mající C 2 až C 4 alkylovou skupinu.
- 11Způsob podle nároku 10, vyznačený tím, že ester je ethylester.
- 12Způsob podle nároku 11, vyznačený tím, že ester je ethylacetát.
- 13Způsob podle kteréhokoli z nároků 5 až 12, vyznačený tím, že ester je jediný zdroj kyslíku v tekuté směsi.
- 14Způsob podle kteréhokoli z nároků 1 až 13, vyznačený tím, že tekutá směs je plynná směs.
- 15Způsob podle kteréhokoli z nároků 1 až 14, vyznačený tím, že způsob se provádí přímým nanášením během výrobního procesu výroby skla float a substrát je skleněný pás.
- 16Způsob podle nároku 15, vyznačený tím, že se pro-35• 9· ·♦ ·· 99 99 99 9 9 9 9 9 9 9 9 9 · ··· 999 9999 9 9 9 9 9 9 9 9 vádí v plavící lázni procesu float.
- 17Způsob podle kteréhokoli z nároků 1 až 16, vyznačený tím, že se provádí při v podstatě atmosférickém tlaku.
- 18Fotokatalyticky aktivní povlakovaný substrát, mající na jednom svém povrchu fotokatalyticky aktivní vrstvu oxidu titanu, vyznačený tím, že povlečený povrch substrátu má fotokatalytickou aktivitu vyšší než 5 χ 10 -3 .cm -1 .min -1 , přičemž povlakovaný substrát má odraz viditelného světla naměřený na povlečené straně 35% nebo nižší.
- 19Fotokatalyticky aktivní povlakovaný substrát podle nároku 18, vyznačený tím, že povlečený povrch substrátu má fotokatalytickou aktivitu vyšší než 1 x 10 _2 cm“ 1 min“ 1 .
- 20Fotokatalyticky aktivní povlakovaný substrát podle nároku 19, vyznačený tím, že povlečený povrch substrátu má fotokatalytickou aktivitu vyšší než 3 x 10 -2 cm -1 min _1 .
- 21Fotokatalyticky aktivní povlakovaný substrát podle kteréhokoli z nároků 18 až 20, vyznačený tím, že povlakovaný substrát má odraz viditelného světla, naměřený na povlečené straně, 20% nebo nižší.
- 22Fotokatalyticky aktivní povlakovaný substrát podle nároku 21, vyznačený tím, že povlakovaný substrát má odraz viditelného světla, naměřený na povlečené straně, 15% nebo nižší.
- 23Fotokatalyticky aktivní povlakovaný substrát pod-36• 9* 99 99 • · 9 9 9 99 9 • · · 9 9 · • 99999 9 9 • 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 99 99 9 9 9 9 9 9 9 9 9 9 99 9999 le kteréhokoli z nároků 18 až 22, vyznačený tím, že obsahuje skleněný substrát.
- 24Fotokatalyticky aktivní povlakovaný substrát podle kteréhokoli z nároků 18 až 23, vyznačený tím, že povlakovaný substrát obsahuje mezi povrchem substrátu a fotokatalyticky aktivním povlakem oxidu titanu podkladní vrstvu blokující ionty alkalických kovů.
- 25Fotokatalyticky aktivní povlakovaný substrát podle nároku 24, vyznačený tím, že vrstva blokující ionty alkalických kovů je vrstva oxidu křemíku.
- 26Fotokatalyticky aktivní povlakovaný substrát podle kteréhokoli z nároků 18 až 25, vyznačený tím, že fotokatalyticky aktivní povlak oxidu titanu má tloušťku 30 nm nebo nižší.
- 27Fotokatalyticky aktivní povlakovaný substrát podle kteréhokoli z nároků 18 až 26, vyznačený tím, že fotokatalyticky aktivní povlak oxidu titanu má tloušťku 20 nm nebo nižší.
- 28Fotokatalyticky aktivní povlakovaný substrát podle nároku 27, vyznačený tím, že fotokatalyticky aktivní povlak oxidu titanu má tloušťku v rozmezí od 2 nm do 20 nm.
- 29Fotokatalyticky aktivní povlakovaný substrát podle kteréhokoli z nároků 18 až 28, vyznačený tím, že povlečený povrch substrátu má statický krajní úhel ve styku s vodou 20° nebo nižší. -37• ·· ·« ·· ·· • · · · · · · · » ·· « • · · · · · · · · • ··· ··· · · · · · • · · · · ··· ·»· ·· ·· ···· *« ··*·
- 30Fotokatalyticky aktivní povlakovaný substrát podle kteréhokoli z nároků 18 až 29, vyznačený tím, že povlakovaný substrát má zamlžení nižší než 1%.
- 31Fotokatalyticky aktivní povlakovaný substrát podle kteréhokoli z nároků 18 až 30, vyrobený způsobem podle kteréhokoli z nároků 1 až 17.
- 32Fotokatalyticky aktivní povlakovaný substrát podle kteréhokoli z nároků 18 až 31, vyznačený tím, že povlečený povrch substrátu je trvanlivý v oděru, takže povlečený povrch zůstává fotokatalyticky aktivní po té, co byl vystaven 300 přesuvových tahů podle Evropské normové zkoušky v oděru.
- 33Fotokatalyticky aktivní povlakovaný substrát podle nároku 32, vyznačený tím, že povlečený povrch zůstává fotokatalyticky aktivní po té, co byl vystaven 500 přesuvových tahů podle Evropské normové zkoušky v oděru.
- 34Fotokatalyticky aktivní povlakovaný substrát podle nároku 33, vyznačený tím, že povlečený povrch zůstává fotokatalyticky aktivní po té, co byl vystaven 1000 přesuvových tahů podle Evropské normové zkoušky v oděru.
- 35Fotokatalyticky aktivní povlakovaný substrát podle kteréhokoli z nároků 32 až 34, vyznačený tím, že zamlžení povlakovaného substrátu je po té, co byl podroben Evropské normové zkoušce v oděru, 2% nebo nižší. • 9 -38• 4 · · 9 * 4 9 •••44 4 · 9 · · « • 4 « 9 4*9 « ·· 44 44·« 44 9 4 4 4
- 36Fotokatalyticky aktivní povlakovaný substrát podle kteréhokoli z nároků 18 až 35, vyznačený tím, že povlakovaný substrát je trvanlivý vůči cyklickým změnám teploty při zvlhčení, takže povlečený povrch zůstává fotokatalyticky aktivní po té, co byl povlakovaný substrát podroben 200 cyklů zkoušky na cyklické změny teploty při zvlhčení.
- 37Trvanlivé fotokatalyticky aktivní povlakované sklo, obsahující skleněný substrát mající na svém povrchu povlak, který obsahuje podkladní vrstvu blokující ionty alkalických kovů a vnější fotokatalyticky aktivní vrstvu oxidu titanu, přičemž povlečený povrch substrátu je trvanlivý v oděru tak, že zůstává fotokatalyticky aktivní po té, co byl vystaven 300 přesuvových tahů podle Evropské normové zkoušky v oděru.
- 38Trvanlivé fotokatalyticky aktivní povlakované sklo podle nároku 37, vyznačené tím, že povlakované sklo má odraz viditelného světla, naměřený na povlečené straně, 35% nebo nižší, přičemž fotokatalyticky aktivní vrstva oxidu titanu má tloušťku 30 nm nebo nižší.
- 39Povlakované sklo obsahující skleněný substrát mající na svém jednom povrchu fotokatalyticky aktivní povlak oxidu titanu, vyznačené tím, že sklo má fotokatalytickou aktivitu vyšší než 8 x 10 _2 cm“ 1 min“ 1 a povlakované sklo má odraz viditelného světla, naměřený na povlečené straně, menší než 20%.
- 40Násobné izolační sklo obsahující první tabuli povlakovaného substrátu podle kteréhokoli z nároků 18 až 39, uloženou v odstupu od druhé tabule izolačního skla.
- 41Vrstvené sklo obsahující první vrstvu z povlakovaného skla podle kteréhokoli z nároků 18 až 39, mezivrstvu z polymeru a druhou vrstvu ze skla.
Independent claims41
329 paragraphs in 16 sections, as filed
Process for the production of coated photocatalytically active substrate, photocatalytically active and durable coated substrate and glass, articles thereof and process for their manufacture
Technical field
The invention relates to a process for the production of photocatalytically active substrates, and in particular, but not exclusively, to a process for the production of coated photocatalytically active glass and glasses thus produced.
BACKGROUND OF THE INVENTION
It is known to deposit thin coatings having one or more layers, with different properties, on substrates including glass substrates. One property of interest is the photocatalytic activity that results from the light generation (photogeneration) of a hole-electron pair in a semiconductor when the semiconductor is illuminated by light of a particular frequency. The hole-electron pair can be formed in sunlight and can react in humid air to form hydroxide and peroxide radicals on the surface of the semiconductor. Radicals oxidize the deposition of organic impurities on the surface. This property finds application in self-cleaning substrates, especially in self-cleaning windows for windows.
The effective photocatalyst may be titanium dioxide, which may be deposited on substrates to form a transparent coating with photocatalytic self-cleaning properties. Titanium oxide photocatalytic coatings are described in EP 0 901 991 A2, WO 97/07069, WO 97/10186, WO 98/41480, in abstract 745 of the 187-th Electrchemical Society Meeting (Reno, NV, 96-1, p.1102) and in New magazine
<img file="CZ20014395A3_D0001.tif" />
Scientist (August 26, 1995, p.19). WO 98/06675 describes a chemical vapor deposition method for coating titanium dioxide on a hot flat glass at a high deposition rate and using a precursor gas mixture of titanium chloride and an organic compound as the oxygen source to form a titanium dioxide coating.
It has been found that relatively thick oxide coatings are required to provide good photocatalytic activity. For example, WO 98/41480 discloses that a photocatalytically active self-cleaning coating must be sufficiently thick to provide an acceptable level of activity, and it is preferred that such a coating has a thickness of at least 200 Å (the measured thickness of titanium oxide coatings in the examples is always ranging from 400 Å to 2100 Å).
However, the problem of relatively thick titanium oxide coatings is the high visible light reflection and hence the relatively low visible light transmittance. This problem has been noted in a New Scientist article on coated vehicle windshields, where it is proposed to reduce the effect of high reflection so that dashboards are coated with black velvet or other material that does not reflect light into the coated windshield.
EP 0 901 992 A2 referred to above relates to titanium oxide coated photocatalytic glass panes having a particularly crystalline structure characterized by the presence of particular peaks in the X-ray diffraction pattern. The specification contemplates a range of coating thicknesses (with particular examples, all of which have a thickness ranging from 20 nm to 135 nm).
-3, with thinner coatings than thicker coatings). Describing from values as low as 750 ° C, but yields 400 ° C to 600 ° C, while finding in the preferred coating range less photocatalytically active also indicates a temperature range of as low as 300 ° C to values so preferred temperatures ranging from all specific examples of titanium dioxide at or below temperature.
SUMMARY OF THE INVENTION
The Applicant has now found that by coating titanium oxide coatings at higher temperatures, in particular temperatures above 600 ° C, it is possible to achieve coatings with increased photocatalytic activity for a given thickness, allowing the same photocatalytic efficiency to be obtained with thinner coatings. Such thinner coatings tend to have preferably lower light reflection and improved durability, apparently due to higher deposition temperature, especially against abrasion and cyclic temperature changes in humid air.
The present invention provides a method of producing a photocatalytically active coated substrate by applying a titanium oxide coating to a substrate surface by contacting the substrate surface with a liquid composition comprising a titanium source and an oxygen source, wherein the substrate has a temperature of at least 600 ° C to obtain substrate surface photocatalytic activity higher than 5 χ 10 “<sup>3</sup>.cm<sup>-1</sup>.min "<sup>1</sup> and a visible light reflection measured on the coated side of 35% or less.
Preferably, the substrate has a temperature in the range of 625 ° C to 720 ° C, preferably the substrate has a temperature in the range of 645 ° C to 720 ° C.
-4• · ·· ♦ · ·· ·· • ····· · · ·· · · • ···· · · · ··· ·· ·· ···· ·· ····
Preferably, the liquid mixture comprises titanium chloride as the source of titanium and an ester other than the methyl ester. Thus, in a preferred embodiment, the invention provides a process for producing a photocatalytically active substrate, wherein a titanium oxide having a thickness of less than 40 nm is deposited on the substrate by contacting the substrate surface with a liquid mixture comprising a chloride oxide and an ester other than the methyl ester.
The method may be carried out when the surface of the substrate with which the liquid composition is contacted is at a temperature in the range of 600 ° C to 750 ° C.
Preferably, the ester is an alkyl ester having an alkyl group with β hydrogen (the alkyl group of the alkyl ester is a group derived from an alcohol in ester synthesis and β hydrogen is hydrogen bonded to the carbon atom β, which is bonded to the oxygen of the ether bond in the ester). Preferably, the ester is a carboxylate ester.
Suitable esters may be alkyl esters having C<sub>2</sub> to C<sub>1Q </sub>but preferably the ester is an alkyl ester having a C 1-6 alkyl group<sub>2</sub> to C<sub>4</sub> an alkyl group.
Preferably, the ester is a compound of the formula:
RC (O) -OC (X) (X ') - C (Y) (Y') - R ', wherein R and R' are hydrogen or alkyl, X, X ', Y and Y' are monovalent substituents, preferably alkyl or hydrogen atoms, wherein at least one of Y and Y 'is hydrogen.
Suitable esters that can be used in the process of the invention include: ethyl formate, ethyl acetate, ethyl propionate, ethyl butyrate, n-propyl formate,
-5 n-propyl acetate, n-propyl propionate, n -propyl butyrate, isopropyl formate, isopropyl acetate, isopropyl propionate, isopropyl butyrate, n-butyl formate, n-butyl acetate and t-butyl acetate.
The ester is preferably an ethyl ester, more preferably ethyl formate, ethyl acetate or ethyl propionate. Most preferably, the ester is ethyl acetate.
The liquid mixture may be in the form of a liquid, in particular dispersed as a fine spray (a process often referred to as spray application), but preferably the liquid mixture is in the form of a gaseous mixture. The deposition process carried out using the gas mixture as a precursor is often referred to as chemical vapor deposition (CVD). A preferred form of CVD is laminar flow CVD, although turbulent flow CVD may also be used.
The process may be carried out on substrates of various dimensions, including flat substrates, in particular on cut glass sheets, or preferably on-line direct application in the production of float glass on a continuous glass ribbon. Thus, the process is preferably carried out by direct deposition in the production of float glass and the substrate is a glass ribbon. If the method is carried out on-line, it is preferably carried out on a glass web when it is in a float.
The advantage of direct coating in the on-line process is that directly applied coatings tend to be durable and in particular have good abrasion and chemical resistance.
-64· 44 ·· 44
4 *··· 4*4
44444 4 4 44 4 · • 4444 444 ··· ·4 44 4444 44 444
The direct deposition is preferably carried out at substantially atmospheric pressure, and other deposition processes are preferably carried out under these conditions.
In a particularly preferred embodiment, a method of producing permanently photocatalytically active coated glass is provided, wherein a photocatalytically active titanium oxide layer is deposited on the glass substrate surface by contacting a substrate surface having a temperature in the range of 645 ° C to 720 ° C, preferably in the range of 670 ° C to 720 ° C, with a liquid mixture containing a titanium source.
As noted above, the Applicants have found that by coating titanium oxide at high temperature, a coating with relatively high photocatalytic activity can be formed on its thickness, and that the invention also provides, since the coatings of smaller thickness tend to have less reflection, statements having advantageous combination of high photocatalytic activity with low or low light reflection.
Thus, according to a further feature of the invention, there is provided a photocatalytically active coated substrate comprising a substrate having a photocatalytically active titanium oxide coating on one surface thereof, characterized in that the surface of the coated substrate has a photocatalytic activity greater than 5 x 10<sup>_3</sup>cm "<sup>1</sup>min<sup>_1</sup>and that the coated substrate has a visible light reflection, measured on the coated side, of 35% or less.
High photocatalytic activity is advantageous because
The amount of contaminants (including dirt deposition) on the surface of the coated photocatalytic substrate will be reduced more rapidly than on substrates with relatively low photocatalytic activity. The relatively rapid removal of surface contaminants will also occur at relatively low levels of UV radiation.
Photocatalytic activity for the purposes of this specification is taught by measuring the rate of reduction of the integrated absorbance of infrared absorption peaks corresponding to CH strips of stearic acid in the form of a thin film formed on a coated substrate under UV light from a UVA lamp having an intensity of about 32 W / m<sup>2</sup> on the surface of the coated substrate and a peak wavelength of 351 nm. Stearic acid can be formed on the coated substrate by centrifugally casting a solution of stearic acid in methanol as described below.
Preferably, the coated substrate surface has a photocatalytic activity of greater than 1 x 10<sup>-2</sup>cm "<sup>1</sup>min<sup>-1</sup>, more specifically greater than 3 x 10 "<sup>2</sup>cm "<sup>1</sup>min "<sup>1</sup>.
Low visible light reflection is advantageous because it is less intrusive than high reflection, and low visible light reflection, in particular for glass substrates, corresponds to the high transmittance often required in the building and automotive glass sectors.
Preferably, the coated substrate has a low visible light reflection, measured on the coated side, of 20% or less and preferably 17% or less, and most preferably 15% or less.
444 * 4 9 9 9φ 4 9 •> 949 499 ··· ·· * · 4944 4 «4994 or lower.
In most embodiments of the invention, the substrate will be substantially transparent, and in a preferred embodiment of the invention, the substrate is a glass substrate. Typically, the glass substrate will be a soda-lime glass substrate.
Where the soda-lime glass substrate or other substrate comprises alkali metal ions, the coated substrate preferably has an alkali metal ion blocking substrate between the substrate surface and the photocatalytically active titanium oxide coating. This reduces the tendency of alkali metal ions to migrate from the substrate into the photocatalytically active titanium oxide coating, which is advantageous in view of the well-known activity of reducing the activity of alkali metal ions as a poison for semiconductor oxide coatings.
The alkali metal ion blocking backing layer may comprise a metal oxide, but preferably the alkali metal ion blocking layer is a silicon oxide layer. The silicon dioxide may be silicon dioxide but may not necessarily be stoichiometric and may contain impurities such as carbon (often referred to as silicon oxycarbide and deposited as described in GB 2 199 848) or nitrogen (often referred to as silicon oxinitride).
It is preferred that the alkali metal ion blocking backing layer is so thin that it has no significant effect on the coating, in particular by reducing the permeability of the coated transparent substrate or causing the formation of interferen-9-.
<td rowspan="2"> * ·♦ • · 9</td><td rowspan="2"> 9 « « 9</td><td rowspan="2"> 9 9 9 9</td><td colspan="2"> 99</td><td rowspan="2"> • 9 •</td>
<td> •</td><td> •</td>
<td> • 99· ·</td><td> • ·</td><td> 9 9</td><td> •</td><td> 9</td><td> •</td>
<td> • · 99 ··</td><td> • 9 99</td><td> 9 9*,«9</td><td> 9 99</td><td> 9</td><td> • 999</td>
colors in reflection or transmission. A suitable thickness range will depend on the properties of the material used to form the alkali metal ion blocking substrate (particularly its refractive index), but typically the alkali metal ion blocking substrate has a thickness of less than 60 nm and preferably less than 40 nm. Where present, the alkali metal blocking backing layer should always be sufficiently thick to reduce or block the penetration of alkali metal ions from the glass into the titanium oxide coating layer.
An advantage of the invention is that the photocatalytically active titanium oxide coating is thin (contributes to low reflection of visible light from the coated substrate), but the coated substrate still has sufficient photocatalytic activity. Preferably, the titanium oxide coating has a thickness of 30 nm or less, more preferably a thickness of 20 nm or less, and most preferably the titanium oxide coating has a thickness ranging from 2 nm to about 20 nm.
The invention is also advantageous in that the deposition of thin titanium oxide coatings requires less precursor and the layers can be deposited in a relatively short time. A thin titanium oxide coating is also less likely to cause color interference in reflection or transmission. However, a particular advantage is that the visible light reflection by the titanium oxide coating is low, which is particularly important when the coated substrate is glass. Usually, the desired permeability of the coated glass determines the thickness of the titanium oxide coating.
Preferably, the coated substrate surface has a static extreme angle in contact with water of 20 ° or less. Freshly prepared or cleaned glass has a hydrophilic surface (static
<img file="CZ20014395A3_D0002.tif" />
an extreme angle in contact with water of less than about 40 ° indicates a hydrophilic surface). A particular benefit of the coated substrates (and especially of the coated glasses) is that even if the coated surface is dirty, the irradiation of the coated surface with UV light of the correct wavelength will reduce the extreme angle by disrupting the contaminants. Another advantage is that water spills over the low edge angle surface, which will reduce the disruptive effect of water drops on the surface (for example, from rain) and will tend to rinse any dirt or other contaminants that have not been destroyed by photocatalytic surface activity. The static extreme angle is the angle formed by the meniscus of the water drop on the glass surface, and can be determined in a known manner by measuring the diameter of the water drop of a known volume on the glass surface and calculated using an iterative procedure.
Preferably, the coated substrate has a haze of 1% or less, which is beneficial because it allows clear viewing of the transparent coated substrate.
In preferred embodiments, the coated substrate surface is abrasion resistant so that the coated substrate remains photocatalytically active even when subjected to 300 strokes of the European Standard Abrasion Test. Preferably, the coated surface remains photocatalytically active after it has been subjected to 500 shear strokes of the European Standard Abrasion Test and most preferably the coated surface remains photocatalytically active after it has been subjected to 1000 shear strokes of the European Standard Abrasion Test.
This is advantageous since the self-cleaning coated substrates of the invention will often be used with
<img file="CZ20014395A3_D0003.tif" />
a surface exposed to the outside (eg coated glass with a coated glass surface as the outer surface of the window) where the coating is abrasive vulnerable.
The European Standard Abrasion Test is a test described in European Standard BS EN 1096 Part 2 (1999) and involves the reciprocating movement of a felt pad at a set speed and pressure over the sample surface.
In this document, a coated substrate is considered to remain photocatalytically active if, after being subjected to the European Standard Abrasion Test, UV irradiation (e.g., a peak wavelength of 351 nm) reduces the static extreme angle in contact with water below 15 °. Achieving this extreme angle after abrasion of the coated substrate will generally take less than 48 hours of irradiation at an intensity of approximately 32 W / m<sup>2</sup> on the surface of the coated substrate.
Preferably the misting of the coated substrate is 2% or less after being subjected to a European abrasion test.
The durable coated substrates of the invention may also be durable to cyclic changes in humidification temperature (which are believed to have a similar effect to weathering). Thus, in preferred embodiments of the invention, the coated substrate is durable to cyclic wetting temperature changes in the sense that it is photocatalytically active after being subjected to 200 cycles of cyclic wetting temperature test. In this document, the cyclic humidification test refers to a test in which the coating is subjected to a temperature cycle from 35 ° C to 75 ° C and then
-12 to 35 ° C in 4 hours at a humidity close to 100% relative humidity. The coated substrate is considered to remain photocatalytically active if, after the test, UV irradiation reduces the static extreme angle in contact with water to below 15 °.
In another preferred embodiment, the invention provides a durable photocatalytically active coated glass comprising a glass substrate having a coating on one surface, the coating comprising an alkali metal ion blocking substrate and a photocatalytically active titanium oxide layer, wherein the coated substrate surface is abrasion resistant such that the coated surface it remains photocatalytically active after being subjected to 300 shifts according to the European Standard Abrasion Test. In this embodiment, the coated glass preferably has a visible light reflection measured on the coated side of 35% or less, and the photocatalytically active titanium oxide layer preferably has a thickness of 30 nm or less. Thin coatings are abrasion-resistant, which is surprising since it was previously assumed that only thick coatings had good durability.
According to yet another embodiment, the invention provides glass with a coating comprising a glass substrate provided on one of the surfaces with a photocatalytically active titanium oxide coating, the solution being characterized in that the coated glass surface has a photocatalytic activity of greater than 4 x 10<sup>_2</sup>cm ”<sup>1</sup>min ”<sup>1</sup>, preferably greater than 8 x 10<sup>-2</sup>cm<sup>-1</sup>min<sup>-1</sup>wherein the coated glass has a visible light reflectance measured on the coated side of less than 20%.
<img file="CZ20014395A3_D0004.tif" />
The coated substrates of the invention find application in a number of areas, such as glazing windows including insulating glass comprising a first sheet of coated substrate spaced from the second glass sheet, or when the coated substrate is coated glass, such as laminated glass comprising a first coated glass layer, an intermediate layer of a polymer (e.g., polyvinyl butyral) and a second layer of glass.
In addition to use in self-cleaning substrates (especially self-cleaning windows for windows), the coated substrates of the invention may find application for reducing the concentration of atmospheric contaminants. For example, a coated glass can irradiate atmospheric contaminants such as nitrogen oxides, ozone, and organic pollutants adsorbed to the coated glass surface when exposed to UV wavelengths (including UV wavelengths present in sunlight). This use is particularly advantageous in open built-up areas (for example in city streets) where the concentration of organic contaminants can be relatively high (especially in intense sunlight), but where the available glass surface area is also relatively high. Alternatively, coated glass (with a coated surface on the inside) can be used to reduce the concentration of atmospheric contaminants inside buildings, especially in office buildings having a relatively high concentration of atmospheric contaminants.
The invention is further illustrated by the following non-limiting examples.
-14• ·
<img file="CZ20014395A3_D0005.tif" />
BRIEF DESCRIPTION OF THE DRAWINGS
In the drawings, FIG. 1 is a diagram of the photocatalytic activity of a coated glass produced by the process of the present invention as a function of the thickness of the titanium oxide layer; and FIG.
DETAILED DESCRIPTION OF THE INVENTION
The glasses whose photocatalytic activity is demonstrated by FIG. 1 were produced using the direct chemical vapor deposition methods described in the examples below. Rings 1 denote titanium oxide layers deposited using titanium tetrachloride as titanium precursor and crosses 2 denote titanium oxide layers deposited using titanium tetraethoxide as titanium precursor.
The coating layers may be applied by on-line application to the glass substrate by chemical vapor during the glass manufacturing process. Fig. 2 shows an apparatus 10 suitable for manufacturing a coated glass article according to the invention, comprising a float section 11, an oven 12 and a cooling section 13. The float section 11 comprises a bath bottom 14 with a molten tin bath 15, a ceiling 16, side walls (not shown) and end walls 17 which define a tightly closed zone 18 in which a non-oxidizing atmosphere is maintained to prevent oxidation of the tin bath 15. During operation of the apparatus 10, the molten glass 19 is poured into a bath 20 from which it flows under the metering slide wall 21 and then downwardly to the surface of the tin bath 15 to form a float glass belt 37 collected by the pickup rollers 22 and conveyed by the furnace 12. Section 13.
-15• · 9 9 9 9 · • 9 9 9 9 9 9 9
999 99 99 99·· 99 9999
A non-oxidizing atmosphere is maintained in the float section 11 by introducing a suitable gas, such as nitrogen containing gas and 2% hydrogen, into the zone 18 via lines 23 connected to the manifold 24. The non-oxidizing gas is supplied to the zone 18 from line 23 at a sufficient flow rate. to compensate for gas losses (a portion of the non-oxidizing atmosphere leaves the zone 18 below the end walls 17) and to maintain a slight overpressure above ambient pressure. The tin bath 15 and the closed zone 18 are heated by radiant heat directed downward from the heaters 25. The zone 18 is generally maintained at a temperature of about 721 ° C to 760 ° C (1330 ° F to 1400 ° F). The atmosphere in the furnace 12 is typically air, and the cooling section 13 is open. The ambient air is blown on the glass by fans 26.
The apparatus 10 also includes coats 27, 28, 29 and 30 arranged in line in the float zone 11 above the float glass belt 37. The precursor gas mixtures for the individual layers of the coating are fed to the respective coatings, which in turn direct the precursor gas mixtures to the hot surface of the float glass web 37. The temperature of the float glass belt 37 is highest at the point of the liner 27 closest to the tub 20 and lowest at the point of the liner 30 closest to the furnace 12.
The invention is further elucidated by the following examples in which the coatings were deposited by laminar flow chemical vapors in a float bath on a moving float ribbon during the glass manufacturing process. In the examples, two-layer coatings were applied to the glass web.
All gas volumes were measured at standard temperature and pressure unless otherwise noted. Thickness values indicate-16 • 4 94 • 4 4 4 • · 4
9 4 4 • 94
9449 • 9 44 • 4 4 4
4 4
4 4
4 4
4449 They were determined using a high resolution scanning electron microscope and optical modeling of reflection and transmission spectra for coated glass. The coating thickness was measured with an uncertainty of approximately 5%. The transmission and reflection properties of coated glasses were determined using a Hitachi U-4000 spectrophotometer. The a, b, and L * values given herein for the color of the transmission and / or reflection glass refer to the CIE Lab colors. The reflection and transmission of visible light through the coated glass were determined using D65 illuminant and a CIE 2 ° standard observer according to ISO 9050 (Parry Moon airmass 2). Fogging of the coated glasses was measured using a WYK-Gardner Hazeguard + haze meter.
The photocatalytic activity of the coated glasses was determined from the rate of decrease in the area of infrared peaks corresponding to the CH bands of the stearic acid film on the coated glass surface under UVA light illumination. The stearic acid film was formed on 7-8 cm square glass samples by centrifugal casting of a 20 μΐ solution of stearic acid in methanol (8.8 x 10 “<sup>3</sup>mol drn '<sup>3</sup>) on a coated glass surface at 2000 rpm. Infrared spectra in the transmission were measured and the peak height of the peak corresponding to the CH bands was measured (at approximately 2700 to 3000 cm ').<sup>1</sup>) of the stearic acid film and the corresponding peak peak area was determined from the peak area calibration curve against peak height. The coated side of the glass was irradiated with a UVA-351 lamp (from Q-Panel Co., Cleveland, Ohio, USA) having a peak wavelength of 351 nm with an intensity on the surface of the coated glass of approximately 32 W / m<sup>2</sup>. The photocatalytic activity in this description is expressed as either the rate of decrease of the IR area
9*
-17 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 999 9 in cm ”<sup>1</sup>min ”<sup>1</sup>) or as t<sub>go</sub>% (in minutes as units), which is the time of exposure to UV radiation required to reduce the peak height (absorption) of the peak in the respective wavelength range to 10% of the original value.
The static extreme angle of the coated glass was determined by measuring the diameter of a water drop (1 to 5 μ 1 volume) deposited on the surface of the coated glass after irradiation of the coated glass using a UVA 351 lamp for approximately 3 hours (or as otherwise indicated).
EXAMPLES 1-15
A 1 mm soda-lime glass web, passing through an oven at 300 m / h, was coated with a two-layer coating as the web was moved across the float bath at a position where the glass temperature was in the range of about 650 ° C to about 670 ° C. The atmosphere above the float bath contained a flowing gas mixture of nitrogen and 9% hydrogen at a bath pressure of approximately 15 Pa (0.15 mbar).
Layer 1 (the first layer deposited on glass) was a silicon oxide layer. Layer 1 was applied by gaseous mixture of monosilane (SiH<sub>4</sub>, 60 ml / min), oxygen (120 ml / min), ethylene (360 ml / min) and nitrogen (8 l / min) were brought into contact with the glass surface while flowing parallel to it, in the direction of glass movement, using a coating the apparatus described in GB 1 507 966 (see in particular Fig. 2 and the corresponding description on page 3, line 73, to page 4, line 75), with a path of movement of the gaseous mixture over the glass surface of approximately 0.15 m The extraction was at about 90 to 120 Pa (0.9 to 1.2 mbar). The strip of glass was coated over a width of approximately 10 cm at the point where its temperature was
-18 about 670 ° C. The thickness of the silica layer was approximately 20 to 25 nm.
Layer 2 (second deposited layer) was a titanium dioxide layer. Layer 2 was applied by combining separate gas streams containing titanium tetrachloride in the flowing nitrogen carrier gas, ethyl acetate in the flowing nitrogen carrier gas, and a main nitrogen stream of 8 l / min (flow measured at 138 kPa or 20 psi) into a gas mixture and subsequent dispensing maintained at a temperature of approximately 250 ° C) of a gaseous mixture to a coating apparatus consisting of a double-jet oil-cooled coating. The pressure of the nitrogen carrier gas and the main nitrogen stream was approximately 138 kPa (20 psi). The gaseous mixture came into contact with the glass surface and flowed along the surface both in parallel to the upstream movement of the glass ribbon and upstream. The downstream path of the gaseous mixture was approximately 0.15 m and upstream of approximately 0.15 m with an offtake of approximately 15 Pa. Titanium tetrachloride and ethyl acetate were entrained in separate streams of flowing nitrogen carrier gas by passing nitrogen through either the titanium tetrachloride bubbler or the ethyl acetate bubbler. The nitrogen carrier gas flow rates are described in Table 1 (flow rates measured at 138 kPa or 20 psi). The bubbler was maintained at 42 ° C. Table 1 also lists the estimated entrained titanium tetrachloride and entrained ethyl acetate flow rates for each of Examples 1 to 15.
The properties of the two-layer coatings were measured. The thickness values of layer 2 (titanium oxide layer) and the reflectance values of the detectable radiation measured on the coated side, L * and fogging of the coated glasses are described in Table 2 for Examples 1 to 15. The fogging of each coated glass was less than 0, 2%
The photocatalytic activity and static extreme angle in contact with water were determined. Initial peak height and initial peak area of IR peaks corresponding to CH bands of stearic acid, photocatalytic activity, static extreme angle in contact with water and t<sub>go</sub>% for Examples 1-15 are shown in Table 3. The thickness of the titanium oxide layer has surprisingly little effect on photocatalytic activity.
EXAMPLES 16-19
Examples 16-19 were performed under the same conditions as Examples 1-15, except that the bath pressure was approximately 11 Pa (0.11 mbar, the bottom coating (Layer 1) collection for silica was approximately 7 Pa (0). 7 mbar), the titanium tetrachloride bubbler was maintained at about 100 ° C, the ethyl acetate bubbler was held at about 45 ° C, and the feed line was maintained at about 220 ° C.
The flow rates of nitrogen carrier gas and estimated flow rates of entrained titanium tetrachloride and ethyl acetate for each of Examples 16-19 are shown in Table 1.
The estimated thickness of the layer 2 (titanium oxide layer), and the visible reflection values measured on the coated side, L *, and haze of the coated glasses are described in Table 2 for each of Examples 16-19.
-20 Initial peak height and initial peak area of IR peaks corresponding to CH bands of stearic acid, photocatalytic activity, t<sub>90</sub>and the static extreme angle, for each of Examples 16-19, are shown in Table 3.
The photocatalytic activity in Examples 16-19 was not significantly greater than in Examples 1-15 despite the thicker (and therefore more reflective) titanium oxide coatings.
TAB.l
<td rowspan="2">Ex.</td><td colspan="2" rowspan="2">Carrier flow rate N to bubblers (1 / min, measured at 138 kPa)</td><td colspan="2">TiCl<sub>4</sub> Ethyl acetate</td>
<td>Flow rates</td><td>1 / min)</td>
<td> 1</td><td>TiCl bubbler<sub>4</sub> 0,16</td><td>Bubble with ethyl acetate 1</td><td> 0,032</td><td> 0,46</td>
<td> 2</td><td> 0,12</td><td> 0,3</td><td> 0,024</td><td> 0,14</td>
<td> 3</td><td> 0,12</td><td> 0,45</td><td> 0,024</td><td> 0,21</td>
<td> 4</td><td> 0,08</td><td> 0,2</td><td> 0,016</td><td> 0,09</td>
<td> 5</td><td> 0,12</td><td> 0,15</td><td> 0,024</td><td> 0,07</td>
<td> 6</td><td> 0,12</td><td> 0,75</td><td> 0,024</td><td> 0,35</td>
<td> 7</td><td> 0,08</td><td> 0,3</td><td> 0,016</td><td> 0,14</td>
<td> 8</td><td> 0,08</td><td> 0,5</td><td> 0,016</td><td> 0,23</td>
<td> 9</td><td> 0,04</td><td> 0,1</td><td> 0,008</td><td> 0,05</td>
<td> 10</td><td> 0,04</td><td> 0,15</td><td> 0,008</td><td> 0,07</td>
<td> 11</td><td> 0,04</td><td> 0,25</td><td> 0,008</td><td> 0,12</td>
<td> 12</td><td> 0,16</td><td> 0,1</td><td> 0,032</td><td> 0,05</td>
<td> 13</td><td> 0,08</td><td> 0,1</td><td> 0,016</td><td> 0,05</td>
<td> 14</td><td> 0,16</td><td> 0,4</td><td> 0,032</td><td> 0,19</td>
<td> 15</td><td> 0,16</td><td> 0,2</td><td> 0,032</td><td> 0,09</td>
-21TAB.1-continued
<td> 16</td><td> 0,1</td><td> 0,5</td><td> 0,088</td><td> 0,27</td>
<td> 17</td><td> 0,08</td><td> 0,4</td><td> 0,070</td><td> 0,22</td>
<td> 18</td><td> 0,06</td><td> 0,3</td><td> 0,053</td><td> 0,16</td>
<td> 19</td><td> 0,04</td><td> 0,2</td><td> 0,035</td><td> 0,11</td>
TAB.2
<td>Ex</td><td>. Thickness layers of oxide titanium (nm)</td><td>Reflection visitor. coated glass radiation (%)</td><td>L * for coated glass</td><td>Fogging (%)</td>
<td> 1</td><td> 15</td><td> 14,1</td><td> 44</td><td> 0,12</td>
<td> 2</td><td> 14,3</td><td> 13,9</td><td> 44</td><td> 0,07</td>
<td> 3</td><td> 14,2</td><td> 13,2</td><td> 43</td><td> 0,12</td>
<td> 4</td><td> 11,3</td><td> 11,4</td><td> 40</td><td> 0,08</td>
<td> 5</td><td> 12,1</td><td> 12,1</td><td> 41</td><td> 0,08</td>
<td> 6</td><td> 11,0</td><td>and</td><td>and</td><td> 0,07</td>
<td> 7</td><td> 8</td><td>and</td><td>and</td><td> 0,11</td>
<td> 8</td><td> 7,2</td><td> 9,7</td><td> 37</td><td> 0,04</td>
<td> 9</td><td> 6,1</td><td> 9,1</td><td> 36</td><td> 0,05</td>
<td> 10</td><td> 5,6</td><td> 9</td><td> 36</td><td> 0,07</td>
<td> 11</td><td> 4,6</td><td> 8,7</td><td> 35</td><td> 0,06</td>
<td> 12</td><td> 15,6</td><td> 15,4</td><td> 46</td><td> 0,1</td>
<td> 13</td><td> 16,0</td><td>and</td><td>and</td><td> 0,13</td>
<td> 14</td><td> 17,5</td><td> 16,2</td><td> 47</td><td> 0,14</td>
<td> 15</td><td> 20,3</td><td> 19,5</td><td> 51</td><td> 0,1</td>
<td> 16</td><td>and</td><td> 28,4</td><td> 47,8</td><td> 0,3</td>
<td> 17</td><td>ca 68</td><td> 29,1</td><td> 58,4</td><td> 0,37</td>
<td> 18</td><td>ca 3 2</td><td> 25,9</td><td> 55,6</td><td> 0,24</td>
<td>19 Dec and</td><td>ca 27 Not measured</td><td> 20,5</td><td> 50,2</td><td> 0,2</td>
-22TAB.3
Ex
IR peaks corresponding to CH bands of stearic acid film (2700-3000 cm<sup>-1</sup>)
Fotokatalyt. State. extreme activity (x 10<sup>-2</sup>cm<sup>-1</sup> angle min<sup>-1</sup>) with water <sup>t</sup>90% (min)
Initial peak height (arbitrary units)
Initial peak area (cm<sup>-1</sup>) (°)
<td> 1</td><td> 0,030</td><td> 1,04</td><td> 9,4</td><td> 17±5</td><td> 10</td>
<td> 2</td><td> 0,0331</td><td> 1,15</td><td> 10,4</td><td> 15±1</td><td> 10</td>
<td> 3</td><td> 0,0311</td><td> 1,08</td><td> 12,2</td><td> 13±2</td><td> 8</td>
<td> 4</td><td> 0,0324</td><td> 1,13</td><td> 6,8</td><td> 14±1</td><td> 15</td>
<td> 5</td><td> 0,0287</td><td> 1,00</td><td> 8,2</td><td> 16±3</td><td> 11</td>
<td> 6</td><td> 0,028</td><td> 0,98</td><td> 8,8</td><td> 15+1</td><td> 10</td>
<td> 7</td><td> 0,0343</td><td> 1,20</td><td> 10,8</td><td> 15±1</td><td> 10</td>
<td> 8</td><td> 0,0289</td><td> 1,03</td><td> 6,6</td><td> 16±1</td><td> 14</td>
<td> 9</td><td> 0,0289</td><td> 1,01</td><td> 6,5</td><td> 14±2</td><td> 14</td>
<td> 10</td><td> 0,0278</td><td> 0,97</td><td> 6,2</td><td> 18±2</td><td> 14</td>
<td> 11</td><td> 0,0344</td><td> 1,20</td><td> 5,4</td><td> 18±1</td><td> 20</td>
<td> 12</td><td> 0,0291</td><td> 1,02</td><td> 10,2</td><td> 12±1</td><td> 9</td>
<td> 13</td><td> 0,0289</td><td> 1,01</td><td> 9,1</td><td> 14±2</td><td> 10</td>
<td> 14</td><td> 0,0269</td><td> 0,94</td><td> 9,4</td><td> 15±2</td><td> 9</td>
<td> 15</td><td> 0,0331</td><td> 1,15</td><td> 8,7</td><td> 15±2</td><td> 12</td>
<td> 16</td><td> 0,0227</td><td> 0,79</td><td> 17,8</td><td> 12</td><td> 4</td>
<td> 17</td><td> 0,026</td><td> 0,91</td><td> 10,2</td><td> 12</td><td> 8</td>
<td> 18</td><td> 0,0225</td><td> 0,79</td><td> 10,1</td><td> 13</td><td> 7</td>
<td> 19</td><td> 0,0258</td><td> 0,90</td><td> 10,1</td><td> 16</td><td> 8</td>
-23 EXAMPLES 20-27
Examples 20-27 were performed under the same conditions as Examples 1-15, except that Layer 2 was deposited from a gaseous mixture containing titanium tetraethoxide contained in a nitrogen carrier gas passing through a titanium tetraethoxide bubbler maintained at 170 ° C. The flow rates of nitrogen carrier gas (measured at 138 kPa or 20 psi) and titanium tetraethoxide are shown in Table 4 for each of Examples 20-27. The main flow rate of nitrogen gas was 8.5 l / min (measured at 138 kPa or 20 psi).
The properties of two-layer coatings were measured. The values of the layer 2 thickness (titanium oxide layer) and the visible reflection values measured on the coated side and the haze of the coated glasses are given for Examples 20-27 in Table 5. The fogging of each coated glass was below 0.7%.
Photocatalytic activity and static extreme angle in contact with water were determined. Initial peak height and initial peak area of IR peaks corresponding to CH bands of stearic acid, photocatalytic activity and t<sub>go</sub>%, <sup>and</sup> static edge angle in contact with water for each of Examples 20-27 are described in Table 6.
EXAMPLES 28 and 29
Examples 28 and 29 were performed under the same conditions as Examples 20 to 27 except that the titanium tetraethoxide bubbler was maintained at 168 ° C and the bath pressure was 11 Pa (0.11 mbar). Data relating to Examples 28-29, equivalent to the data for Examples 20-27, are described in Tables 4, 5 and 6.
-24TAB.4
Ex. Nitrogen flow rates as carrier Flow of gas ethoxide into the titanium bubbler (1 / min) titanium tetraethoxide (1 / min, measured at 138 kPa)
<td> 20</td><td> 0,25</td>
<td> 21</td><td> 0,15</td>
<td> 22</td><td> 0,2</td>
<td> 23</td><td> 0,25</td>
<td> 24</td><td> 0,3</td>
<td> 25</td><td> 0,35</td>
<td> 26</td><td> 0,2</td>
<td> 27</td><td> 0,1</td>
<td> 28</td><td> 0,6</td>
<td> 29</td><td> 0,4</td>
0,014
0,008
0,011
0,014
0,017
0,019
0,011
0,006
0,030
0,020
<td colspan="4">TAB.5</td>
<td>Ex.</td><td>Layer thickness titanium oxide (nm)</td><td>Reflection of the visible glass radiation with coating (%)</td><td>Fogging (%)</td>
<td> 20</td><td> 13</td><td>and</td><td> 0,4</td>
<td> 21</td><td> 13</td><td>and</td><td> 0,29</td>
<td> 22</td><td> 16</td><td> 15,7</td><td> 0,29</td>
<td> 23</td><td> 18</td><td>and</td><td> 0,28</td>
<td> 24</td><td> 24</td><td>and</td><td>and</td>
<td> 25</td><td> 26</td><td>and</td><td> 0,61</td>
<td> 26</td><td> 9,9</td><td> 10,9</td><td> 0,19</td>
-25TAB.5-continued
4,7
38,3
31,9
8,8
35,2
28,4
0,29
0,29
0.22 and Not Measured
TAB.6
<td colspan="3">Ex. IR peaks, corresponds-</td><td rowspan="2">Fotokatalyt. activity (x l0 ”<sup>2</sup>cm<sup>-1 </sup>min ”<sup>1</sup>)</td><td rowspan="2">Static extreme angle with water (°;</td><td rowspan="2"><sup>Ť</sup>90% (min) )</td>
<td></td><td colspan="2">giving CH bands of stearic acid (2700-3000 cm<sup>-1</sup>)</td>
<td></td><td>Počát.vrchol.</td><td>Počát.vrchol</td><td> . ·</td><td></td><td></td>
<td></td><td>height (</td><td>flat</td><td></td><td></td><td></td>
<td></td><td>vol.jednotky)</td><td>(cm ”)<sup>1</sup>)<sup>)</sup></td><td></td><td></td><td></td>
<td> 20</td><td> 0,027</td><td> 0,953</td><td> 5,7</td><td> 19±5</td><td> 15</td>
<td> 21</td><td> 0,031</td><td> 1,095</td><td> 5,7</td><td>and</td><td> 17</td>
<td> 22</td><td> 0,024</td><td> 0,838</td><td> 3,6</td><td> 15±2</td><td> 21</td>
<td> 23</td><td> 0,030</td><td> 1,029</td><td> 7,1</td><td> 11±3</td><td> 13</td>
<td> 24</td><td> 0,029</td><td> 1,015</td><td> 7</td><td> 17±3</td><td> 13</td>
<td> 25</td><td> 0,031</td><td> 1,071</td><td> 7,4</td><td> 13±4</td><td> 13</td>
<td> 26</td><td> 0,031</td><td> 1,085</td><td> 4,4</td><td> 21±3</td><td> 22</td>
<td> 27</td><td> 0,029</td><td> 0,998</td><td> 3,2</td><td> 16±5</td><td> 28</td>
<td> 28</td><td> 0,021</td><td> 0,733</td><td> 3,6</td><td> 13</td><td> 18</td>
<td> 29</td><td> 0,024</td><td> 0,848</td><td> 3,3</td><td> 14</td><td> 23</td>
and Not measured
-26 EXAMPLES 30-42
In Examples 30-42, two-layer coatings were deposited by direct CVD by chemical vapor deposition on a float glass strip at its full width of approximately 3.35 meters in a float bath during the float manufacturing process. The apparatus used for coating is illustrated in FIG. The bathing atmosphere contained nitrogen and 2% v / v hydrogen. The bath pressure was 15 Pa (0.15 bar).
The two-layer coating consisted of a silicon oxide layer deposited on the float glass ribbon and a titanium oxide layer deposited on the silicon oxide layer. The precursor chemistry of the gaseous mixtures used for coating was the same as used in Examples 1-15. The coating temperature was varied using different coaters 27, 28, 29 or 30 (referring to or.2). The liner 27 closest to the tub had the highest temperature, and the liner 30 closest to the furnace would be coldest. In Examples 30-33 and 42, two coatings (28 and 29 in Examples 30-33 and coatings 27 and 28 in Example 42) were used for silicon oxide deposition. The advantage of using two coats to apply a layer of silicon oxide is that longer run times are possible.
The gas mixture used to apply the silicon oxide layer for Examples 30 to 41 consisted of the following gases at the following flow rates: helium (250 rpm), nitrogen (385 rpm), monosilane (2.5 rpm), ethylene (15 L / min) and oxygen (10 L / min). For Example 42, the same flow rates were used except for monosilane (2.3 L / min), ethylene (13.8 L / min) and oxygen (9.3 L / min). Where two coats were used to apply the silicon oxide layer in Examples 30 to 42, the above flow rates were used for each coater.
<img file="CZ20014395A3_D0006.tif" />
• · ·»·· · · ····
In Examples 30-42, the deposition temperatures (ie, the temperatures of the float glass strip under the coating corresponding to each of the coatings were 27-30). as shown in Table 7. The temperatures in Table 7 have an uncertainty of approximately + 28 ° C (± 50 ° F). Sampling for each coating was at approximately 200 Pa (2 mbar).
TAB.7
Liner
Approximate
721 ° C
690 ° C
677 ° C
621 ° C glass strip temperature (1330 ° F) (1275 ° F) (1250 ° F) (1150 ° F)
Titanium tetrachloride (TiCl<sub>4</sub>) and ethyl acetate were entrained in separate nitrogen / helium carrier gas streams. For evaporation of TiCl<sub>4</sub> a thin film evaporator was used. Liquid TiCl<sub>4</sub> was held in a pressure vessel (overpressure approx
34.4 kPa or 5 psi). This was used to dispense liquid to a metering pump and a flow measurement system based on the Coriolis force principle. The measured precursor stream was then fed to a thin film evaporator at a temperature of 43 ° C (110 ° F). TiCl<sub>4</sub> was then entrained in the carrier gas (helium) and fed to the mixing point through lines maintained at 121 ° C (250 ° F). Ethyl acetate was supplied in a similar manner. Liquid ethyl acetate was held in a pressure vessel (gauge pressure of about 34.4 kPa or 5 psi). This was used to dispense liquid to a metering pump and a flow measurement system based on the Coriolis force principle. The measured precursor current was then fed to a thin evaporator
<img file="CZ20014395A3_D0007.tif" />
film at 131 ° C (268 ° F). Evaporated ethyl acetate was then carried in the carrier gas (helium / nitrogen mixture) and conveyed to the mixing point through pipes maintained at 121 ° C (250 ° F).
TiCl gas streams<sub>4</sub> and ethyl acetate were combined to form a gaseous mixture to deposit a titanium oxide layer. This mixing point lay just in front of the liner.
Line speed of float glass strip, silicon oxide deposition temperature and titanium oxide deposition temperature, and He / N main carrier gas flow rates<sub>2</sub> and TiCl flow rate<sub>4</sub> and ethyl acetate are shown in Table 8 for Examples 30-42.
The coated strip of float glass was cooled and cut to determine the optical properties and photocatalytic activity of the samples. Table 9 shows haze, transmission and reflection optical properties (percent transmittance and visible light reflection, and color coordinates using the LAB system) of the samples. The coated glasses were subjected to an abrasion test according to BS EN 1096, in which a sample of 300 mm x 300 mm is rigidly fixed at four corners to the test bed, ensuring that no movement of the sample is possible. An unused felt pad of the dimensions specified in the standard (BS EN 1096, Part 2 (1999)) was then mounted on a test finger which was lowered onto the glass surface. The 4 N pressure applied to the test finger and test was then adjusted. has started. The finger was reciprocated through the sample in 500 strokes at 60 strokes per minute ± 6 strokes / min. Upon completion of this abrasion, the sample was removed and examined optically for photocatalytic
<img file="CZ20014395A3_D0008.tif" />
activities. A sample is considered compliant if the abrasion results in a change in transmittance of not more than ± 5% when measured at 550 nm and the coated substrate remains photocatalytically active, which means that after a 2-hour UV irradiation test, it decreases static extreme angle below 15 °.
The glasses were also subjected to a cyclic humidification temperature change test where the coating was subjected to a temperature cycle of 35 ° C-75 ° C-35 ° C for 4 hours at a humidity close to 100% relative humidity.
Static extreme angle of coated glass, as manufactured and after 130 minutes of UV irradiation (UVA 351 nm lamp at approximately 32 W / m)<sup>2</sup>) and after 300, 500 and / or 1000 draws of the European Standard Abrasion Test, see Table 10. The extreme angle of the abraded samples was determined after irradiation for 2 hours.
Samples applied at higher temperatures of 721 ° C to 677 ° C (1330-1250 ° F) were photocatalytically active even after 1000 strokes according to the European Standard Abrasion Test or after 200 cycles of humidification temperature changes. Photocatalytic activity of coated glass in the form of t-value<sub>go</sub>%, in the fabricated state and after 300, 500 and / or 1000 draws of the European Standard Abrasion Test and after 200 cycles of temperature changes under humidification are given in Table 11 for individual examples. In Table 11, the term active indicates that the coated glasses were photocatalytically active, but that t<sub>go</sub>% not specified.
-30«·· · · «· · · » · ♦ • · · · · · · · · • ····· · · · · · · ··· ·· ·· ···· ·· ····
TAB.8
<td colspan="2">Ex. Speed</td><td rowspan="4">Temperature application layers oxide (° C)</td><td colspan="5">Titanium oxide layer</td>
<td rowspan="3"></td><td rowspan="3">lines (m / min)</td><td rowspan="3">Temp. at U.S. Si (° C)</td><td colspan="4">Nose Flows- Nose Flows-</td>
<td colspan="2">gas</td><td colspan="2" rowspan="2">cursors TiCl<sub>4</sub> Ethyl acetate (cm<sup>3</sup>/ min)</td>
<td>He (1 /</td><td><sup>N</sup>2 Ln)</td>
<td> 30</td><td> 10,9</td><td> 690 & 677</td><td> 621</td><td> 300</td><td> 300</td><td> 6,3</td><td> 16,3</td>
<td> 31</td><td> 10,9</td><td> 690 & 677</td><td> 621</td><td> 300</td><td> 300</td><td> 6,3</td><td> 16,3</td>
<td> 32</td><td> 10,9</td><td> 690 & 677</td><td> 621</td><td> 300</td><td> 300</td><td> 6,3</td><td> 16,3</td>
<td> 33</td><td> 10,9</td><td> 690 & 677</td><td> 621</td><td> 300</td><td> 300</td><td> 6,3</td><td> 16,3</td>
<td> 34</td><td> 10,9</td><td> 690</td><td> 621</td><td> 300</td><td> 300</td><td> 6</td><td> 16</td>
<td> 35</td><td> 10,9</td><td> 690</td><td> 621</td><td> 300</td><td> 300</td><td> 6</td><td> 16</td>
<td> 36</td><td> 10,9</td><td> 690</td><td> 621</td><td> 300</td><td> 300</td><td> 6</td><td> 14,7</td>
<td> 37</td><td> 10,9</td><td> 690</td><td> 677</td><td> 300</td><td> 300</td><td> 5,5</td><td> 14,7</td>
<td> 38</td><td> 10,9</td><td> 690</td><td> 677</td><td> 300</td><td> 300</td><td> 5,5</td><td> 14,7</td>
<td> 39</td><td> 10,9</td><td> 690</td><td> 677</td><td> 300</td><td> 300</td><td> 5,5</td><td> 14,7</td>
<td> 40</td><td> 10,9</td><td> 690</td><td> 677</td><td> 300</td><td> 300</td><td> 5,5</td><td> 14,7</td>
<td> 41</td><td> 6,5</td><td> 721</td><td> 690</td><td> 300</td><td> 300</td><td> 4</td><td> 10,7</td>
<td> 42</td><td> 12,1</td><td> 721 & 690</td><td> 677</td><td> 300</td><td> 300</td><td> 9,5</td><td> 25,4</td>
TAB.9
<td rowspan="2">Ex.</td><td rowspan="2">Reflection R (%)</td><td colspan="3">movie sideways</td><td rowspan="2">t (%:</td><td rowspan="2">Transmission 1 L *</td><td rowspan="2">and</td><td rowspan="2">b</td><td rowspan="2">Fogging (%)</td>
<td>L *</td><td>and</td><td>b</td>
<td> 30</td><td> 14,2</td><td> 44,5</td><td> 0,3</td><td> -10,3</td><td> 84,3</td><td> 93,6</td><td> -1,2</td><td> 3,6</td><td> 0,11</td>
<td> 31</td><td> 14,6</td><td> 45,1</td><td> 0,3</td><td> -10,4</td><td> 84,5</td><td> 93,7</td><td>-i, i</td><td> 3,4</td><td> 0,30</td>
<td> 32</td><td> 14,6</td><td> 45,1</td><td> 0,3</td><td> -10,5</td><td> 84,3</td><td> 93,6</td><td>-i, i</td><td> 3,6</td><td> 0,12</td>
<td> 33</td><td> 13,8</td><td> 44,0</td><td> 0,3</td><td> -9,8</td><td> 85,5</td><td> 94,1</td><td> -1,1</td><td> 2,9</td><td> 0,15</td>
<td> 34</td><td> 13,6</td><td> 43,7</td><td>o, i</td><td> 8,7</td><td> 84,8</td><td> 93,8</td><td> -1,1</td><td> 2,7</td><td> 0,12</td>
<td> 35</td><td> 13,8</td><td> 43,9</td><td>o, i</td><td> -8,8</td><td> 85,4</td><td> 94,1</td><td>-i, i</td><td> 2,6</td><td> 0,11</td>
-31TAB.9-continued
<td> 36</td><td> 12,9</td><td> 42,6</td><td> 0,1</td><td> -8,2</td><td> 85,8</td><td> 94,2</td><td> 1,1</td><td> 2,5</td><td> 0,14</td>
<td> 37</td><td> 12,6</td><td> 42,2</td><td> 0,1</td><td> -7,9</td><td> 86,1</td><td> 94,4</td><td> -1,1</td><td> 2,3</td><td> 0,08</td>
<td> 38</td><td> 11,9</td><td> 41,0</td><td> 0,1</td><td> -6,9</td><td> 87,1</td><td> 94,8</td><td>-i, i</td><td> 1,7</td><td> 0,07</td>
<td> 39</td><td> 11,5</td><td> 40,4</td><td> 0,0</td><td> -6,5</td><td> 87,2</td><td> 94,8</td><td> -1,1</td><td> 1,8</td><td> 0,10</td>
<td> 40</td><td> 11,6</td><td> 40,6</td><td> 0,0</td><td> —6,6</td><td> 86,9</td><td> 94,7</td><td>-i, i</td><td> 1,8</td><td> 0,08</td>
<td> 41</td><td>and</td><td>and</td><td>and</td><td>and</td><td>and</td><td>and</td><td>and</td><td>and</td><td>and</td>
<td> 42</td><td> 14</td><td> 44,3</td><td> 0,1</td><td> -9,9</td><td> 84,8</td><td> 93,8</td><td> -1,1</td><td> 3,1</td><td> 0,14</td>
and Not measured
TAB.10
Example
Static extreme angle (° C) after the number of abrasion test moves
<td></td><td> 0</td><td>0 (after irradiation)</td><td> 300</td><td> 500</td>
<td></td><td></td><td>130 min UV)</td><td></td><td></td>
<td> 30</td><td> 2,3</td><td> 3,3</td><td>did not</td><td></td>
<td> 31</td><td> 2,0</td><td> 3,2</td><td>did not</td><td></td>
<td> 32</td><td>and</td><td>and</td><td>did not</td><td></td>
<td> 33</td><td> 2,0</td><td> 3,2</td><td>did not</td><td></td>
<td> 34</td><td>and</td><td>and</td><td>did not</td><td></td>
<td> 35</td><td> 2,0</td><td> 3,2</td><td>did not</td><td></td>
<td> 36</td><td> 2,1</td><td> 3,4</td><td>did not</td><td></td>
<td> 37</td><td> 2,2</td><td> 3,3</td><td></td><td> <15</td>
<td> 38</td><td> 2,0</td><td> 3,1</td><td></td><td> <15</td>
<td> 39</td><td> 1,9</td><td> 3,1</td><td></td><td> <15</td>
<td> 40</td><td> 2,2</td><td> 3,2</td><td></td><td> <15</td>
<td> 41</td><td> 7,8</td><td> 7,8</td><td></td><td></td>
<td> 42</td><td> 4,7-5,3</td><td> 4,7-5,3</td><td></td><td></td>
1000
10,1
5.6-9.8 a Not Measured ·· ·· ·· ·· ·· · · · · · · · · · · · · · ·
-32··· ··· · · · · · • · · · « · · ·· ·· ···· ·· ····
TAB.ll
<td>Example</td><td colspan="3">tgo ^ min) after the number of abrasion test moves</td><td>t<sub>9</sub>% (mi<sup>n</sup>) after 200 cycles of temperature change</td>
<td></td><td></td><td></td><td></td><td>when moistened</td>
<td></td><td> 0</td><td> 300</td><td> 500 1000</td><td></td>
<td> 30</td><td> 7,5</td><td>did not</td><td></td><td>did not</td>
<td> 31</td><td> 18,5</td><td>did not</td><td></td><td>did not</td>
<td> 32</td><td> 8,5</td><td>did not</td><td></td><td>did not</td>
<td> 33</td><td> 8</td><td>did not</td><td></td><td>did not</td>
<td> 34</td><td> 21</td><td>did not</td><td></td><td>did not</td>
<td> 35</td><td> 4</td><td>did not</td><td></td><td>did not</td>
<td> 36</td><td> 8,5</td><td>did not</td><td></td><td>did not</td>
<td> 37</td><td> 15,5</td><td></td><td>ca.2160</td><td>active</td>
<td> 38</td><td> 18,5</td><td></td><td>ca.2160</td><td>active</td>
<td> 39</td><td> 17</td><td></td><td>ca.2160</td><td>active</td>
<td> 40</td><td> 18,5</td><td></td><td>ca.2160</td><td>active</td>
<td> 41</td><td>and</td><td></td><td>ca.2160</td><td>active</td>
<td> 42</td><td> 45</td><td></td><td> 2800</td><td>active</td>
and Not measured
Contents16
10 sheets
Sheet 1 Sheet 2 Sheet 3 Sheet 4 Sheet 5 Sheet 6 Sheet 7 Sheet 8 Sheet 9 Sheet 10
45 members in 23 offices
Priority claims4
| Document | Office | Kind | Date |
|---|---|---|---|
| 9913315 | United Kingdom | A | |
| 9913315 | United Kingdom | A | |
| 19999913315 | – | – | – |
| GB19990013315 | – | – | – |
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| AU5092400A | Australia | A | |
| BR0011382A | Brazil | A | |
| KR20020026874A | Republic of Korea | A | |
| EP1198431A1 | European Patent Office (EPO) | A1 | |
| CN1354732A | China | A | |
| TR2001003541T2 | Türkiye | T2 | |
| TR200103541T2 | Türkiye | T2 | |
| EA200200002A1 | Eurasian Patent Organization (EAPO) | A1 | |
| IL146661A0 | Israel | A0 | |
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| HK1044328A | Hong Kong, China | A | |
| HK1044328A1 | Hong Kong, China | A1 | |
| EP1254870A2 | European Patent Office (EPO) | A2 | |
| EP1254870A3 | European Patent Office (EPO) | A3 | |
| JP2003501338A | Japan | A | |
| US2003064231A1 | United States of America | A1 | |
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| EA004759B1 | Eurasian Patent Organization (EAPO) | B1 | |
| US6840061B1 | United States of America | B1 | |
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| CA2375662C | Canada | C | |
| JP4716631B2 | Japan | B2 | |
| EP1198431B1 | European Patent Office (EPO) | B1 | |
| EP1254870B1 | European Patent Office (EPO) | B1 |
Numbers
- Publication, DOCDB
- 20014395
- Publication, EPODOC
- CZ20014395
- Application
- 20014395
- Application, DOCDB
- 20014395
- Application, EPODOC
- CZ20010004395
Titles2
- Czech
- Způsob výroby fotokatalyticky aktivního substrátu s povlakem, fotokatalyticky aktivní a trvanlivý povlakovaný substrát a sklo, výrobky z něj a způsob jejich výroby
- English
- Process for the production of a photocatalytically active durable coated substrate, the photocatalytically active durable coated substrate and glass, articles made therefrom as well as process of their manufacture
Classification
- CPC, 6
- C03C17/2456
- C23C16/405
- C03C17/3417
- C03C2217/212
- C03C2217/71
- C03C2218/152
- IPC, 7
- B01J21 06
- B01J35 00
- C03C17 245
- C03C17 34
- C03C27 06
- C03C27 12
- C23C16 40
