Process for the production of photocatalytic coatings on substrates.
6 claims: 4 independent, 2 dependent
- 1REIVINDICACIONES 1. Un proceso para la producción de vidrio revestido, activo fotocatalíticamente, durable, el cual 5 comprende depositar sobre la superficie de un substrato de vidrio, una capa de óxido de titanio, activo fotocatalíticamente, que tiene un espesor menor de 40 nm, por el contacto de la superficie del substrato, el cual se encuentra a una temperatura en el intervalo de 645 a 720°C, 10 con una mezcla de fluidos que contiene una fuente de titanio.
- 2Un proceso, según se reclama en la reivindicación 1, en que el substrato está a una temperatura en el intervalo de 670 a 720°C. 15 3. Un proceso, según se reclama en cualquiera de las reivindicaciones 1 ó 2, en que la mezcla de fluidos es una mezcla gaseosa que comprende el tetraalcóxido de titanio como la fuente de titanio. 4. Un proceso, según se reclama en cualquiera de 20 las reivindicaciones precedentes, en que la mezcla de fluidos es una mezcla gaseosa que comprende el tetraetóxido de titanio, como la fuente del titanio. 5. Un proceso, según se reclama en cualquiera de las reivindicaciones precedentes, en que la mezcla de fluidos comprende el cloruro de titanio como la fuente del titanio y un éster, además del éster de metilo. 5 6. Un proceso para la producción de un substrato revestido, activo fotocatalíticamente, el cual comprende depositar un revestimiento del óxido de titán, que tiene un espesor menor de 40 nm, sobre el substrato, por el contacto de una superficie del substrato con una mezcla de fluidos, 10 que comprende el cloruro de titanio, y un éster, además del éster de metilo. 7. Un proceso, según se reclama en la reivindicación 6, en que la superficie del substrato se pone en contacto con la mezcla de fluidos, cuando el substrato 15 está a una temperatura en el intervalo de 500 a 750°C. 8. Un proceso, según se reclama en cualquiera de las reivindicaciones 5 a 7, en que el éster comprende un éster de alquilo, que tiene un grupo de alquilo con un hidrógeno β. 2 0 9. Un proceso, según se reclama en cualquiera de las reivindicaciones 5 a 8, en que el éster comprende un éster de carboxilato. 10. Un proceso, según se reclama en cualquiera de las reivindicaciones 5 a 9, en que el éster es un éster de alquilo que tiene un grupo de alquilo C 2 hasta C 4 . 11. Un proceso, según se reclama en la 5 reivindicación 10, en que el éster comprende un éster de etilo. 12. Un proceso, según se reclama en la reivindicación 11, en que el éster comprende el acetato de etilo. 10 13. Un proceso, según se reclama en cualquiera de las reivindicaciones 5 a 12, en que el éster es la única fuente del oxígeno en la mezcla de fluidos. 14. Un proceso, según se reclama en cualquiera de las reivindicaciones precedentes, en que la mezcla de 15 fluidos es una mezcla gaseosa. 15. Un proceso, según se reclama en cualquiera de las reivindicaciones precedentes, en que este proceso se realiza en línea, durante el proceso de producción de vidrio flotante y el substrato es una cinta de vidrio. 20 16. Un proceso, según se reclama en la reivindicación 15, en que el proceso se realiza en el baño de flotación. 17. Un proceso, según se reclama en cualquiera de las reivindicaciones precedentes, en que el proceso se realiza a la presión substancialmente atmosférica. 18. Un substrato revestido, activo foto5 catalíticamente, que comprende un substrato que tiene un revestimiento de óxido de titanio, activo fotocatalíticamente, sobre una de sus superficies, caracterizado porque la superficie revestida del substrato tiene una actividad fotocatalítica mayor de 5 x 10‘ 3 cm' 1 min' 1 y porque 10 el substrato revestido tiene una reflexión de la luz visible, medida sobre el costado revestido, del 35% o menor. 19. Un substrato revestido, activo fotocatalíticamente, según se reclama en la reivindicación 18, en que la superficie revestida del substrato tiene una 15 actividad fotocatalítica mayor de 1 x 10' 2 cm' 2 min' 1 . 20. Un substrato revestido, activo fotocatalíticamente, según se reclama en la reivindicación 19, en que las superficie revestida del substrato tiene una actividad fotocatalítica mayor de 3 x 10 2 cm 1 min' 1 . 20 21. Un substrato revestido, activo fotocatalíticamente, según se reclama en cualquiera de las reivindicaciones 18 a 20, en que el substrato revestido tiene una reflexión de la luz visible, medida sobre el costado revestido, del 20% o menor. 22. Un substrato revestido, activo fotocatalíticamente, según se reclama en la reivindicación 21, 5 en que el substrato revestido tiene una reflexión de la luz visible, medida sobre el costado revestido, del 15% o menor. 23. Un substrato revestido, activo fotocatalíticamente, según se reclama en cualquiera de las reivindicaciones 18 a 22, en que el substrato comprende un 10 substrato de vidrio. 24. Un substrato revestido, activo fotocatalíticamente, según se reclama en cualquiera de las reivindicaciones 18 a 23, en que el substrato revestido tiene un bloqueo de iones de metales alcalinos bajo la capa, 15 entre la superficie del substrato y el revestimiento de óxido de titanio, activo fotocatalíticamente. 25. Un substrato revestido, activo fotocatalíticamente, según se reclama en la reivindicación 24, en que la capa de bloqueo de iones de metales alcalinos es 20 una capa de óxido de silicio. 26. Un substrato revestido, activo fotocatalíticamente, según se reclama en cualquiera de las reivindicaciones 18 a 25, en que el revestimiento de óxido de titanio, activo fotocatalíticamente, tiene un espesor de
- 33 0 nm o menor. 27. Un substrato revestido, activo fotocatalíticamente, según se reclama en cualquiera de las 5 reivindicaciones 18 a 26, en que el revestimiento de óxido de titanio, activo fotocatalíticamente, tiene un espesor de 20 nm o menor. 28. Un substrato revestido, activo fotocatalíticamente, según se reclama en la reivindicación 27, 10 en que el revestimiento de óxido de titanio, activo fotocatalíticamente, tiene un espesor en el intervalo de 2 nm hasta 20 nm. 29. Un substrato revestido, activo fotocatalíticamente, según se reclama en cualquiera de las 15 reivindicaciones 18 a 28, en que la superficie revestida del substrato tiene un ángulo de contacto con el agua estática de 20° o menor. 30. Un substrato revestido, activo fotocatalíticamente, según se reclama en cualquiera de las 20 reivindicaciones 18 a 29, en que el substrato revestido tiene un empañamiento menor del 1%. 31. Un substrato revestido, activo fotocatalíticamente, según se reclama en cualquiera de las reivindicaciones 18 a 30, producido por un proceso según se reclama en cualquiera de las reivindicaciones 1 a 17. 32. Un substrato revestido, activo fotocatalíticamente, según se reclama en cualquiera de las 5 reivindicaciones 18 a 31, en que la superficie revestida del substrato es durable a la abrasión, de manera que la superficie revestida permanezca activa fotocatalíticamente después que se ha sometido a 3 00 pasadas de la prueba de abrasión estándar europea. 10 33. Un substrato revestido, activo fotocatalíticamente, según se reclama la reivindicación 32, en que la superficie revestida permanece activa fotocatalíticamente después que se ha sometido a 500 pasadas de la prueba de abrasión estándar europea. 15 34. Un substrato revestido, activo fotocatalíticamente, según se reclama la reivindicación 33, en que la superficie revestida permanece activa fotocatalíticamente después que se ha sometido a 1000 pasadas de la prueba de abrasión estándar europea. 20 35. Un substrato revestido, activo fotocatalíticamente, según se reclama en cualquiera de las reivindicaciones 32 a 34, en que el empañamiento del substrato revestido es del 2% o menor, después de ser sometido a la prueba de abrasión europea. 36. Un substrato revestido, activo fotocatalíticamente, según se reclama en cualquiera de las 5 reivindicaciones 18 a 35, en que la superficie revestida del substrato es durable a los ciclos de humedad, de manera que la superficie revestida permanezca activa fotocatalíticamente después que el substrato revestido se ha sometido a 200 ciclos de la prueba de ciclado de humedad. 10 37. Un vidrio revestido, durable, activo fotocatalíticamente, que comprende un substrato de vidrio, que tiene un revestimiento sobre una de sus superficies, dicho revestimiento comprende una sub-capa de bloqueo de iones de metales alcalinos y una capa de óxido de titanio, 15 activa fotocatalíticamente, donde la superficie revestida del substrato es durable a la abrasión, de modo que la superficie revestida permanezca activa fotocatalíticamente, después que se ha sometido a 3 00 pasadas de la prueba de abrasión estándar europea. 20 38. Un vidrio revestido, durable, activo fotocatalíticamente, según se reclama en la reivindicación 37, en que este vidrio revestido tiene una reflexión de la luz visible, medida sobre el costado revestido, del 35% o t menor, y donde la capa de óxido de titanio, activa fotocatalíticamente, tiene un espesor de 30 nm o menor. 39. Un vidrio revestido, que comprende un substrato de vidrio, que tiene un revestimiento de óxido de
- 45 titanio, activo fotocatalíticamente sobre una de sus superficies, caracterizado porque la superficie revestida del vidrio tiene una actividad fotocatalítica mayor de 8 x IO 2 cm' 1 min' 1 , y porque el vidrio revestido tiene una reflexión de la luz visible, medida sobre el costado
- 510 revestido, menor del 20%. 40. Una unidad de cristales múltiples, que comprende una primera hoja de cristal de un substrato revestido, según se reclama en cualquiera de las reivindicaciones 18 a 39, opuesta con relación a la segunda
- 615 hoja de cristal. 41. Un vidrio laminado, que comprende una primera capa de vidrio de un vidrio revestido según se reclama en cualquiera de las reivindicaciones 18 a 39, una capa interna de polímero y una segunda capa de vidrio. t*/aZza i/ οι,2.5¼
Independent claims6
328 paragraphs in 12 sections, as filed
(54) Title: PROCESS FOR THE PRODUCTION OF PHOTOCATALYTIC COATINGS ON SUBSTRATES.
(54) Title: PROCESS FOR THE PRODUCTION OF PHOTOCATALYTIC COATINGS ON SUBSTRATES.
(57) Summary
A process for the production of a photocatalytically active, self-cleaning, coated substrate, especially a glass substrate, is disclosed. This process comprises depositing a titanium oxide coating on the surface of the substrate, by contacting it with a mixture of fluids, containing a titanium source and an oxygen source, this substrate is at a temperature of at least 600YC. The coated surface has good durability, high photocatalytic activity and low reflection of visible light. More preferably, the deposit temperature is in the range of 645 to 720YC, which provides especially good durability. The fluid mixture preferably contains titanium chloride and an ester, especially ethyl acetate. Also disclosed is a self-cleaning coated substrate, especially a glass substrate, which has high photocatalytic activity and low reflection of visible light, and a durable, self-cleaning coated glass.
(57) Abstract
A process for the productlon of a photocatalytlcally active self-cleanlng coated substrate, especlally a glass substrate, which comprises deposltlng a tltanlum oxide coatlng on the surface of the substrate by contactlng ¡t with a fluid mixture contalnlng a source of tltanlum and a source of oxygen, the substrate belng at a temperature of at least 600 YC. The coated surface has good durablllty, a hlgh photocatalytlc activity and a low visible light reflectlon. Most preferably the deposltlon temperature ¡s ¡n the range 645 YC to 720 YC which provldes especlally good durablllty. The fluid mixture preferably contalns tltanlum chlorlde and an ester, especlally ethyl acétate. Also disclosed ¡sa self cleanlng coated substrate, especlally a glass substrate, having hlgh photocatalytlc activity and low visible light reflectlon and a durable self-cleanlng coated glass.
(12) INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT) (19) World Inteilectual Property Organization International Bureau (43) International Publication Date 14 December 2000 (14.12.2000)
<img file="MXPA01012578A_D0001.tif" />
PCT
HIB1II (10) International Publication Number
WO 00/75087 Al (51) International Patent Classification<sup>7</sup>: 17/34, C23C 16/40
C03C 17/245, (21) International Application Number: PCT / GBOO / 02111, (22) International Filing Date:
(25) Filing Language:
(26) Publication Language: (30) Priority Dat #
I June 2000 (01.06.20007
English
English
9913315.9/
June 1999 (08.06.1999J GB (71) Applicants (for¿ll designated States except US) i PILKINGTON PLC [GB / GB]; Prescot Road, Sl Helens, Merseyside WA10 3ΊΤ (GB). LIBBEY-OWENS-FORD CO. [ US / US]; 811 Madison Avenue, Toledo, OH 43697-0799 (US).
(72) Inventors; and (75) Inventors / Applicants (for US only): AMMERLAÁN,
Johannes, Andreas, María [NL / NX / J; Aalsterweg 132y NL-5615 CJ Eindhoven (NL). hiCCURDY, Richard, Joseph [US / US]; 14 Ashwood Zourt, Aurora, tt, 60506 (US). HURST, Simón, Jame / [GB / GB]; 8 Glastonbury Cióse, Sandymoor, Runcom, Cheshire WA7 1QW (GB).
(74) Agents: HALLIWELL, Anthony, Charles et al .; Pffldngton.plc, Group Inteilectual Property Department, PilkingΊοη European Technical Center, Hall Lañe, Lathom, Ormstírk, Lancashire L40 5UF (GB).
(81) Designated States (national): AE, AL, AM, AT, AU, AZ, BA, BB, BG, BR, BY, CA, CH, CN, CR, CU, CZ, DE, DK, DM, EE , ES, FI, GB, GD, GE, GH, GM, IWHU, ID, IL, IN, IS, JP, KE, KG, KP, KR, KZ LC, LK / LR, LS, LT, LU, LV, MA, MD, MG, MK, MN, MW, MX NO, NZ PL, PT, RO, RU, SD, SE, SG, SL SK, SL, TJ, TM, TR, TT, TZ, UA, UG, US , UZ, VN, YU, ZA, ZW.
(84) Designated States (regional): ARIPO patent (GH, GM, KE, LS, MW, MZ, SD, SL, SZ TZ, UG, ZW), Eurasian patent (AM, AZ BY, KG, KZ MD, UK , TJ, TM), European patent (AT, BE, CH, CY, DE, DK, ES, H, FR, GB, GR, IE, ΓΓ, LU, MC, NL, PT, SE), OAPI patent (BF , BJ, CF, CG, CI, CM, GA, GN, GW, ML, MR, NE, SN, TD, TG).
Published:
- With intemational search report.
For two-letter codes and other abbreviations, refer to the Guidartce Notes on Codes and Abbreviations appearing at the beginning of each regular issue pf the PCT Gazette.
WO 00/75087 Al (54) Title: PROCESS FOR THE PRODUCTION OF PHOTOCATALYTIC COATTNGS ON SUBSTRAIES (57) Abstract: A process for the production of a photocatalytically active self-cleaning coated substrate, especially a glass substrate, which comprises depositing a titanium oxide coating on the surface of the substrate by contacting it with a fluid mixture containing a source of titanium and a source of oxygen, the substrate being at a temperarme of at least 600 ° C. The coated surface has good durability, a high photocatalytic activity and a low visible light reflection. Most preferably the deposition temperature is in the range 645 ° C to 720 ° C which ptovides especially good durability. The fluid mixture preferably contares titanium chloride and an ester, especially ethyl acétate. Also disclosed is a self cleaning coated substrate, especially a glass substrate, having high photocatalytic activity and low visible light reflection and a durable self-cleaning coated glass.
/; t
PROCESS FOR THE PRODUCTION OF COATINGS
PHOTOCATALYTICS ON SUBSTRATES
This invention relates to a process for the production of photocatalytically active coated substrates, in particular, but not exclusively, relates to a process for producing photocatalytically active coated glass, and to coated glass itself
It is known to deposit thin coatings having one or more layers, with a variety of properties, on substrates, including glass substrates. A property of interest is the photocatalytic activity that arises from the photogeneration, in a semiconductor, of a hole-electron pair, when the semiconductor is illuminated by light of a particular frequency. This hole-electron pair can be generated in sunlight and can react in humid air to form hydroxy and peroxy radicals on the semiconductor surface. Radicals oxidize organic dirt on the surface. This property has an application in the self-cleaning of substrates, especially in the self-cleaning of window glass.
Titanium dioxide can be an efficient photocatalyst and can be deposited on substrates to form a transparent coating, with photocatalytic self-cleaning properties. Photocatalytic coatings of titanium oxide are described in EP 0 901 991 A2, WO 97/07069, WO 97/10186, WO 98/41480, in Extract 735 of the Board of the Electrochemical Society (Reno, NV, 95 -1, p. 1102) and in New Scientist magazine (August 26, 1995, p. 19). In WO 98/06675, a chemical vapor tank is described for depositing titanium oxide coatings on hot flat glass, at a high deposit rate, using a mixture of titanium chloride precursor gas and an organic compound such as a source of oxygen, for the formation of the titanium oxide coating.
It had been thought that thick titanium oxide coatings need to be deposited to provide good photocatalytic activity. For example, WO 98/41480 states that the photocatalytically active self-cleaning coating should be thick enough to provide an acceptable level of activity, and it is preferred that such a coating be at least about 200A and more preferably at least about 500A thick (the measured thickness of the titanium oxide coatings produced in the Examples are all in the range of 400A to 2100A).
However, a problem with relatively thick titanium oxide coatings is the high reflection of visible light and thus the relatively low transmission of visible light. This problem is recognized in the article in the New Scientist magazine in relation to coated windshields, where it is suggested that to reduce the effect of high reflection, the dashboards can be coated in black velvet or some other material that does not reflect the light on a coated screen.
Patent EP 0 901 991 A2, mentioned above, refers to photocatalytic glass sheets with a titanium oxide coating of a particular crystal structure, characterized by the presence of particular ridges in their X-ray diffraction pattern. This specification considers a range of the coating thickness (with the specific Examples all having a thickness in the range of 20 to 135 nm, the thinner coatings being less photocatalytically active than the thicker coatings). The specification also considers a range of deposition temperatures from as low as 300 ° C to as high as 750 ° C, but prefers temperatures in the range of 400 to 600 ° C, and in all specific Examples of the invention, the titanium dioxide layer is deposited at a temperature of or below this preferred range.
Applicants have now found that, by depositing titanium oxide coatings at higher temperatures, especially at temperatures above 600 ° C, they are able to achieve coatings with increased photocatalytic activity for a given thickness, making it possible to achieve the same photocatalytic performance with thinner coatings. Such thinner coatings tend to advantageously have a lower reflection of visible light and apparently, as a consequence of their higher deposit temperature, improved durability, especially abrasion and temperature cycling in a humid atmosphere.
Therefore, the present invention provides a process for the production of a photocatalytically active coated substrate, which comprises depositing a titanium oxide coating on the surface of a substrate, by contacting the substrate surface with a fluid mixture containing a source of titanium and a source of oxygen, said substrate is at a temperature of at least 600 ° C, whereby the coated surface of the substrate has a photocatalytic activity greater than 5 x IO<sup>-3</sup> cm '<sup>1</sup> min<sup>1</sup>, and a reflection of visible light measured on the coated side of 35% or less.
Preferably, the substrate is at a temperature in the range of 625 to 720 ° C, more preferably5, the substrate is at a temperature in the range of 645 to 720 ° C.
Advantageously, the fluid mixture comprises titanium chloride as the titanium source and an ester, in addition to the methyl ester. Thus, in a preferred embodiment, the present invention provides a process for the production of a photocatalytically active coated substrate, which comprises depositing a titanium oxide coating, having a thickness of less than 40 nm, on a substrate, by the contact of a substrate surface with a fluid mixture comprising titanium chloride and an ester, in addition to the vinyl ester.
The process can be performed where the surface of the substrate is in contact with the fluid mixture, when the substrate is at a temperature in the range of 600 to
750 ° C.
Preferably, the ester is an alkyl ester, which has an alkyl group with a beta hydrogen (the alkyl group of an alkyl ester is the group derived from alcohol in the synthesis of an ester and a beta hydrogen is a bonded hydrogen to the β-carbon atom to oxygen from an ether bond in an ester). Preferably, the ester is a carboxylate ester.
Suitable esters can be alkyl esters, which have an alkyl group with C<sub>2</sub> a Cio, but preferably the ester is an alkyl ester having an alkyl group C<sub>2</sub> a C<sub>4</sub>.
Preferably, the ester is a compound of the formula:
R - C (0) - 0 - C (X) (X ') - C (Y) (Y') - R ', where R and R' represent hydrogen or an alkyl group, X, X ', Y and Y 'represent monovalent substituents, preferably alkyl groups or hydrogen atoms and where at least one of the Y and Y' represent hydrogen.
Suitable esters that can be used in the process of the present invention include: the ethyl format, ethyl acetate, ethyl propionate, ethyl butyrate, n-propyl format, n-propyl acetate, n-propyl propionate, n-propyl butyrate, isopropyl format, isopropyl acetate, isopropyl propionate, isopropyl butyrate, n-butyl format, n- acetate
<td>butyl</td><td>and t-butyl acetate.</td><td></td><td></td><td></td><td></td>
<td> 20</td><td>Preferably the</td><td>ester</td><td>understands</td><td>an ester</td><td>of</td>
<td>ethyl,</td><td>more preferably the</td><td>ester</td><td>understands</td><td>the format</td><td>of</td>
<td>ethyl,</td><td>ethyl acetate or</td><td colspan="2">propionate</td><td>ethyl.</td><td>Plus</td>
preferably, the ester comprises ethyl acetate.
The fluid mixture can be in the form of a liquid, especially dispersed as a fine spray (a process often referred to as dew deposition), but preferably the fluid mixture is a gas mixture. A deposition process carried out using a gaseous mixture as a precursor is often referred to as a chemical vapor deposition (CVD). The preferred form of the CVD is a laminar flow CVD, although a turbulent flow CVD can also be used.
The process can be performed on substrates of various dimensions, including substrates on sheets, especially on cut glass sheets, or preferably in-line, during the floating glass production process, on a continuous glass ribbon. Thus, preferably, the process is performed online, during the production process of the floating glass and this substrate is a glass ribbon. If the process is performed online, it is run on a glass ribbon, while in the float bath.
An advantage of performing the process online is that the coatings deposited online tend to be durable and in particular have good abrasion and chemical resistance.
An online deposit process is preferred, and other deposit processes can be performed at substantially atmospheric pressure.
In a particularly preferred embodiment, a process is provided for the production of a durable, photocatalytically active glass, which comprises depositing on the surface of a glass substrate a layer of titanium oxide, photocatalytically active, by contact of the surface of the substrate, which is at a temperature in the range of 645 to 720 ° C, preferably in the range of 670 to 720 ° C, with a fluid mixture, containing a titanium source.
As noted above, applicants have found that by depositing titanium oxide at high temperature, a coating of relatively high photocatalytic activity can be produced, for its thickness it can, and since coatings of reduced thickness tend to have less reflection. , the invention also provides novel products having an advantageous combination of high photocatalytic activity with moderate or low light reflection.
<td>So,</td><td>the present</td><td colspan="2">invention in</td><td>other aspect,</td>
<td>supplies a</td><td>substrate</td><td></td><td>coated,</td><td>active photo-</td>
<td>catalytically,</td><td colspan="2">that includes</td><td>a substrate</td><td>who has a</td>
<td>25 liner</td><td>oxide</td><td>of</td><td>titanium,</td><td>active photo-</td>
catalytically ,, on its surface, characterized in that the coated surface of the substrate has a photocatalytic activity greater than 5 x 10<sup>3</sup> cm '<sup>1</sup> min '<sup>1</sup>, and because the coated substrate has a reflection of visible light measured on the coated side of 35% or less.
High photocatalytic activity is advantageous due to the amount of contaminants (including dirt) on the coated surface of the coated, photocatalytically active substrate, will decrease more rapidly than on substrates with relatively low photocatalytic activity. Similarly, the relatively rapid removal of surface contaminants will tend to occur at low levels of light intensity
UV.
Photocatalytic activity, for the purposes of this specification, is determined by measuring the rate of decrease in the integrated absorbance of the infrared absorption peaks, which correspond to the CH extensions of a thin film of stearic acid formed on the coated substrate, under illumination by UV light from a UVA lamp, which has an intensity of approximately 32 W / m<sup>2</sup> at the surface of the coated substrate and a peak wavelength of 51 nm. Stearic acid can be formed on the coated substrate by rotationally molding a solution of stearic acid in methanol, as described below.
Preferably, the coated surface of the substrate has a photocatalytic activity of more than 1 x 10 '<sup>22</sup> cm '<sup>2</sup> min '<sup>1</sup>, more preferably 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 disturbing than high reflection and, especially for glass substrates, low visible light reflection corresponds to high visible light transmission, which is often required in architecture and especially in automotive glass applications.
Preferably, the coated surface has a visible reflection, measured on the coated side of 20% or less, more preferably 17% or less, and especially preferred 15% or less.
In most embodiments of the invention, the substrate will be substantially transparent and, in a preferred embodiment of the invention, the substrate comprises a glass substrate. Usually, this glass substrate will be a soda-lime glass substrate.
Where the substrate is a soda-lime glass substrate or other substrate containing alkali metal ions, the coated substrate preferably has an alkali metal ion blocking sublayer between the surface of the substrate and the titanium oxide coating, photocatalytically active. This reduces the tendency of alkali metal ions from the substrate to migrate into the photocatalytically active titanium oxide coating, which is advantageous due to the well-known tendency of alkali metal ions to poison oxide coatings. of semiconductors, reducing their activity.
The alkali metal ion blocking sublayer may comprise a metal oxide, but preferably the alkali metal ion blocking layer is a silicon oxide layer. This silicon oxide may be silica, but it will not necessarily be stoichiometric and may comprise impurities, such as carbon (often referred to as silicon oxy-carbide and deposited as described in GB 2,199,848B) of nitrogen (often referred to as silicon oxy-nitride).
It is advantageous if the alkali metal ion blocking sublayer is thin so that it does not have a significant effect on the optical properties of the coating, especially by reducing the transparency of a transparent coated substrate or causing interference colors in reflection or transmission. The appropriate thickness range will depend on the properties of the material used
<td>to form</td><td> A layer</td><td>of</td><td>blocking</td><td>of</td><td>ions</td><td>of</td><td>metals</td>
<td>alkaline (</td><td>especially</td><td>its</td><td>index</td><td>of</td><td colspan="2">refraction)</td><td>, but</td>
<td>usually</td><td>the sublayer</td><td>of</td><td>blocking</td><td>of</td><td>ions</td><td>of</td><td>metals</td>
alkaline is less than 60nm thick and preferably less than 40nm thick. When present, the alkali metal ion blocking sublayer should always be thick enough to reduce or block the migration of the alkali metal ions from the glass into the titanium oxide coating.
An advantage of the present invention is that the photocatalytically active titanium oxide coating is thin (which contributes to the reflection of visible light from the coated substrate) but this coated substrate still has a photocatalytic activity.
Preferably, the titanium oxide coating has a thickness of 30nm or less, more preferably the titanium oxide coating has a thickness of 20nm or less, and especially preferred, this titanium oxide coating has a thickness in the range of 2nm to about 20nm.
The present invention is also advantageous because 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 interference colors in reflection or transmission. However, a particular advantage is that the visible light reflection of a thin titanium oxide coating is low, which is especially important when the coated substrate is glass. Usually, the required transmission of visible light from the coated glass will determine the thickness of the titanium oxide coating.
Preferably, the coated surface of the substrate has a static water contact angle of 20 ° or less. Freshly prepared or cleaned glass has a hydrophilic surface (a static water contact angle less than about 40 °, indicating a hydrophilic surface), but organic contaminants quickly adhere to the surface, which increases the contact angle. A particular benefit of the coated substrates (and especially the coated glass) of the present invention is that even if the coated surface becomes dirty, irradiation of the coated surface by straight wavelength UV light will reduce the contact angle, reducing or destroying those pollutants. A further advantage is that the water will be scattered on the surface with a low contact angle, reducing the distracting effect of the water droplets on the surface (for example from the rain) and tends to wash and separate any dirt or other contaminants that have not been destroyed by photocatalytic activity on the surface.
<td>The angle</td><td>of</td><td>contact of</td><td>Water</td><td>static</td><td>is</td><td>the angle</td>
<td>underrated</td><td>by</td><td>the meniscus of</td><td>a</td><td>droplet of</td><td colspan="2">water on the</td>
<td>5 surface</td><td>of</td><td>glass and can</td><td>to be</td><td>determined</td><td>of</td><td>a way</td>
known, measuring the diameter of a water droplet of known volume, on a glass surface and calculated using an iterative procedure.
Preferably, the coated substrate has a fogging of 1% or less, which is beneficial, as this allows clarity of view through a transparent coated substrate.
In preferred embodiments, the coated surface of the substrate is durable to abrasion, so that the coated surface remains photocatalytically active after 300 passes of the European standard abrasion test. Preferably, the coated surface remains photocatalytically active, after it has been subjected to 500 passes of said European standard abrasion test and, more preferably, the coated surface remains photocatalytically active after it has been subjected to 1000 passes or operations of the abrasion test. European standard.
This is advantageous, because the self-cleaning coated substrates of the present invention will often be used with the coated surface exposed to the outside (eg, glass coated with the glass-coated surface, such as the external surface of a window). ), where the lining is vulnerable to abrasion.
The European standard abrasion test refers to the abrasion test described in the European standard BS EN
1096 Part 2 (1999) and includes the reciprocal movement of a felt pad at a speed and pressure established on the surface of the sample.
In the present specification, a coated substrate is considered to remain photocatalytically active if, after being subjected to said European abrasion test, irradiation by UV light (for example, peak wavelength of 351 nm) reduces the static contact angle below 15 °. To achieve this contact angle, after abrasion of the coated substrate, it will usually take less than 48 hours of irradiation at an intensity of around 32 W / m<sup>2</sup> on the surface of the coated substrate.
Preferably, the fogging of the coated substrate is 2% or less, after it is subjected to said European standard abrasion test.
Durable coated substrates, according to the invention, can also be durable to moisture cycles (which are intended to have an effect similar to the environment). Thus, in preferred embodiments of the invention, the coated surface of the substrate is durable to moisture cycles, such that the coated surface remains photocatalytically active after the coated substrate has been subjected to 200 cycles of the moisture cycling test. In this specification, the moisture cycle test refers to a test where the coating is subjected to a temperature cycle of 35 ° C to
75 ° C to 35 ° C in 4 hours, at a relative humidity of
100% The coated substrate is considered to remain photocatalytically active if, after testing, irradiation by UV light reduces the contact angle of the static water below 15 °.
In a further preferred embodiment, the present invention provides a photocatalytically active coated glass comprising a glass substrate having a coating on one of its surfaces, said coating comprising an alkali metal ion blocking sublayer and an oxide layer titanium, photocatalytically active, in that the coated surface of the substrate is durable to abrasion, so that the coated surface remains photocatalytically active, after 3 00 passes of the European standard abrasion test. In this embodiment, the coated glass preferably has a light reflection
<td>visible,</td><td>measure in</td><td>the</td><td>side stand</td><td>coated</td><td>3-5% or less, and</td>
<td>the layer</td><td>oxide</td><td>of</td><td>titan,</td><td>active</td><td>photocatalytically,</td>
<td>have a</td><td>thickness</td><td>of</td><td>30nm</td><td>or less.</td><td>The coatings</td>
Thin are durable to abrasion, the lime is surprising, because it had previously been thought that only relatively thick coatings would have good durability.
In yet another embodiment, the present invention provides a coated glass, comprising a glass substrate, having a photocatalytically active titanium oxide coating on one of its surfaces, characterized in that the coated surface of the glass has a photocatalytic activity , which is greater than 4 x 10 '<sup>2</sup> cm '<sup>1</sup> min '<sup>1</sup>, preferably greater than 6 x 10 '<sup>2</sup> cm<sup>1</sup> min<sup>1</sup> and more preferably greater than 8 x 10 '<sup>2</sup>cm '<sup>1</sup>min '<sup>1</sup> and because coated glass has a reflection of visible light on the coated side, less than 20%.
Coated substrates, in accordance with the present invention, have uses in many areas, for example as window panes, including multi-paned units, including a first sheet of glass of the coated substrate in an opposite relationship, spaced from one second sheet of glass or, when the coated substrate is coated glass, such as laminated glass comprising a first layer of glass, of this coated glass an internal polymer layer (of, for example, polyvinylbutyral) and a second layer of glass.
In addition to using self-cleaning substrates (especially self-cleaning window glass), the coated substrates of the present invention may also be useful in reducing the concentration of air pollutants. For example, glass coated under irradiation by UV wavelength light (which includes the UV wavelengths present in sunlight) can destroy air pollutants, for example, nitrogen oxides, ozone, and organic contaminants, adsorbed on the glass coated surface. This use is particularly advantageous in openings in construction areas (for example, on city streets) where the concentration of organic pollutants can be relatively high (especially in strong sunlight), but where the available surface area glass is relatively high too. Alternatively, coated glass (with the coated surface inside) can be used to reduce the concentration of air pollutants inside buildings, especially office buildings, which have a relatively high concentration of air pollutants.
The invention is illustrated, but not limited, by the following drawings.
Figure 1 is a graph of the photocatalytic activity of coated glass produced by a process according to the invention as a function of the thickness of the titanium oxide layer, and Figure 2 illustrates an apparatus for chemical vapor deposition. online coatings according to the invention.
In Figure 1, the coated glasses are produced using an online CVD process, as described in the following Examples. Open circles 1 refer to layers of titanium oxide deposited using titanium tetrachloride as the titanium precursor, and crosses 2 refer to layers of titanium oxide deposited using titanium tetraethoxide as the titanium precursor.
The coating layers can be applied in line on the glass substrate by the chemical vapor deposit, during the glass manufacturing process. Figure 2 illustrates an apparatus, generally indicated at 10, useful for in-line production of the coated glass article of the present invention, comprising a flotation section 11, a glass tempering furnace 12, and a cooling section 13. The floatation section 11 has a bottom 14, containing a molten tin bath 16, a roof 16, side walls (not shown) and end walls 17, which together form a seal, such as provided in an enclosed area 18, where a non-oxidizing atmosphere is maintained, to prevent oxidation of the tin bath 15. During operation of the apparatus 10, the molten glass 19 melts in a crucible 20 and flows to a metering wall 21, then down onto the surface of the tin bath 15, which forms a floating glass ribbon 37, which is removed by raising and separating the rollers 22 and transported through the tempering furnace 12 and immediately through the cooling section 13.
A non-oxidizing atmosphere is maintained in flotation section 11 by introducing a suitable gas, such as, for example, one comprising nitrogen and 2% by volume of hydrogen, into zone 18, via line 23, in which operably connects to a collector 24. Non-oxidizing gas is introduced into zone 18 from conduits 23 at a rate sufficient to compensate for gas losses (some of the atmosphere or oxidant leaves zone 18 by flowing under end walls 17 (and to maintain a positive pressure cam above ambient pressure Tin bath 15 and enclosed area 18 are heated by radiant heat directly down from heaters 25. Heat zone 18 is generally maintained at a temperature of 721 to 760 ° C. The atmosphere in the tempering furnace 12 is typically air, and the cooling section 13 is not enclosed. The ambient air is blown onto the glass by means of fans 26.
The apparatus 10 also includes the coating devices 27, 28, 29 and 30, located in series in the floatation zone, above the floating glass strip 37.
The precursor gas mixtures for the individual coating layers are supplied to the respective coating devices, which, in turn, direct the precursor gas mixtures to the adjacent surface of the floating glass strip 37. The temperature of the floating glass strip 37 is highest at the location of the coating device 27, closest to the crucible 2 0 and lowest at the location of the coating device 30, closest to the tempering furnace 12.
The invention is further illustrated by the following Examples, in which the coatings are applied by depositing laminar flow chemical vapor in the flotation bath on a moving belt of floating glass, during the glass production process. In the Examples, two-layer coatings were applied to the glass ribbon.
All gas volumes were measured at standard temperature and pressure, unless otherwise noted. The thickness values for the layers were determined using high resolution scanning electron microscopy and the optical model of the reflection and transmission spectra of the coated glass. The thickness of the coatings was measured with an approximation of about 5%. The transmission and reflection properties of the coated glasses were determined using a Hitachi Y-4000 spectrophotometer. The values of a, b and L *, mentioned here, of the transmission color and / or reflection of the glasses refer to the CIE Lab colors. The visible reflection and the visible transmission of the coated glasses were determined using Illuminant D65 and the 2nd CIE standard observer, in accordance with ISO 9060 (Parry Moon, air mass 2). The fogging of the coated glasses was measured using a WYK Garnder Hazeguard + fogging meter.
The photocatalytic activity of the coated glasses was determined by the rate of decrease in the area of the infrared ridges, which correspond to the CH extensions of a stearic acid film on the coated surface of the glass, under illumination by UVA light. The stearic acid film was formed on samples of the glasses, of 7-8 square centimeters, by rotational molding of 2 0 μΐ of a solution of stearic acid in methanol (8.8 x 10-3 mol dm '<sup>3</sup>) on the glass coated surface at 2000 revolutions per minute (rpm) for 1 minute. Infrared spectra were measured in transmission, and the peak height of the peak corresponding to the CH extensions (at about 2700 to 3000 cm '<sup>1</sup>) of the stearic acid film was measured and the corresponding peak area was determined from a calibration curve of the peak area against the height of the peak. The coated side of the glass was illuminated with a UVA-351 lamp (obtained from Q-Panel Co., Cleveland, Ohio, USA) having a peak wavelength of 351 nm and a surface intensity of the coated glass of approximately 32 W / m<sup>?</sup>. Photocatalytic activity is expressed in this specification or as the rate of decrease in the area of the IR ridges (in units of cm '' min '<sup>1</sup>) or as t<sub>90</sub>% (in units of minutes) which is the UV exposure time taken to reduce the peak height (absorption) of a peak in the wavelength area down to 10% of its initial value.
The static water contact angle of the coated glasses was determined by measuring the diameter of a water droplet (volume in the range of 1 to 5 μΐ) placed on the surface of the coated glass, after irradiation of the coated glass, using a lamp
<td colspan="6">UVA 351 for about 2 hours (or as specified another way).</td><td>of</td>
<td>Examples</td><td> 1 -</td><td> 15</td><td></td><td></td><td></td><td></td>
<td></td><td>A</td><td colspan="2">floating glass ribbon</td><td>of</td><td>soda-lime,</td><td>with</td>
<td>thickness</td><td>of 1</td><td>mm What</td><td>advance in an oven</td><td>of</td><td>tempered to</td><td>a</td>
At a speed of 300 m / hour, it was coated with a two-layer coating, as the tape advanced over the flotation bath, to a position where the glass temperature was in the approximate range of 650 to 670 ° C. The atmosphere of the flotation bath comprised a flowing gas mixture of nitrogen and 9% hydrogen, at a bath pressure of approximately 0.15 mbar.
Layer 1 (the first layer to be deposited on the glass) was a layer of silicon oxide. Layer 1 was deposited causing the gaseous mixture to be monosilane (SiH<sub>4</sub>, 60 ml / min), oxygen (120 ml / min), ethylene (360 ml / min) and nitrogen (8 liters / minute), make contact and flow parallel to the glass surface in the direction of movement of the glass, using a coating apparatus, such as that described in GB patent specification 1 507 966 (referring in particular to Figure 2 and the corresponding description on page 3 line 73 to page 4 line 75) with a route of journey of the gaseous mixture on the glass surface, approximately
0.15 m. The extraction was at approximately a pressure of
0.9 to 1.2 mbar. The glass ribbon was coated across a width of approximately 10 cm at a point where its temperature was approximately 670 ° C. The thickness of the silica layer was around 20 to 25 m.
Layer 2 (the second layer to be deposited) is a layer of titanium dioxide. This layer 2 is deposited by combining separate gas streams comprising titanium tetrachloride in a flowing nitrogen carrier gas, ethyl acetate in this flowing nitrogen carrier gas and an aggregated nitrogen flow of 8 1 / min (rate flow measured at 1.4 kg / cm<sup>2</sup>) in a gas mixture and then delivery (via lines maintained at approximately 250 ° C) of the gas mixture to the coating apparatus consisting of a double coating apparatus, oil-cooled. The pressure of the nitrogen carrier and the added nitrogen gases was approximately 1.4 kg / cm<sup>2</sup>. The gaseous mixture contacted and flowed parallel to the glass surface, both upstream and downstream along the glass ribbon. The travel path of the downstream gas mixture was around 0.15 m and upstream it was also 0.15 m with extraction of around 0.15 mbar. Titanium tetrachloride and ethyl acetate were carried in separate streams of the flowing nitrogen carrier gas, the nitrogen passing through bubble-forming apparatus, containing either titanium tetrachloride or ethyl acetate. The flow rates of the nitrogen-bearing gases are described in Table 1 (the flow rates were measured at 1.4 kg / cm<sup>2</sup>). The titanium tetrachloride bubble apparatus was maintained at a temperature of 69 ° C and the ethyl acetate bubble apparatus was maintained at a temperature of 42 ° C. The estimated flow rates of entrained titanium tetrachloride and entrained ethyl acetate are also described in Table 1 for each of the
Examples 1 to 15.
The properties of the two-layer coatings were measured. The values of the thicknesses of layer 2 (the titanium oxide layer) and the values of the visible reflection were measured on the coating side, L * and the fogging of the coated glasses are described in the
Table 2 for Examples 1 to 15. The fogging of each coated glass was below 0.2%.
Photocatalytic activity and static water contact angle of the coated glasses were determined. The height of the initial peak and the area of the initial peak of the infrared (IR) ridges, which corresponds to the CH extensions of stearic acid, the photocatalytic activity, the angle of contact with static water and the t<sub>90</sub>% for Examples 1 to 15 are described in Table 3. The thickness of the titanium dioxide layer surprisingly has little effect on photocatalytic activity.
Examples 16 to 19
Examples 16 to 19 were conducted under the same conditions as Examples 1 to 15, except that the bath pressure was approximately 0.11 mbar, the extraction for the deposit of the silica sub-coating (layer 1) was approximately 0.7 mbar , the titanium tetrachloride bubble apparatus was maintained at a temperature of approximately 100 ° C, the ethyl acetate bubbler was maintained at a temperature of approximately 45 ° C and the delivery lines were maintained at a temperature of approximately 220 ° C.
The flow rates of the nitrogen carrier gas and the estimated flow rates of the entrained titanium tetrachloride and the entrained ethyl acetate are described for each of Examples 16a in Table 1.
The values of the estimated thickness of the layer (the titanium oxide layer), and the values of the visible reflection, measured on the coated side, L * and the fogging of the coated glasses are described in Table 2, for each one of Examples 16 to 19.
The initial peak height and the initial peak area of the infrared (IR) crests, which correspond to the CH extensions of stearic acid, the catalytic activity, t<sub>90</sub>% and static water contact angle, for each of Examples 16 to 19, are described in Table 3.
The photocatalytic activity of Examples 16 to 10 19 was not substantially greater than this catalytic activity of Examples 1 to 15, despite the thicker coatings of titanium oxide (and thus more reflection).
TABLE 1
<td>Example</td><td colspan="2">Flow Rates of the Nitrogen Carrier Gas to the Bubble Apparatus (l / mln, measured at 1.4 kg / cm<sup>2</sup>)</td><td rowspan="2">TiCI flow rate<sub>4 </sub>(l / min)</td><td rowspan="2">Ethyl acetate flow rate (l / mln)</td>
<td></td><td>TiCI Bubble Apparatus<sub>4</sub></td><td>Ethyl Acetate Bubble Apparatus</td>
<td> 1</td><td> 0.16</td><td> 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>
<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>
TABLE 2
<td>Example</td><td>Thickness of titanium oxide layer (nm)</td><td>Visible reflection of coated glass (%)</td><td>L * value of 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>to</td><td>to</td><td> 0.07</td>
<td> 7</td><td> 8</td><td>to</td><td>to</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>to</td><td>to</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>to</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 32</td><td> 25.9</td><td> 55.6</td><td> 0.24</td>
<td> 19</td><td>ca27</td><td> 20.5</td><td> 50.2</td><td> 0.2</td>
a = not measured
TABLE 3
<td rowspan="2">Example</td><td colspan="2">IR ridges, which correspond to the CH extensions of the stearic acid film (2700-3000 cm '<sup>1</sup>)</td><td rowspan="2">Photocatalytic activity (x 10<sup>2</sup>cm '' min '<sup>1</sup>)</td><td rowspan="2">Angle of contact with the aguí astática (')</td><td rowspan="2">Í90% (min)</td>
<td>Initial Crest Height (arbitrary units)</td><td>Initial Crest Height (cm j</td>
<td> 1</td><td> 0.030</td><td> 1.04</td><td> 9.4</td><td>17x5</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>13x2</td><td> 8</td>
<td> 4</td><td> 0.0324</td><td> 1.13</td><td> 6.8</td><td>14x1</td><td> 15</td>
<td> 5</td><td> 0.0287</td><td> 1.00</td><td> 8.2</td><td>16x3</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 x 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>18x2</td><td> 14</td>
<td> 11</td><td> 0.0344</td><td> 1.20</td><td> 5.4</td><td>18 x 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>14x2</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>15x2</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>
Examples 20-27
Examples 20 to 27 were conducted under the same conditions as Examples 1 to 15, except that layer 2 was deposited from a gaseous mixture comprising the titanium tetraethoxide entrained in the nitrogen carrier gas, this carrier gas passing through a bubble apparatus containing titanium tetraethoxide maintained at a temperature of 170 ° C. Nitrogen carrier gas flow rates (measured at 1.4 kg / cm<sup>2</sup>) and titanium tetraethoxide are described in Table 4, for each of Examples 20 to 27. The flow rate of the nitrogen gas by volume was 8.5 liters / minute (measured at 1.4 kg / cm<sup>2</sup>).
The properties of the two-layer coatings were measured. The values of the thickness of layer 2 (the titanium oxide layer) and the values of the visible reflection, measured on the coating side and the fogging of the coated glasses are described in Table 5, for Examples 20 to 27 The fogging of each coated glass
<td colspan="4">it was below 0.7%.</td>
<td>The</td><td>photocatalytic activity and</td><td>the angle</td><td>of</td>
<td>contact of</td><td>static glass water</td><td>coated</td><td>I know</td>
<td>determined.</td><td>The initial crest height</td><td>and the area</td><td>of</td>
<td>initial ridge</td><td colspan="2">from the crests of infrared (IR) light,</td><td>than</td>
correspond to the CH extensions of stearic acid, photocatalytic activity and t<sub>90</sub>%, and the static water contact angle of each of Examples 20 to 27, are described in Table 6.
Examples 28 and 29
Examples 28 and 29 were carried out under the same conditions as those of Examples 20 to 27, except that the titanium tetraethoxide bubble apparatus was maintained at a temperature of 168 ° C and a bath pressure of 0.11 mbar. The data related to
Examples 28 and 29, which are equivalent to the data of Examples 20 to 27 are described in Tables 4, 5 and
6.
TABLE 4
<td>Example</td><td>Nitrogen Carrier Gas Flow Rates for the titanium tetraethoxide bubble apparatus l / min. measured at 1.4 kq / cm<sup>2</sup>)</td><td>Flow regime of titanium ethoxide (l / min)</td>
<td> 20</td><td> 0.25</td><td> 0.014</td>
<td> 21</td><td> 0.15</td><td> 0.008</td>
<td> 22</td><td> 0.2</td><td> 0.011</td>
<td> 23</td><td> 0.25</td><td> 0.014</td>
<td> 24</td><td> 0.3</td><td> 0.017</td>
<td> 25</td><td> 0.35</td><td> 0.019</td>
<td> 26</td><td> 0.2</td><td> 0.011</td>
<td> 27</td><td> 0.1</td><td> 0.006</td>
<td> 28</td><td> 0.6</td><td> 0.030</td>
<td> 29</td><td> 0.4</td><td> 0.020</td>
TABLE 5
<td>Example</td><td>Thickness of titanium oxide layer (nm)</td><td>Visible reflection of coated glass</td><td>Fogging (%)</td>
<td> 20</td><td> 13</td><td>to</td><td> 0.4</td>
<td> 21</td><td> 13</td><td>to</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>to</td><td> 0.28</td>
<td> 24</td><td> 24</td><td>to</td><td>to</td>
<td> 25</td><td> 26</td><td>to</td><td> 0.61</td>
<td> 26</td><td> 9.9</td><td> 10.9</td><td> 0.19</td>
<td> 27</td><td> 4.7</td><td> 8.8</td><td> 0.29</td>
<td> 28</td><td> 38.3</td><td> 35.2</td><td> 0.29</td>
<td> 29</td><td> 31.9</td><td> 28.4</td><td> 0.22</td>
a = not measured
TABLE 6
<td rowspan="2">Example</td><td colspan="2">IR ridges, which correspond to the CH extensions of the stearic acid film (2700-3000 cm '')</td><td rowspan="2">Photocatalytic activity (x 10 '<sup>2</sup> cm '<sup>1 </sup>min '<sup>1</sup>)</td><td rowspan="2">Static water contact angle C)</td><td rowspan="2">t90% (min)</td>
<td>Initial Crest Height (arbitrary units)</td><td>Initial Crest Height (cníj</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>to</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>
a = not measured
Examples 30 to 42
In Examples 30 to 42, two-layer coatings were applied by an in-line CVD to a floating glass ribbon, across its full width of approximately
3.35 meters in the floatation bath, during the production process of this floating glass. The apparatus used to deposit the coating is illustrated in Figure 2. The atmosphere of the floating bath comprises nitrogen and 2% by volume of hydrogen. The bath pressure was 0.15 mbar.
The two-layer coating consisted of a layer of silicon oxide, first deposited on the floating glass ribbon, and the layer of titanium oxide, deposited on the silicon oxide layer. The chemistry of the precursor of the gaseous mixtures used to deposit the coating was the same as that used in the
Examples 1 to 15. The temperature of the deposit of the layers was varied using different coatings, 17, 18, 29 or
<td colspan="2">30 (reference is made to</td><td>Figure 2).</td><td>The</td><td colspan="2">coating</td><td> 27</td>
<td>placed more</td><td>near to</td><td>crucible is the</td><td colspan="3">hotter and</td><td>the</td>
<td>coating</td><td>30 placed</td><td>closer to</td><td colspan="2">oven</td><td>tempering</td><td>is</td>
<td>the coldest.</td><td>In the</td><td>Examples 30</td><td>to</td><td> 33</td><td>and 42,</td><td>two</td>
<td>coatings</td><td>(28 and 29</td><td colspan="2">in the examples</td><td> 30</td><td>to 33 and</td><td>the</td>
<td>coatings</td><td colspan="2">27 and 2 8 in the Example</td><td> 42)</td><td>I know</td><td colspan="2">used to</td>
<td>deposit the</td><td colspan="3">oxide coating</td><td>of</td><td>silicon.</td><td>The</td>
The benefit of using two coatings to deposit the silicon oxide layer is that longer production run times are possible.
The gaseous mixture used to deposit the silicon oxide layer for Examples 30 to 41, consisted of the following gases, with the following flow regimes: (helium (240 1 / min), nitrogen (285 (1 / min), monosilane (2.4
1 / min), ethylene (15 1 µm) t oxygen (10 1 / min). For him
Example 42, the same gases and flow rates were used, except for monosilane (2.3 1 / min), ethylene (13.8 1 / min) and oxygen (9.2 1 / min). When two coating devices were used to deposit the silicon oxide layer in Examples 30 to 42, the above flow rates were used for each coating device.
In Examples 30 to 42, the deposition temperatures (i.e., the temperature of the float glass belt, under the coating device corresponding to each of the coating devices at 30) were as shown in Table 7. The temperatures in Table 7 have an uncertainty of + 28 ° C. The extraction for each coating device was approximately 2 mbar.
TABLE 7
<td>Device</td><td>Approximate temperature</td>
<td>Coating</td><td>Glass Tape</td>
<td> 27</td><td>721 ° C</td>
<td> 28</td><td>690 ° C</td>
<td> 29</td><td>677 ° C</td>
<td> 30</td><td>621 ° C</td>
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. TiCl<sub>4</sub> liquid was kept in a container under pressure (column pressure of about 0.35 kg / cm<sup>2</sup>). This was used to deliver the liquid to a metering pump and the Coriolis force flow measurement system. The metered flow of the precursor was then fed into a thin film evaporator at a temperature of 43 ° C. TiCl<sub>4</sub> it was then dragged into the carrier gas (helium) and delivered to the downlines at the mixing point at 121 ° C. Ethyl acetate was delivered in a similar way. Liquid ethyl acetate was kept in a container under pressure (column pressure of about 0.35 kg / cm<sup>2</sup>). This was used to deliver the liquid to a metering pump and the Coriolis force flow measurement system. The metered flow of the precursor was then fed into a thin film evaporator at a temperature of 131 ° C. The evaporated ethyl acetate was then entrained in a carrier gas (helium / nitrogen mixture) and delivered to the downlines of the mixing point, maintained at approximately 121 ° C.
TiCl gas streams<sub>4</sub> and ethyl acetate, combined to form a gas mixture, used to deposit the titanium oxide layer. This mixing point was just before the coating device.
the line speed of the floating glass ribbon, the temperature of the silicon oxide deposit and the temperature of the deposition of the titanium oxide layers and the flow rates of the carrier gas by volume of He / N<sub>2</sub> and the TiCl flow rate<sub>4</sub> and ethyl acetate, are described for Examples 30 to 42 in Table 8.
The coated floating glass ribbon was cooled and cut and the optical properties and photocatalytic activity of the samples were determined. Table 9 describes the fogging, transmission and reflection optical properties (percent transmission / reflection visible and color coordinates, using the LAB system) of the samples. The coated glasses were subjected to the abrasion test, in accordance with BS EN 1096, where a sample of size 300 mm x 300 mm was rigidly fixed, at all four corners, to the test bed, ensuring that there was no movement of sample it as much as possible. An unused felt pad, trimmed to the dimensions outlined in the standard (BS EN 1096 Part 2 (1999)) was then mounted on the test finger and this finger lowered to the glass surface. A loading pressure on the 4N test finger was then established and the test started. The finger was allowed to reciprocate through the sample for 500 passes at a rate of 60 passes / minute + 6 passes / minute. Upon completion of this abrasion, the sample was removed and inspected optically and in terms of photocatalytic activity. The sample was deemed to have passed the test if the abrasion results in a change in transmission of only ± 5%, when measured at 550 nm and the coated substrate remains photocatalytically active, which means that, after test irradiation by UV light for 2 hors, reduce the angle of contact with static water below 15 °.
The glasses were then also subjected to a humidity cycle test where the coating was subjected to a temperature cycle from 3 ° C to 75 ° C to 35 ° C in 4 hours, at about 1100% relative humidity.
The static water contact angle of the coated glasses, as produced and after 13 0 minutes of UV irradiation (351 nm UVA lamp at approximately 32 W / m<sup>2</sup>) and after 300, 500 and / or 1000 passes of the European standard abrasion test, described in Table 10. The contact angle of the samples subjected to abrasion was determined after the 2-hour irradiation.
Samples deposited at temperatures higher than 721 to 677 ° C, were photocatalytically activated, even after 1000 passes of European standard abrasion or after 200 cycles of humidity. The photocatalytic activity in terms of tgo% of the coated glasses, as produced and after 300, 500 and / or 1000 passes of the European standard abrasion test and after 200 cycles of the humidity test, are described in the Table eleven. In this table 11, the term Active, indicates that the coated glasses were photocatalytically active but that the t<sub>90</sub>% was not determined.
<img file="MXPA01012578A_D0002.tif" />
<img file="MXPA01012578A_D0003.tif" />
<td rowspan="5">Titanium Oxide Coating</td><td rowspan="2">Precursor Flow Regimes</td><td>Ethyl acetate cc / min</td><td>16.3 I</td><td>CO "•4</td><td>cn im ·!</td><td>CO</td><td>\OR ""4</td><td>SW</td><td>SW</td><td> 14.7</td><td>[14-7 I</td><td>r- rt</td><td>rt</td><td>or</td><td>i 25.4</td>
<td>c AND or or * OR i-</td><td>I 6.3 I</td><td>1_63 I</td><td>í_63 i</td><td>cn went</td><td>\OR</td><td>SW</td><td>\OR</td><td>iri</td><td>a</td><td>V) Ή</td><td>Ei_1</td><td>Μ<sup>-</sup></td><td>VS you</td>
<td rowspan="2">Flow Regimes of Carrier Gases</td><td>c AND z</td><td> 300 |</td><td> 300 |</td><td> 300 |</td><td>or or co</td><td> | 300 <sup>1</sup></td><td> | 300 ¡</td><td>I 300 j</td><td>or or co</td><td> 1 300</td><td>Γ 300</td><td>or or co</td><td> 1 300</td><td>Γ 300</td>
<td>I have l / min</td><td> 300 |</td><td> 300 |</td><td> 300 |</td><td>OR or ro</td><td> 1 300 |</td><td> 1 300 1</td><td>or or co</td><td>I 300 <sup>1</sup></td><td> 1 300 !</td><td>or or co</td><td>σ or co</td><td>or or co</td><td>or or co</td>
<td>Tank temperature / ° C</td><td></td><td>CM Vo</td><td> 1 621 |</td><td> 1 621 |</td><td> 1 621 1</td><td> 1 621 |</td><td> 1 621 |</td><td>I £ 9 |</td><td>t— c ~ SW</td><td> 1 677</td><td>í 677</td><td> 1 677</td><td> 1 690</td><td> 1 677</td>
<td>Layer Deposit Temperature</td><td>Silica / ° C</td><td></td><td>θ ' (- SW OR You SW</td><td> , 690 & 677 |</td><td> 1 690 & 677 |</td><td> | 690 & 677 1</td><td> ¡ 069 1</td><td> 1 690 ]</td><td> 1 690</td><td> 1 069 1</td><td> 069 |</td><td>i 690</td><td> | 690</td><td> 1 721</td><td> | 721 & 690</td>
<td>Line Speed (m / min)</td><td></td><td></td><td>| 6ΌΙ</td><td>You or</td><td> ¡ 10.9 |</td><td>You or</td><td> 1 10.9 <sup>1</sup></td><td>You OR W — 4</td><td>Γ 10.9</td><td>6ΌΙ |</td><td>You OR</td><td> | 10.9</td><td> | 10.9</td><td>«N yes</td><td>í 12.1</td>
<td>Example</td><td></td><td></td><td> 1_30_1</td><td>* —1 cn</td><td>1_32_I</td><td>cn CO</td><td>I 34 |</td><td>«N in</td><td> 36</td><td>r- cn</td><td> 1 38</td><td>σ \ cn</td><td> | 40</td><td> ^4</td><td><~ Ί yes</td>
or
<img file="MXPA01012578A_D0004.tif" />
<td colspan="2">one Fogging (%) one</td><td>1 ΠΌ</td><td> 0.30</td><td>0.12 I</td><td>0.15 I</td><td>hey ^ 4 OR</td><td>1 ΠΌ 1</td><td>I 0.14 1</td><td>| 80Ό |</td><td> | 0.07 1</td><td>1 EYE 1</td><td>| 80Ό |</td><td>ctí</td><td> 0.14</td>
<td rowspan="4">one Transmission 1</td><td>-OR</td><td><5 cñ</td><td>X co</td><td>3.6 I</td><td>2.9 I</td><td>2.7 I</td><td>'or hey</td><td>1 2.5 J</td><td>L 23. J</td><td>Γ;</td><td> 1 18</td><td> 00</td><td>CS</td><td> 3.1</td>
<td>EC</td><td>ts one</td><td> 1</td><td> 1</td><td>-ΓΓΊ</td><td>^ 4 4 t</td><td> 4—1 1</td><td>1- -.- Μ.- I</td><td>1 -ii</td><td> ·—4 »</td><td> - n- - .1</td><td> ^4 1</td><td>is</td><td> ^4 ^•4 1</td>
<td> *</td><td>93.6 I</td><td> 93.7 |</td><td> 93.6 |</td><td> 94.1 |</td><td> 93.8 |</td><td> 1 94.1 |</td><td> 1 94.2 |</td><td> | 94.4 |</td><td> | 94.8 1</td><td> | 94.8</td><td>t— Tt σ></td><td>ed</td><td>00 tn Ch</td>
<td>£ H</td><td>84.3 I</td><td>i 84.5 J</td><td>CO 00</td><td> | 85.5 |</td><td> | 84.8 |</td><td> 1_85.41</td><td>I 85.8 |</td><td>| I '98 |</td><td> | 87.1 1</td><td> | 87.2</td><td>σ ' d oo</td><td><S</td><td>00 oo</td>
<td rowspan="4">Reflection of the Side of the Film</td><td>ha</td><td> -10.3 |</td><td> -10.4 |</td><td> -10.5 |</td><td> -9.8 |</td><td> -8.7 |</td><td> 1 -8.8 |</td><td>ί -8.2 J</td><td>OR) one</td><td> 1 -6.9 !</td><td>I -6.5</td><td>\ £> d one</td><td>is</td><td> -9.9</td>
<td>is</td><td> 0.3 |</td><td> 0.3 |</td><td> 0.3 |</td><td>i_Q3 |</td><td>OR</td><td>or</td><td>d</td><td>F— · 4 d</td><td>d</td><td>1 οό 1</td><td>σ d</td><td>CS</td><td>ΙΌ</td>
<td> *</td><td><o xr</td><td> 45.1 |</td><td> 45.1 1</td><td> [ 44.0 |</td><td>i_43 / 7 I</td><td> 1 43.9 |</td><td>1_42 ^ 6 I</td><td> 1 42.2 1</td><td>1 41.0 i</td><td> | 40.4</td><td>Γ 40.6</td><td>is</td><td>(OR 4</td>
<td>g Dad</td><td>ts rt</td><td> 1 14.6 |</td><td> !14.6 ,|</td><td>I 13.8 |</td><td> 1 13.6 |</td><td> 1_13.8 , 1</td><td> 1_12-9-,,1</td><td>I 12.6 |</td><td> 1 11.9 1</td><td> 1 11.5 1</td><td>Vo</td><td>cS</td><td rowspan="2"></td>
<td colspan="2">Example</td><td>OR co</td><td>CO</td><td>OJ co</td><td>CO co</td><td>TT co</td><td>co</td><td>L36</td><td>Γ ** co</td><td>I 38 1</td><td> 1 39</td><td>I 40</td><td> 5</td>
Not measured
TABLE 10
<td rowspan="2">Example</td><td colspan="5">Static water contact angle (°) Number of Abrasion Passes</td>
<td> 0</td><td>0 (after 130 min irradiation UV light)</td><td> 300</td><td> 500</td><td> 1000</td>
<td> 30</td><td> 2.3</td><td> 3.3</td><td>failure</td><td></td><td></td>
<td> 31</td><td> 2.0</td><td> 3.</td><td>failure</td><td></td><td></td>
<td> 32</td><td>to</td><td>to</td><td>failure</td><td></td><td></td>
<td> 33</td><td> 2.0</td><td> 3.2</td><td>failure</td><td></td><td></td>
<td> 34</td><td>to</td><td>to</td><td>failure</td><td></td><td></td>
<td> 35</td><td> 2.0</td><td> 3.2</td><td>failure</td><td></td><td></td>
<td> 36</td><td> 2.1</td><td> 3.4</td><td>failure</td><td></td><td></td>
<td> 37</td><td> 2.</td><td> 3.3</td><td></td><td> <15</td><td></td>
<td> 38</td><td> 2.0</td><td> 3.1</td><td></td><td> <15</td><td></td>
<td> 39</td><td> 1.9</td><td> 3.1</td><td></td><td> <15</td><td></td>
<td> 40</td><td> 2.2</td><td> 3.2</td><td></td><td> <15</td><td></td>
<td> 41</td><td> 7.8</td><td> 7.8</td><td></td><td></td><td> 10.1</td>
<td> 42</td><td> 4.7-5.3</td><td> 4.7.5.3</td><td></td><td></td><td> 5.6-9.8</td>
a = Not Measured
TABLE 11
<td>Example</td><td colspan="4">tgoo<sub>/or</sub> (mln), after a Number of Abrasion Passes</td><td>t<sub>90</sub>% (mln) after 200 cycles Humidity</td>
<td></td><td> 0</td><td> 300</td><td> 500</td><td> 1000</td><td></td>
<td> 30</td><td> 7.5</td><td>failure</td><td></td><td></td><td>failure</td>
<td> 31</td><td> 18.5</td><td>failure</td><td></td><td></td><td>failure</td>
<td> 32</td><td> 8.5</td><td>failure</td><td></td><td></td><td>failure</td>
<td> 33</td><td> 8</td><td>failure</td><td></td><td></td><td>failure</td>
<td> 34</td><td> 21</td><td>failure</td><td></td><td></td><td>failure</td>
<td> 35</td><td> 4</td><td>failure</td><td></td><td></td><td>failure</td>
<td> 36</td><td> 8.5</td><td>failure</td><td></td><td></td><td>failure</td>
<td> 37</td><td> 15.5</td><td></td><td>approx. 2160</td><td></td><td>Active</td>
<td> 38</td><td> 18.5</td><td></td><td>approx. 2160</td><td></td><td>Active</td>
<td> 39</td><td> 17</td><td></td><td>approx. 2160</td><td></td><td>Active</td>
<td> 40</td><td> 18.5</td><td></td><td>approx. 2160</td><td></td><td>Active</td>
<td> 41</td><td>to</td><td></td><td></td><td>approx. 2160</td><td>Active</td>
<td> 42</td><td> 45</td><td></td><td></td><td> 2800</td><td>Active</td>
a = Not measured.
Contents12
6 sheets
Sheet 1 Sheet 2 Sheet 3 Sheet 4 Sheet 5 Sheet 6
45 members in 23 offices
Priority claims2
| Document | Office | Kind | Date |
|---|---|---|---|
| 9913315 | United Kingdom | A | |
| 0002111 | United Kingdom | W |
Members45
| Document | Office | Kind | |
|---|---|---|---|
| CA2375662A1 | Canada | A1 | |
| WO0075087A1 | World Intellectual Property Organization (WIPO) | A1 | |
| 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 | |
| AR024312A1 | Argentina | A1 | |
| 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 | |
| HU0203433A2 | Hungary | A2 | |
| HUP0203433A2 | Hungary | A2 | |
| ZA200109801B | South Africa | B | |
| PL352478A1 | Poland | A1 | |
| MXPA01012578AThis record | Mexico | A | |
| CZ20014395A3 | Czechia | A3 | |
| TW591116B | Taiwan Province of China | B | |
| AU775906B2 | Australia | B2 | |
| EA004759B1 | Eurasian Patent Organization (EAPO) | B1 | |
| US6840061B1 | United States of America | B1 | |
| US6929862B2 | United States of America | B2 | |
| IL146661A | Israel | A | |
| UA74550C2 | Ukraine | C2 | |
| US2006019104A1 | United States of America | A1 | |
| MY125239A | Malaysia | A | |
| SA00210544B1 | Saudi Arabia | B1 | |
| SA1419B1 | Saudi Arabia | B1 | |
| KR20070068488A | Republic of Korea | A | |
| KR100783308B1 | Republic of Korea | B1 | |
| AR059303A2 | Argentina | A2 | |
| CN101219861A | China | A | |
| SA05260312B1 | Saudi Arabia | B1 | |
| SA2064B1 | Saudi Arabia | B1 | |
| CA2375662C | Canada | C | |
| JP4716631B2 | Japan | B2 | |
| EP1198431B1 | European Patent Office (EPO) | B1 | |
| EP1254870B1 | European Patent Office (EPO) | B1 |
1 legal event, as the office reported them to INPADOC
Events
| Event | Code | |
|---|---|---|
| Abandonment or withdrawalAbandonedFA | FA |
Numbers
- Application
- 1012578
Titles2
- English
- PROCESS FOR THE PRODUCTION OF PHOTOCATALYTIC COATINGS ON SUBSTRATES.
- Spanish
- PROCESO PARA LA PRODUCCION DE REVESTIMIENTOS FOTOCATALITICOS SOBRE SUBSTRATOS.
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
