EP1005578A1 - Procede de phosphatation accelere par n-oxydes - Google Patents

Procede de phosphatation accelere par n-oxydes

Info

Publication number
EP1005578A1
EP1005578A1 EP98943785A EP98943785A EP1005578A1 EP 1005578 A1 EP1005578 A1 EP 1005578A1 EP 98943785 A EP98943785 A EP 98943785A EP 98943785 A EP98943785 A EP 98943785A EP 1005578 A1 EP1005578 A1 EP 1005578A1
Authority
EP
European Patent Office
Prior art keywords
oxide
phosphating
phosphating solution
solution according
ions
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
Application number
EP98943785A
Other languages
German (de)
English (en)
Other versions
EP1005578B1 (fr
Inventor
Bernd Mayer
Peter Kuhm
Pietro Balboni
Markus Senner
Horst-Dieter Speckmann
Jürgen Geke
Jan-Willem Brouwer
Annette Willer
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority claimed from DE19733978A external-priority patent/DE19733978A1/de
Priority claimed from DE1997150301 external-priority patent/DE19750301A1/de
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP1005578A1 publication Critical patent/EP1005578A1/fr
Application granted granted Critical
Publication of EP1005578B1 publication Critical patent/EP1005578B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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
    • 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
    • C23C22/06—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 aqueous acidic solutions with pH less than 6
    • C23C22/34—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 aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
    • C23C22/36—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 aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates
    • C23C22/364—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 aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates containing also manganese cations
    • 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
    • C23C22/06—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 aqueous acidic solutions with pH less than 6
    • C23C22/07—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 aqueous acidic solutions with pH less than 6 containing phosphates
    • C23C22/08—Orthophosphates
    • C23C22/12—Orthophosphates containing zinc cations

Definitions

  • the invention relates to a phosphating solution, a phosphating concentrate and a method for phosphating metal surfaces with aqueous, acidic phosphating solutions which contain zinc and phosphate ions and at least one organic N-oxide, and their use as pretreatment of the metal surfaces for a subsequent coating, in particular a Electro dip painting.
  • the method is applicable for the treatment of surfaces made of steel, galvanized or alloy galvanized steel, aluminum, aluminized or alloy aluminized steel.
  • the phosphating of metals pursues the goal of producing firmly adherent metal phosphate layers that already improve corrosion resistance and, in conjunction with paints and other organic coatings, contribute to a significant increase in adhesion and resistance to infiltration when exposed to corrosion.
  • Such phosphating processes have long been known in the prior art.
  • the low-zinc phosphating processes are particularly suitable, in which the phosphating solutions have comparatively low contents of zinc ions of e.g. B. 0.5 to 2 g / 1.
  • An important parameter in these low-zinc phosphating baths is the weight ratio of phosphate ions to zinc ions, which is usually in the range> 12 and can take values up to 30.
  • phosphate layers with significantly improved corrosion protection and paint adhesion properties can be formed.
  • z. B. 0.5 to 1.5 g / l of manganese ions and z. B. 0.3 to 2.0 g / l of nickel ions as a so-called trication process for the preparation of metal surfaces for painting, for example for the cathodic electrocoating of car bodies, wide application.
  • DE-A-40 13 483 discloses phosphating processes with which similarly good corrosion protection properties can be achieved as with the trication processes. These processes do without nickel and instead use copper in low concentrations, 0.001 to 0.03 g / l. Oxygen and / or other oxidizing agents with the same effect are used to oxidize the divalent iron formed in the pickling reaction of steel surfaces to the trivalent stage. Nitrite, chlorate, bromate, peroxy compounds and organic nitro compounds such as nitrobenzenesulfonate are specified as such.
  • German patent application DE 42 10 513 modifies this process by adding hydroxylamine, its salts or complexes in an amount of 0.5 to 5 g / l hydroxylamine as a modifying agent for the morphology of the phosphate crystals formed.
  • EP-A-315 059 specifies as a special effect of the use of hydroxylamine in phosphating baths the fact that the phosphate crystals still form in a desired columnar or knot-like form on steel when the Zinc concentration in the phosphating bath exceeds the range customary for low-zinc processes.
  • Hydroxylamine has the great procedural advantage that it generally does not decompose by itself in the phosphating bath and in phosphating concentrates. This enables phosphate bath concentrates and supplementary solutions for phosphate baths to be produced that contain the required amounts of accelerator directly. This eliminates the need for expensive separate metering, as is required, for example, when using nitrite or hydrogen peroxide as an accelerator.
  • the phosphating solution contains copper ions, which is currently a technical trend, hydroxylamine gradually decomposes under the catalytic influence of these ions. In this case, the accelerator must be separated from the phosphating bath and added in increased amounts. There is therefore a need for new accelerators which, like hydroxylamine, can be incorporated into phosphating baths, their concentrates and supplementary solutions without them decomposing in a short time. They should still have this property even when copper ions are present.
  • the object of the invention is to provide a phosphating process which has the advantages of hydroxylamine-accelerated processes, but not the disadvantages thereof with regard to decomposition in the presence of copper ions.
  • the phosphating process should be applicable in the spray, splash immersion or immersion process.
  • the invention accordingly relates to an acidic, aqueous phosphating solution containing
  • Preferred organic N-oxides are those which have a saturated, unsaturated or aromatic five- or six-membered ring system and in which the N atom of the N-oxide is part of this ring system.
  • Examples of such compounds are the N-oxides of substituted or unsubstituted pyrroles, imidazoles, oxazoles, pyridines, pyrimidines, pyrazines, oxazines or their hydrogenation products which have saturated or partially unsaturated rings.
  • N-oxides of substituted or unsubstituted pyridines and morpholines such as, in particular, pyridine-N-oxide, 2-methylpyridine-N-oxide, 4-methylpyridine-N-oxide, morpholine-N-oxide and N-methylmorpholine-N is particularly preferred -Oxide. The latter is particularly preferred.
  • the phosphating solution can contain one or more of these N-oxides.
  • the total concentration of the N-oxides in the phosphating solution is preferably in the range from 0.1 to 3 g / l and in particular in the range from 0.3 to 2 g / l. At lower concentrations, the accelerating effect diminishes, higher concentrations do no harm, but have no technical advantage and are therefore economically disadvantageous.
  • phosphating baths In addition to zinc ions, phosphating baths generally contain sodium, potassium and / or ammonium ions to adjust the free acid.
  • free acid is familiar to the person skilled in the phosphating field. The method of determining free acid and total acid chosen in this document is given in the example section. Free acid values between 0 and 1.5 points and total acid between about 15 and about 35 points are within the technical range and are suitable for the purposes of this invention.
  • the zinc contents are preferably in the range from 0.4 to 2 g / l and in particular from 0.5 to 1.5 g / l, as are customary for low-zinc processes.
  • the weight ratio of phosphate ions to zinc ions in the phosphating baths can vary within a wide range, provided it is in the range between 3.7 and 30. A weight ratio between 10 and 20 is particularly preferred
  • a phosphating solution according to the invention is therefore preferably used which additionally contains about 0.3 to about 4 g / l of chlorate ions.
  • the chlorate concentration is preferably in the range between 1 and 3 g / l.
  • the phosphating solution can contain one or more of the following accelerators in addition to the organic N-oxide:
  • Hydrogen peroxide can be added to the phosphating solution as such. However, it can also be used in bound form in the form of compounds which form or split off hydrogen peroxide in the phosphating bath. Examples of such compounds are perborates, percarbonates, salts of peroxy acids such as peroxodisulfate or peroxides such as sodium or potassium peroxide.
  • Chlorate ions and / or m-nitrobenzenesulfonate ions are preferably used in the form of their water-soluble salts, for example their alkali metal salts.
  • phosphating solutions are preferably used which contain further mono- or divalent metal ions, which experience has shown to have a favorable effect on the paint adhesion and the corrosion protection of the phosphate layers produced thereby. Accordingly, the phosphating solution according to the invention preferably additionally contains one or more of the following cations:
  • the phosphating solutions can additionally contain nickel ions.
  • phosphating baths are preferred which have the lowest possible nickel ion content or, if desired, can also be nickel-free.
  • the phosphating solution according to the invention contains, in addition to zinc ions, 0.1 to 4 g / l of manganese ions and 0.002 to 0.2 g / l of copper ions as additional cations and not more than 0.05 g / l, in particular not more than 0.001 g / l nickel ions.
  • phosphating baths according to the invention can be used which, in addition to zinc ions, contain 0.1 to 4 g / l manganese ions and additionally 0.1 to 2.5 g / l nickel ions.
  • the form in which the cations are introduced into the phosphating baths is in principle irrelevant. It is particularly useful to use oxides and / or carbonates as the cation source.
  • nitrate content of the phosphating bath When phosphating zinc-containing surfaces, it has proven to be advantageous to limit the nitrate content of the phosphating bath to a maximum of 0.5 g / l. This suppresses the problem of so-called speck formation and improves corrosion protection, especially when using nickel-free phosphating baths. Phosphating baths which contain no nitrate are particularly preferred.
  • phosphating baths can be prepared directly on site by dissolving the individual components in the water in the desired concentration range.
  • concentrates that contain the individual components in the desired proportions and from which the usable phosphating bath is prepared on site by dilution with water, or that are added to a working phosphating bath as a supplementary solution to compensate for the consumption of the active components.
  • phosphating concentrates are strongly acidic for stabilization. After dilution with water, the pH and / or the free acid must therefore often be blunted to the desired range.
  • alkaline substances such as sodium hydroxide solution or sodium carbonate or basic salts or hydroxides of Ca, Mg, Zn are added.
  • the invention also relates to an aqueous concentrate which, after dilution with water by a factor between 10 and 100 and, if appropriate, adjustment of the pH to a working range between 2.5 and 3.6, a phosphating solution according to one or more of Claims 1 to 13 results.
  • the invention comprises a method for phosphating metal surfaces made of steel, galvanized or alloy-galvanized steel and / or aluminum.
  • the metal surfaces are brought into contact with the phosphating solution according to the invention by spraying or dipping or by a combination thereof.
  • the temperature of the phosphating solution is preferably in the range between about 40 and about 60 ° C.
  • the phosphating process can be used to phosphate steel or galvanized steel strips in conveyor systems.
  • the phosphating times are in the range from about 3 to about 20 seconds.
  • the method can be used in particular in automobile construction, where treatment times between 1 and 8 minutes are common.
  • the phosphating process is to be seen as a sub-step of the technically usual pretreatment chain.
  • the steps of cleaning / degreasing, rinsing and activating are generally preceded by the phosphating, the activation usually being carried out using activating agents containing titanium phosphate.
  • the phosphating according to the invention can, if appropriate after an intermediate rinse, be followed by a passivating aftertreatment. Treatment baths containing chromic acid are widely used for such a passivating aftertreatment.
  • the phosphating processes and comparative processes according to the invention were checked on steel sheets (St 1405), as are used in automobile construction.
  • the free acid score for all examples and comparative examples means the consumption in ml of 0.1 normal sodium hydroxide solution in order to titrate 10 ml of bath solution up to a pH of 3.6. Similarly, the total acid score indicates consumption in ml up to a pH of 8.2. Exceptions to this definition (Examples 19-31, Comparative Examples 6-11) are given there.
  • the mass per unit area was determined by dissolving in 5% chromic acid solution in accordance with DIN 50942.
  • the concentration of the accelerators was measured immediately after the phosphating bath had been prepared. Immediately afterwards, 3 steel sheets were phosphated. The phosphating results are entered in Table 2. After the 3 sample sheets had been phosphated, the phosphating bath was stirred at a temperature of 55 ° C. for a period of 24 hours with a magnetic stirrer so strongly that air was drawn into the phosphating bath through the stirring funnel. The concentration of the accelerator was then determined again.
  • the automotive-typical substrates cold-rolled steel St 1405 (CRS), electrolytically galvanized steel (EG) on both sides and hot-dip galvanized steel (HDG) were used for this exemplary embodiment.
  • CRS cold-rolled steel St 1405
  • EG electrolytically galvanized steel
  • HDG hot-dip galvanized steel
  • VDA 621-415 A typical automotive alternating climate test (VDA 621-415) was carried out with painted metal sheets.
  • the paint infiltration was measured on a scratch (half the scratch width) and the degree of corrosion was determined after a stone chip test in accordance with the VW standard (scale values from 1 to 10 after increasing corrosion).
  • Comparative example 5 differs from embodiment 15 in that instead of N-morpholine-N-oxide 2 g / l of hydroxylammonium sulfate were used as accelerators.
  • Phosphate with phosphate baths according to Table 4, spray at 52 ° C, 30 seconds, spray pressure 1 bar.
  • the phosphating baths contained different amounts of complex-bound fluoride (H 2 SiF 6 ) and had different values of free acid and total acid. These are shown in Table 5 together with the layer weights obtained and the optics of the phosphate layers (examined with scanning electron microscopy).
  • the phosphating solution for Example 18 is included in Table 4. It also contained 1750 ppm of complex-bound fluoride (H 2 SiF 6 ). In this way, the substrates CRS, EG and HDG were phosphated at temperatures of 45 ° C. and 50 ° C. in the aforementioned process. The layer weights are shown in Table 6. In all cases, optically perfect layers were obtained.
  • the phosphating processes and comparative processes according to the invention were checked on steel sheets (St 1405), as are used in automobile construction.
  • the free acid score is understood to mean the consumption in ml of 0.1 normal sodium hydroxide solution in order to titrate 10 ml of bath solution up to a pH of 3.6. Similarly, the total acid score indicates consumption in ml up to a pH of 8.5.

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)

Abstract

L'invention concerne une solution de phosphatation acide aqueuse contenant entre 0,2 et 3 g/l d'ions de zinc, entre 3 et 50 g/l d'ions de phosphate, figurant sous PO43-, ainsi que comme médiateur, entre 0,05 et 4 g/l d'un N-oxyde organique. Le N-oxyde est de préférence sélectionné dans les N-oxydes substitués ou des pyridines et des morpholines non substituées, notamment dans le groupe de pyridine-N-oxyde, 2-méthylpyridine-N-oxyde, 4-méthylpyridine-N-oxyde, morpholine-N-oxyde et N-méthylmorpholine-N-oxyde. La solution de phosphatation contient comme comédiateur, de préférence du chlorate, du peroxyde d'hydrogène, de la nitroguanidine et/ou du sulfonate de m-nitrobenzène.
EP98943785A 1997-08-06 1998-07-25 Procede de phosphatation accelere par n-oxydes Expired - Lifetime EP1005578B1 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
DE19733978A DE19733978A1 (de) 1997-08-06 1997-08-06 Mit N-Oxiden beschleunigtes Phosphatierverfahren
DE19733978 1997-08-06
DE1997150301 DE19750301A1 (de) 1997-11-13 1997-11-13 Mit N-Oxiden und Clorat beschleunigtes Phosphatierverfahren
DE19750301 1997-11-13
PCT/EP1998/004669 WO1999007916A1 (fr) 1997-08-06 1998-07-25 Procede de phosphatation accelere par n-oxydes

Publications (2)

Publication Number Publication Date
EP1005578A1 true EP1005578A1 (fr) 2000-06-07
EP1005578B1 EP1005578B1 (fr) 2002-10-09

Family

ID=26038895

Family Applications (1)

Application Number Title Priority Date Filing Date
EP98943785A Expired - Lifetime EP1005578B1 (fr) 1997-08-06 1998-07-25 Procede de phosphatation accelere par n-oxydes

Country Status (7)

Country Link
US (1) US6379474B1 (fr)
EP (1) EP1005578B1 (fr)
AU (1) AU9156398A (fr)
CA (1) CA2300276A1 (fr)
DE (1) DE59805918D1 (fr)
ES (1) ES2185213T3 (fr)
WO (1) WO1999007916A1 (fr)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19933189A1 (de) * 1999-07-15 2001-01-18 Henkel Kgaa Verfahren zur korrosionsschützenden Behandlung oder Nachbehandlung von Metalloberflächen
US6391384B1 (en) * 2000-07-10 2002-05-21 Carus Corporation Method for providing a corrosion inhibiting solution
DE10155666A1 (de) * 2001-11-13 2003-05-22 Henkel Kgaa Mit Hydroxylamin und organischen Stickstoffverbindungen beschleunigtes Phosphatierverfahren
EP1453989A4 (fr) * 2001-12-13 2005-03-23 Henkel Kgaa Utilisation d'hydroxylamines substituees pour les procedes de phosphatation de metal
DE50310042D1 (de) 2002-07-10 2008-08-07 Chemetall Gmbh Verfahren zur beschichtung von metallischen oberflächen
DE10320313B4 (de) * 2003-05-06 2005-08-11 Chemetall Gmbh Verfahren zum Beschichten von metallischen Körpern mit einer Phosphatierungslösung, Phosphatierungslösung und die Verwendung des beschichteten Gegenstandes
DE10323305B4 (de) * 2003-05-23 2006-03-30 Chemetall Gmbh Verfahren zur Beschichtung von metallischen Oberflächen mit einer Wasserstoffperoxid enthaltenden Phosphatierungslösung, Phosphatierlösung und Verwendung der behandelten Gegenstände
DE102005047424A1 (de) * 2005-09-30 2007-04-05 Henkel Kgaa Phosphatierlösung mit Wasserstoffperoxid und chelatbildenden Carbonsäuren
BRPI0811201A2 (pt) * 2007-06-07 2014-10-29 Henkel Ag & Co Kgaa Composição de matéria líquida útil para a formação de um revestimento de conversão de fosfato sobre um substrato metálico, processo para a produção de um revestimento de conversão de fosfato sobre um substrato metálico, e, artigo de fabricação.
DE102008044143B4 (de) * 2008-11-27 2011-01-13 Atotech Deutschland Gmbh Wässrige Behandlungslösung und Verfahren zur Erzeugung von Konversionsschichten für zinkhaltige Oberflächen

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE432557A (fr) * 1938-02-04
GB1365291A (en) * 1970-09-25 1974-08-29 Ici Ltd Inhibition of corrosion
US4596607A (en) * 1985-07-01 1986-06-24 Ford Motor Company Alkaline resistant manganese-nickel-zinc phosphate conversion coatings and method of application
US4865653A (en) 1987-10-30 1989-09-12 Henkel Corporation Zinc phosphate coating process
DE4013483A1 (de) 1990-04-27 1991-10-31 Metallgesellschaft Ag Verfahren zur phosphatierung von metalloberflaechen
US5268041A (en) 1990-04-27 1993-12-07 Metallgesellschaft Ag Process for phosphating metal surfaces
DE4210513A1 (de) 1992-03-31 1993-10-07 Henkel Kgaa Nickel-freie Phosphatierverfahren
DE4441710A1 (de) * 1994-11-23 1996-05-30 Henkel Kgaa Korrosionsschutz und Reibungsverminderung von Metalloberflächen
US5935348A (en) 1995-11-14 1999-08-10 Henkel Kommanditgesellschaft Auf Aktien Composition and process for preventing corrosion and reducing friction on metallic surfaces

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9907916A1 *

Also Published As

Publication number Publication date
CA2300276A1 (fr) 1999-02-18
ES2185213T3 (es) 2003-04-16
US6379474B1 (en) 2002-04-30
DE59805918D1 (de) 2002-11-14
WO1999007916A1 (fr) 1999-02-18
EP1005578B1 (fr) 2002-10-09
AU9156398A (en) 1999-03-01

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