EP0943701A1 - Verfahren und Reaktionslösung zur Erzeugung einer Patina - Google Patents
Verfahren und Reaktionslösung zur Erzeugung einer Patina Download PDFInfo
- Publication number
- EP0943701A1 EP0943701A1 EP99102955A EP99102955A EP0943701A1 EP 0943701 A1 EP0943701 A1 EP 0943701A1 EP 99102955 A EP99102955 A EP 99102955A EP 99102955 A EP99102955 A EP 99102955A EP 0943701 A1 EP0943701 A1 EP 0943701A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- copper
- patina
- reaction solution
- salts
- carbonate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/04—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in markedly acid liquids
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/60—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using alkaline aqueous solutions with pH greater than 8
- C23C22/63—Treatment of copper or alloys based thereon
Definitions
- the invention relates to a method and a reaction solution for producing a Patina on surfaces of objects made of copper or a copper alloy.
- patina In the air, a thin green protective layer forms on copper surfaces basic copper compounds. This is called the patina. Training natural Depending on the environmental influences, patina sometimes lasts for several decades. The artificial patination, for example by applying soluble copper salts or Ammonium salts often serve to imitate them only in long periods of time forming natural patina. With imitated patina, basic copper compounds are used as color pigments with organic or inorganic film formers on a Copper surface applied.
- reaction solutions do not always bring the desired one Success in terms of layer quality and coloring. Also their handling is partial and storage expensive. They are therefore factory-made for industrial use Creation of a patina or only partially suitable for use on the construction site. Also insists on using some of these reaction solutions on pre-oxidized or already partially patinated copper surfaces, for example for repair purposes of damaged patina, the risk of uneven Layering and coloring.
- the invention is therefore based on the object of a method for producing a mechanically stable patina on preferably pre-weathered copper surfaces create, the patina produced has a reduced copper solubility and as with a natural patina an interaction with the atmosphere is possible is.
- the invention further aims at an improved reaction solution for generation a patina on copper surfaces, which is also easy to use and their storage is.
- a reaction solution consisting of an aqueous solution of copper salts and Salts of inorganic acids applied.
- the copper article treated in this way is then exposed to drying, protected from the weather.
- the patina produced according to the process is mechanically stable and has only a low copper solubility. The time for the production of the patina is comparatively small.
- the patina produced is transparent Provide protective layer made of lacquer.
- a two-component water-based paint is preferably used for this, which contains rubber.
- the paint is colorless.
- the varnish is applied with hardener.
- the ratio of hardener to Lacquer is usually 1: 4.
- the preparation time is a maximum of 20 min.
- the done mixed paint is then preferably applied to the patina using a spray gun applied.
- the varnish After the drying phase, the varnish has hardened and can be weathered. Each according to the prevailing environmental conditions (temperature, humidity, etc.) the drying phase can last 15 to 24 hours.
- the solution of the objective part of the task consists in claim 3 in a reaction solution which consists of an aqueous solution of copper salts and There are salts of inorganic acids.
- the reaction solution according to the invention uses the combination of two different ones Principles for patina education.
- the reaction solution contains reactive ones Components in the form of salts of inorganic acids with the copper oxides of the patinated surfaces react to basic copper compounds.
- the speed this reaction step depends on the weather conditions from.
- the solution already contains those that form during these reactions Copper compounds in the form of copper salts as a kind of color pigment. For this The reason for this immediately becomes a very good color impression immediately after application reached.
- the imitation of the otherwise often only in long periods of time natural patina happens in a short time. Through the subsequent chemical In response, the color impression is intensified and the entire patina layer.
- the best success with the reaction solution according to the invention arises at Use on a pre-oxidized or already partially patinated copper surface.
- the copper objects should undergo appropriate surface pretreatment receive.
- the copper surface can be pre-oxidized at the factory or be pre-patinated.
- the copper surface can also be a natural one Weathering patina layer. An untreated copper surface should be exposed to natural weathering for about two months or more be.
- reaction solution By applying the reaction solution on a pre-oxidized or already partially Patinated copper surface can have a patina layer on site or at the factory be generated. Also copper surfaces that are not completely patinated green are or get damaged patina layers when using the invention Reaction solution an even patina layer. Depending on the composition the color of the reaction solution to be generated Patina varies and can otherwise be adapted to the respective environment.
- the processing and handling of the reaction solution according to the invention is simple.
- the application to the copper surfaces can be done, for example, with a brush, Roll or a spray device.
- copper (I) carbonate Copper (II) carbonate, copper (I) chloride, copper (II) chloride, copper (II) sulfate, Copper acetate, copper nitrate or mixtures thereof are well suited.
- the advantageous one Concentration range is between 5 and 500 g / l.
- the reactive component is preferably sodium carbonate, potassium carbonate, Ammonium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium chloride, Potassium chloride, ammonium chloride, sodium sulfate, sodium hydrogen sulfate, Potassium sulfate, sodium hydrogen sulfate, potassium sulfate, potassium hydrogen sulfate or mixtures of which are used.
- concentration range of these salts is also inorganic Acids is preferably between 5 and 500 g / l.
- the reaction solution according to the invention can be obtained by adding wetting agents or thickeners changed in their consistency and to the respective operating conditions be coordinated.
- wetting agents for example surfactants, and / or known type thickeners. You will be up to the reaction solution added to a share of 5%.
- the reaction solution according to the invention produces a high quality patina basic copper compounds and is particularly good for preoxidized or already partially patinated copper surfaces suitable. Treatment can be done on site at the construction site or at the factory. The reaction solution is also good for that Repair of an existing patina or a color matching of a patina suitable.
- the reaction solution can be prepared and processed at room temperature. It has proven useful to have a patinated surface after treatment be protected from the rain with the reaction solution for at least 48 hours should.
- the patina layer produced in this way can then be used to particular advantage Avoiding damage and reducing copper solubility with a transparent protective layer.
- An aqueous solution containing 200 g / l copper sulfate is first mixed with 200 g / l sodium carbonate added and stirred for one hour at room temperature. After that 200 g / l sodium chloride added and again for one hour at room temperature touched. The solution can then be applied directly to the surface to be patinated be applied.
- a wetting agent for example a Surfactant, added in a concentration of 50 g / l.
- the reaction solution prepared in this way can be stored at room temperature without restriction.
- the copper surface to be patinated usually has a dark brown copper oxide layer that is already partially covered with copper salts (patina).
- the surface is cleaned of grease and loosely adhering dirt before patination. Loose dirt particles can be removed using Water and manual or mechanical aids.
- the copper oxides remaining on the surface and already existing patina are not removed.
- the copper objects are advantageously treated in dry weather, if necessary, the one to be patinated Protect the surface from precipitation with suitable covers.
- the surfaces are taped, that should not be patinated. Then the already prepared reaction solution shaken or stirred and applied. Has been particularly suitable a sprayer has been proven. Depending on the performance of the sprayer used nozzles between 0.2 mm and 0.6 mm in diameter are used. For uniform coating of the surface are spray angles from 60 ° to 90 ° viewed advantageously. Care must be taken during treatment to ensure that drops form is avoided on the surface.
- patination processes can be carried out. In front of everyone Another patination process is to ensure that the surface is complete is dry.
- the protective layer of lacquer can then be applied. Also recommends this the use of a sprayer, preferably with nozzles between 0.2 mm and 0.3 mm in diameter, and a spray angle of 90 °.
- a single application of the protective layer is sufficient.
- the protective layer which varies between 20 minutes and 24 depending on the weather conditions Hours, the copper object should be protected from precipitation become.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Chemical Treatment Of Metals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Sampling And Sample Adjustment (AREA)
Abstract
Description
- Die Lackschicht ist transparent und matt. Sie verändert nicht die optischen Eigenschaften der darunter liegenden Patina.
- Die Lackschicht kann mit Reinigungslösungen behandelt werden. Dementsprechend können beispielsweise Verunreinigungen wie aufgesprühte Graffities mit speziellen Reinigungslösungen rückstandsfrei entfernt werden, ohne daß die Patina beschädigt wird.
- Die Lackschicht ist wasserdampfdiffusionsdurchlässig. Hierdurch kann die darunter liegende Patina weiter mit der Atmosphäre in Wechselwirkung treten.
- Die Lackschicht bewirkt eine Verfestigung der darunter liegenden Patinaoberfläche. Patinierte Kupfergegenstände können folglich mechanisch bearbeitet werden, beispielsweise durch Biegen oder Falzen, ohne daß die Patinierung abplatzt.
Claims (7)
- Verfahren zur Erzeugung einer Patina auf der Oberfläche eines Gegenstands aus Kupfer oder einer Kupferlegierung, wobei die Oberfläche zunächst gereinigt und anschließend auf die Oberfläche eine Reaktionslösung bestehend aus einer wässrigen Lösung von Kupfersalzen und Salzen anorganischer Säuren aufgetragen und dann vor Witterungseinflüssen geschützt der Trocknung ausgesetzt wird.
- Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß auf die Patina eine transparente Lackschicht aufgetragen wird.
- Reaktionslösung zur Erzeugung einer Patina auf Oberflächen von Gegenständen aus Kupfer oder einer Kupferlegierung bestehend aus einer wässrigen Lösung von Kupfersalzen und Salzen anorganischer Säuren.
- Reaktionslösung nach Anspruch 3, dadurch gekennzeichnet, daß Kupfersalz in Form von Kupfer(I)carbonat, Kupfer(II)carbonat, Kupfer(I)chlorid, Kupfer(II)chlorid, Kupfer(II)sulfat, Kupferacetat, Kupfernitrat oder Mischungen hiervon in einer Konzentration zwischen 5 und 500 g/l enthalten ist.
- Reaktionslösung nach Anspruch 3 oder 4, dadurch gekennzeichnet, daß Salze anorganischer Säuren in Form von Natriumcarbonat, Kaliumcarbonat, Ammoniumcarbonat, Natriumhydrogencarbonat, Kaliumhydrogencarbonat, Natriumchlorid, Kaliumchlorid, Ammoniumchlorid, Natriumsulfat, Natriumhydrogensulfat, Kaliumsulfat, Kaliumhydrogensulfat oder Mischungen hiervon in einer Konzentration zwischen 5 und 500 g/l enthalten ist.
- Reaktionslösung nach einem der Ansprüche 3 bis 5, dadurch gekennzeichnet, daß ein Netzmittel bis zu einem Anteil von 5 % zugesetzt ist.
- Reaktionslösung nach einem der Ansprüche 3 bis 6, dadurch gekennzeichnet, daß ein Verdicker bis zu einem Anteil von 5 % zugesetzt ist.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19809904 | 1998-03-07 | ||
| DE19809904A DE19809904A1 (de) | 1998-03-07 | 1998-03-07 | Verfahren und Reaktionslösung zur Erzeugung einer Patina |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0943701A1 true EP0943701A1 (de) | 1999-09-22 |
| EP0943701B1 EP0943701B1 (de) | 2007-07-04 |
Family
ID=7860120
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP99102955A Expired - Lifetime EP0943701B1 (de) | 1998-03-07 | 1999-02-13 | Verfahren und Reaktionslösung zur Erzeugung einer Patina |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US6176905B1 (de) |
| EP (1) | EP0943701B1 (de) |
| KR (1) | KR19990077468A (de) |
| AT (1) | ATE366329T1 (de) |
| DE (2) | DE19809904A1 (de) |
| DK (1) | DK0943701T3 (de) |
| ES (1) | ES2286866T3 (de) |
| PT (1) | PT943701E (de) |
| SG (1) | SG75920A1 (de) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102005059421A1 (de) * | 2005-12-07 | 2007-06-14 | Susan Krieger | Verfahren zur Herstellung von Patina auf textile Oberflächen von aus künstlichen oder natürlichen Fasern bestehenden Geweben |
| EP1619270A3 (de) * | 2004-07-24 | 2008-05-21 | KME Germany AG | Verfahren zur Erzeugung einer anorganischen Deckschicht auf einem Produkt aus Kupfer oder einer Kupferlegierung und tafel-oder bandförmiges Produkt aus Kupfer oder einer Kupferlegierung |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FI20020669A7 (fi) * | 2002-04-09 | 2003-10-10 | Outokumpu Oy | Menetelmä keinotekoisen patinan valmistamiseksi ja patinapasta |
| KR100467939B1 (ko) * | 2002-05-13 | 2005-01-24 | 김부현 | 건축자재 산화 동판 제조용 산화제 조성물 |
| KR20020089223A (ko) * | 2002-08-29 | 2002-11-29 | 서상환 | 녹청동판 제조방법 |
| US7018677B2 (en) * | 2003-07-17 | 2006-03-28 | Crown-Pn L.L.C. | Simulated patina for copper |
| US7060325B2 (en) * | 2003-07-17 | 2006-06-13 | Percy Greenberg | Simulated patina for copper |
| DE10354527B4 (de) * | 2003-11-17 | 2008-08-28 | Kme Germany Ag | Verfahren zur Patinierung von Kupfer |
| US20090045169A1 (en) * | 2004-08-31 | 2009-02-19 | Timothy Ray Poe | Mirror etching composition |
| FI120048B (fi) * | 2004-09-29 | 2009-06-15 | Luvata Espoo Oy | Menetelmä monikerrospatinan valmistamiseksi ja monikerrospatina |
| DE102006053192A1 (de) * | 2006-11-09 | 2008-05-15 | Kme Germany Ag | Verfahren zum Schutz von patinierten Oberflächen von Kupferprodukten sowie patiniertes Kupferprodukt |
| KR100890607B1 (ko) * | 2007-07-02 | 2009-03-27 | 김부현 | 산화 녹청 동판의 제조방법 |
| DE102009012461A1 (de) | 2009-03-12 | 2010-09-16 | Kme Germany Ag & Co. Kg | Schadstoffabbauendes Metallband für das Bauwesen |
| US10119038B2 (en) | 2015-05-08 | 2018-11-06 | PatinaNow, LLC | Patina solution, method for producing patina on object, and patina kit |
| CN114323842B (zh) * | 2021-12-14 | 2022-08-26 | 北京科技大学 | 一种带锈金属文物模拟样品及其制作方法 |
| FR3137924B1 (fr) * | 2022-07-13 | 2025-06-20 | Hermes Sellier | Procédé de réalisation d’une pièce d’apparence noire et auto-cicatrisante ayant un substrat en métal précieux, et pièce obtenue |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3497401A (en) * | 1967-09-20 | 1970-02-24 | Intern Copper Research Ass Inc | Patination of copper |
| JPS55110780A (en) * | 1979-02-15 | 1980-08-26 | Matsushita Electric Works Ltd | Artificial verdigris solution |
| JPS62192586A (ja) * | 1986-02-18 | 1987-08-24 | Yamaki Kogyo Kk | 人工緑青発生液 |
| US5160381A (en) * | 1991-06-26 | 1992-11-03 | Fumigation Maritime Ltee | Method for forming artificially and rapidly patina on copper, products thereof and solutions therefor |
| JPH0967681A (ja) * | 1995-08-31 | 1997-03-11 | Gantan Beauty Kogyo Kk | 緑青皮膜の形成方法及び形成装置 |
| WO1997035046A1 (fr) * | 1996-03-15 | 1997-09-25 | Brumagne Jean Claude | Procede de traitement de surface metallique d'un materiau compose ou revetu de cuivre et/ou de zinc |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4325177A (en) * | 1979-01-19 | 1982-04-20 | Depoorter Lieven L | Modular art wall systems |
| DE4034249A1 (de) * | 1990-10-27 | 1992-04-30 | Kabelmetal Ag | Verfahren zur herstellung von braunen deckschichten auf kupfer |
| DE4041854A1 (de) * | 1990-12-24 | 1992-06-25 | Kabelmetal Ag | Verfahren zur herstellung einer gruenen patina auf aus kupfer bestehendem halbzeug |
| DE4202779A1 (de) * | 1991-12-21 | 1993-06-24 | Guenther Wottrich | Verfahren und mittel zur veredelung des optischen erscheinungsbildes einer oberflaeche |
| JPH0835072A (ja) * | 1994-07-25 | 1996-02-06 | Shigeyoshi Tashiro | 緑青発生用液組成物及び緑青銅板の製作法 |
| DE19548261A1 (de) * | 1995-12-22 | 1997-06-26 | Km Europa Metal Ag | Verfahren zur Herstellung einer Bronchantitpatina auf Kupferhalbzeug |
-
1998
- 1998-03-07 DE DE19809904A patent/DE19809904A1/de not_active Withdrawn
-
1999
- 1999-02-13 DK DK99102955T patent/DK0943701T3/da active
- 1999-02-13 PT PT99102955T patent/PT943701E/pt unknown
- 1999-02-13 DE DE59914396T patent/DE59914396D1/de not_active Expired - Lifetime
- 1999-02-13 AT AT99102955T patent/ATE366329T1/de active
- 1999-02-13 EP EP99102955A patent/EP0943701B1/de not_active Expired - Lifetime
- 1999-02-13 ES ES99102955T patent/ES2286866T3/es not_active Expired - Lifetime
- 1999-02-25 KR KR1019990006228A patent/KR19990077468A/ko not_active Ceased
- 1999-02-27 SG SG1999001034A patent/SG75920A1/en unknown
- 1999-03-05 US US09/263,315 patent/US6176905B1/en not_active Expired - Lifetime
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3497401A (en) * | 1967-09-20 | 1970-02-24 | Intern Copper Research Ass Inc | Patination of copper |
| JPS55110780A (en) * | 1979-02-15 | 1980-08-26 | Matsushita Electric Works Ltd | Artificial verdigris solution |
| JPS62192586A (ja) * | 1986-02-18 | 1987-08-24 | Yamaki Kogyo Kk | 人工緑青発生液 |
| US5160381A (en) * | 1991-06-26 | 1992-11-03 | Fumigation Maritime Ltee | Method for forming artificially and rapidly patina on copper, products thereof and solutions therefor |
| JPH0967681A (ja) * | 1995-08-31 | 1997-03-11 | Gantan Beauty Kogyo Kk | 緑青皮膜の形成方法及び形成装置 |
| WO1997035046A1 (fr) * | 1996-03-15 | 1997-09-25 | Brumagne Jean Claude | Procede de traitement de surface metallique d'un materiau compose ou revetu de cuivre et/ou de zinc |
Non-Patent Citations (3)
| Title |
|---|
| PATENT ABSTRACTS OF JAPAN vol. 004, no. 173 (C - 032) 29 November 1980 (1980-11-29) * |
| PATENT ABSTRACTS OF JAPAN vol. 012, no. 047 (C - 475) 12 February 1988 (1988-02-12) * |
| PATENT ABSTRACTS OF JAPAN vol. 097, no. 007 31 July 1997 (1997-07-31) * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1619270A3 (de) * | 2004-07-24 | 2008-05-21 | KME Germany AG | Verfahren zur Erzeugung einer anorganischen Deckschicht auf einem Produkt aus Kupfer oder einer Kupferlegierung und tafel-oder bandförmiges Produkt aus Kupfer oder einer Kupferlegierung |
| RU2389825C2 (ru) * | 2004-07-24 | 2010-05-20 | КМ Ойропа Метал АГ | Способ получения неорганического покрытия на поверхности изделия и изделие, имеющее форму пластины или ленты |
| DE102005059421A1 (de) * | 2005-12-07 | 2007-06-14 | Susan Krieger | Verfahren zur Herstellung von Patina auf textile Oberflächen von aus künstlichen oder natürlichen Fasern bestehenden Geweben |
| DE102005059421B4 (de) * | 2005-12-07 | 2007-12-20 | Susan Krieger | Verfahren zur Herstellung von Patina auf textile Oberflächen von aus künstlichen oder natürlichen Fasern bestehenden Geweben |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0943701B1 (de) | 2007-07-04 |
| PT943701E (pt) | 2007-08-01 |
| US6176905B1 (en) | 2001-01-23 |
| ATE366329T1 (de) | 2007-07-15 |
| DE19809904A1 (de) | 1999-09-09 |
| KR19990077468A (ko) | 1999-10-25 |
| ES2286866T3 (es) | 2007-12-01 |
| DK0943701T3 (da) | 2007-11-05 |
| DE59914396D1 (de) | 2007-08-16 |
| SG75920A1 (en) | 2000-10-24 |
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