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
  • C23C22/73—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 characterised by the process
• • 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
• • 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
  • C23C22/18—Orthophosphates containing manganese cations
  • C23C22/182—Orthophosphates containing manganese cations containing also zinc cations
  • C23C22/184—Orthophosphates containing manganese cations containing also zinc cations containing also nickel 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
  • C23C22/82—After-treatment
  • C23C22/83—Chemical after-treatment

Definitions

• aluminum is increasingly used in vehicle construction.
• the expression "aluminum” refers not only to pure aluminum but also to aluminum alloys whose main component is aluminum. Examples of commonly used alloying elements are silicon, magnesium, copper, manganese, chromium and nickel, the total proportion by weight of these alloying elements in the alloy normally not exceeding 10 %.
• engine and gear parts, wheels, seat frames, etc. already contain large amounts of aluminum, the use of aluminum in bodywork construction is presently still restricted to parts such as hoods, rear trunk lids, inner door parts and various small parts as well as truck cabins, side walls of transporters or attachments to minivans. Overall, worldwide less than 5 % of the metal surface of automobile bodies is made of aluminum. The increased use of aluminum in this sector is being intensively investigated by the aluminum and automobile industries.
• This invention relates to a process for the corrosion-prevention pretreatment before painting of composite metal structures that contain aluminum and/or aluminum alloy portions in addition to steel and/or galvanized steel portions.
• the process is particularly intended for use in automobile manufacturing.
• car bodies or car body parts that contain structural portions of aluminum and/or its alloys in addition to structural portions of steel and/or galvanized steel are subjected to a conversion-chemical pretreatment before they are painted.
• a cathodic electro-dipcoating is conventionally used at the present time as the first painting stage.
• the process according to the invention is particularly suitable as a pretreatment for this stage.
• the process differs from previous conventional pretreatment processes in automobile manufacturing in that a surface-covering zinc phosphate layer is deposited in a first step on the steel and/or galvanized steel surfaces, without coating the aluminum surfaces to any appreciable extent.
• a second step comprises a treatment with a solution that does not excessively attack the previously formed zinc phosphate layer, and indeed preferably even enhances its corrosion-prevention action, and which simultaneously forms a surface layer on the aluminum surfaces.
• a two-stage process is thus involved, whose first stage comprises a conventional zinc phosphating. It is a necessary condition, of course, that a zinc phosphating solution is used that does not form a layer on aluminum: Such zinc phosphating solutions are known in the prior art and are referred to by the way of example hereinafter.
• a zinc phosphating solution is used that does not form a layer on aluminum:
• Such zinc phosphating solutions are known in the prior art and are referred to by the way of example hereinafter.
• solutions with constituents that are effective to form a protective layer on aluminum are used.
• the nature and concentration of these solutions should be chosen so that on the one hand a layer is reliably formed on the aluminum surfaces; but on the other hand the crystalline zinc phosphation layers formed on the iron and/or zinc surfaces are not excessively damaged.
• the aim of phosphating metals is to produce firmly adhering metal phosphate layers on the metal surface that per se already improve the corrosion resistance, and in conjunction with paints or other organic coatings contribute to a substantial improvement of the coating adhesion and resistance to creepage under corrosive stress.
• Such phosphating processes have been known for a long time.
• low zinc phosphating processes in which the phosphating solutions contain relatively small concentrations of zinc ions, for example 0.5 to 2 grams per liter, hereinafter usually abbreviated as "g/l", are particularly suitable.
• a basic parameter in these low zinc phosphating baths is the weight ratio of phosphate ions to zinc ions, which is normally above 8 and may reach values of up to 30.
• phosphate layers with substantially improved corrosion-prevention and paint adhesion properties can be formed by the co-use of other polyvalent cations in the zinc phosphating baths.
• low zinc processes with the addition of, e.g., 0.5 to 1.5 g/l of manganese ions and, e.g., 0.3 to 2.0 g/l of nickel ions are widely used as so-called "tri-cation" processes for preparing metal surfaces for painting, for example for cathodic electro-dipcoating of car bodies.
• EP-A-459 541 describes phosphating solutions that are essentially free of nickel and that contain, in addition to zinc and phosphate, 0.2 to 4 g/l of manganese and 1 to 30 milligrams per liter, hereinafter usually abbreviated as "mg/l", of copper. From DE-A-42 10 513 nickel-free phosphating solutions are known that contain, in addition to zinc and phosphate, 0.5 to 25 mg/l of copper ions as well as hydroxylamine as accelerator. These phosphating solutions optionally also contain 0.15 to 5 g/l of manganese.
• German patent application DE 196 06 017.6 describes a phosphating solution, with a decreased heavy metal concentration, which contains 0.2 to 3 g/l of zinc ions, 1 to 150 mg/l of manganese ions, and 1 to 30 mg/l of copper ions.
• This phosphating solution may optionally contain up to 50 mg/l of nickel ions and up to 100 mg/l of cobalt ions.
• a further optional constituent is lithium ions in amounts of between 0.2 and 1.5 g/l.
• DE 195 38 778 describes controlling the coating weight of phosphate layers by the use of hydroxylamine as accelerator.
• the use of hydroxylamine and/or its compounds in order to influence the form of the phosphate crystals is known from a number of publications.
• EP-A-315 059 discloses as a special effect of the use of hydroxylamine in phosphating baths the fact that on steel the phosphate crystals still occur in the desired columnar or nodular form, even if the zinc concentration in the phosphating bath exceeds the conventional range for low zinc processes. In this way it is possible to operate the phosphating baths with zinc concentrations up to 2 g/l and with weight ratios of phosphate to zinc of as low as 3.7.
• the required hydroxylamine concentration is given as 0.5 to 50 g/l, preferably 1 to 10 g/l.
• WO 93/03198 discloses the use of hydroxylamine as accelerator in tri-cation phosphating baths with zinc contents of between 0.5 and 2 g/l and nickel and manganese contents of in each case 0.2 to 1.5 g/l, specific weight ratios of zinc to the other divalent cations having to be maintained.
• these baths contain 1 to 2.5 g/l of a "hydroxylamine accelerator", which according to the description denotes salts of hydroxylamine, preferably hydroxylamine ammonium sulfate.
• Particularly effective polymers of this type contain amine substituents and may be obtained by a Mannich reaction between poly(vinylphenols) and aldehydes and organic amines. Such polymers are described for example in EP-B-91 166 , EP-B-319 016 and EP-B-319 017 . Polymers of this type are also used within the scope of the present invention, and accordingly the contents of the immediately aforementioned four documents, except to any extent that may be inconsistent with any explicit teaching herein, are hereby incorporated herein by reference. The use of such polyvinyl phenol derivatives for the surface treatment of aluminum is known, for example, from the aforementioned EP-B-319 016 .
• WO 90/12902 discloses a chromium-free coating for aluminum, the aluminum surfaces being contacted with a treatment solution that has a pH in the range from about 2.5 to about 5.0 and contains, in addition to polyvinyl phenol derivatives, also phosphate ions as well as fluoro acids of the elements zirconium, titanium, hafnium and silicon.
• US-A-5 129 967 discloses treatment baths for a no-rinse treatment (termed there as "dried in place conversion coating") of aluminum, containing:
• DE-C-19 33 013 discloses treatment baths with a pH above 3.5, which besides complex fluorides of boron, titanium or zirconium in amounts of 0.1 to 15 g/l, measured as its stoichiometric equivalent as boron, titanium, or zirconium as appropriate, additionally contain 0.5 to 30 g/l of oxidizing agent, especially sodium meta-nitrobenzenesulfonate.
• DE-C-24 33 704 describes treatment baths to improve paint adhesion and permanent corrosion prevention on, inter alia , aluminum, which may contain 0.1 to 5 g/l of polyacrylic acid or its salts or esters as well as 0.1 to 3.5 g/l of ammonium fluorozirconate, calculated as ZrO 2 .
• the pH of these baths may vary over a wide range. The best results are generally obtained when the pH is between 6 and 8.
• US-A-4 992 116 describes treatment baths for the conversion treatment of aluminum with pH values between about 2.5 and 5, which contain at
• DE-A-27 15 292 discloses treatment baths for the chromium-free pretreatment of aluminum cans, which contain at least 10 parts per million by weight, hereinafter usually abbreviated as "ppm", of titanium and/or zirconium, between 10 and 1000 ppm of phosphate, and a sufficient amount of fluoride, but at least 13 ppm, to form complex fluorides of the titanium and/or zirconium present, and have pH values of between 1.5 and 4.
• ppm parts per million by weight
• WO 92/07973 discloses a chromium-free treatment process for aluminum, which uses as essential components in acid aqueous solution 0.01 to about 18 wt. % of H 2 ZrF 6 and 0.01 to about 10 wt. % of a 3-(N-C 1-4 alkyl-N-2-hydroxyethyl-aminomethyl)-4-hydroxystyrene polymer.
• Optional components include 0.05 - 10 wt. % of dispersed SiO 2 , 0.06 to 0.6 wt. % of a solubilizing agent for the polymer, as well as a surfactant.
• the aforementioned polymer is included among the "reaction products of poly(vinylphenol) with aldehydes and organic hydroxyl group-containing amines" described below and that can be used within the scope of the present invention.
• the fluoride ions mask the aluminum ions by complex formation and/or precipitate these ions as hexa-fluoroaluminates of sodium and/or potassium if the solubility products of the corresponding salts are exceeded. Furthermore free fluoride ions usually lead to an increased etching attack on the aluminum surfaces, with the result that a more or less closed and sealed zinc phosphate layer can form on the latter.
• the joint phosphating of aluminum structural portions with those of steel and/or galvanized steel thus has the technical disadvantage that the phosphating baths have to be very accurately monitored as regards their fluoride content. This increases the control and monitoring work involved and may require stocking and metering fluoride-containing solutions as separate replenishment solutions. Also, the precipitated hexafluoroaluminate salts increase the amount of phosphating sludge and raise the cost of its removal and disposal.
• This object is achieved by a process for the chemical pretreatment, before an organic coating, of composite metal structures that contain aluminum or aluminum alloy portions together with steel, galvanized steel and/or alloy-galvanized steel portions, characterized by:
• a zinc phosphating solution which has a pH in the range from about 2.5 to about 3.6 and a temperature in the range from about 20 to about 65 °C, and which does not contain more free fluoride in g/l than is specified by the expression 8/T, "T" denoting the bath temperature in °C, is preferably used.
• this zinc phosphating solution preferably also comprises:
• step (I) additionally contains one or more of the following cation concentrations:
• the zinc concentration is more preferably in the range between about 0.8 and about 1.6 g/l.
• Such zinc concentrations are adjusted in a working phosphating bath if during the phosphating of galvanized surfaces additional zinc passes into the phosphating bath through its etching action.
• the manganese content may be in the range from about 0.001 to 0.2 g/l. Otherwise manganese contents of about 0.5 to about 1.5 g/l are conventional.
• lithium ions in amounts of about 0.2 to about 1.5 g/l improve the corrosion prevention that can be achieved with zinc phosphating baths.
• Lithium concentrations in the range from 0.2 to about 1.5 g/l and in particular from about 0.4 to about 1 g/l also have a beneficial effect on the resultant corrosion prevention with the phosphating process according to the invention and subsequent posttreatment.
• the phosphating baths as a rule also contain sodium, potassium and/or ammonium ions to adjust the free acid.
• free acid is well known to those skilled in the art in the phosphating field. The method chosen to determine free acid as well as the total acid in this step is specified in the examples. Free acid and total acid represent an important control parameter for phosphating baths, since they have a large influence on the coating weight.
• accelerators are conventionally used in the prior art as components of zinc phosphating baths.
• the term accelerators refers to substances that chemically react with the hydrogen produced on the metal surface by the etching action of the acid in such a way that they are themselves reduced.
• Oxidizing accelerators furthermore have the effect of oxidizing iron(II) ions released by the etching action on steel surfaces to the trivalent oxidation state, so that they can precipitate out as iron (III) phosphate.
• step (II) solutions according to the prior art that produce a conversion layer on aluminum may be used. These solutions must not, however, excessively dissolve the crystalline zinc phosphate layer formed in step (I). The pH of these solutions should therefore lie in the range from 3,5 to 5,5.
• solutions are chosen containing components that additionally passivate the crystalline zinc phosphate layers. Such solutions are mentioned hereinafter by way of example.
• the metal structures are generally brought into contact with the treatment solutions by spraying or by dipping.
• the temperature of the treatment solution for step (II) is preferably chosen in the range from 20 to 70 °C.
• a treatment solution may be used that has a pH in the range from about 5 to about 5.5 and that contains overall about 0.3 to about 1.5 g/l of hexafluorotitanate and/or hexafluorozirconate ions. It may be advantageous for the corrosion protection of the crystalline zinc phosphate layer produced in step (I) if this treatment solution additionally contains about 0.01 to 0.1 g/l of copper ions for step (II).
• a treatment solution may be used in step (II) that has a pH in the range from 3.5 to 5.5 and that contains 10 to 500 mg/l of organic polymers chosen from poly-4-vinylphenol compounds of the immediately following general formula (I): wherein n is an integer between 5 and 100, each of X and Y independently of each other denotes hydrogen or a CRR 1 OH moiety in which each of R and R 1 independently is hydrogen or an aliphatic or aromatic moiety with 1 to 12 carbon atoms.
• step (II) in particular those treatment solutions are preferred that contain polyvinylphenol derivatives according to the teaching of EP-B-319 016 .
• This document also discloses the preparation of such polyvinylphenol derivatives.
• a treatment solution is preferably used that has a pH in the range from 3,5 to 5,5 and contains 10 to 5000 mg/l of organic polymers selected from homopolymer or copolymer compounds containing amino groups, comprising at least one polymer selected from the group consisting of materials ( ⁇ ) and ( ⁇ ), wherein:
• materials ( ⁇ ) and/or ( ⁇ ) predominantly molecules which consist entirely, except for relatively short end groups, of units conforming to one of the general formulas (I) and (II) as described above.
• materials are generally prepared by reacting homopolymers of p -vinyl phenol, for material ( ⁇ ), or phenol-aldehyde condensation products, for material ( ⁇ ), with formaldehyde and secondary amines to graft moieties Z on some of the activated benzene rings in the materials thus reacted.
• material ( ⁇ ) is material in which the polymer chains are at least predominantly copolymers of simple or substituted 4-vinyl phenol with another vinyl monomer such as acrylonitrile, methacrylonitrile, methyl acrylate, methyl methacrylate, vinyl acetate, vinyl methyl ketone, isopropenyl methyl ketone, acrylic acid, methacrylic acid, acrylamide, methacrylamide, n- amyl methacrylate, styrene, m -bromostyrene, p -bromostyrene, pyridine, diallyldimethyl-ammonium salts, 1,3-butadiene, n -butyl acrylate, t -butylamino-ethyl methacrylate, n- butyl methacrylate, t -butyl methacrylate, n -butyl vinyl ether, t -butyl vinyl ether,
• Solutions may be used that do not contain any further active constituents, apart from the polyvinyl phenol derivative and an acid for adjusting the pH, preferably phosphoric acid. Additions of further active constituents may however improve the layer formation on aluminum.
• a solution may be used whose pH lies preferably in the range from about 3.5 to about 5.5 and which contains as organic polymer about 100 to about 5000 mg/l of an organic polymer in the form of a methylethanolamine derivative or N-methylglucamine derivative of polyvinyl phenol and in addition 10 to 2000 mg/l of phosphate ions and 10 to 1000 mg/l of manganese ions.
• step (II) there may be used in step (II) solutions or dispersions of organic polymers selected from homopolymers and/or copolymers of acrylic acid and methacrylic acid as well as their esters.
• these solutions or dispersions have pH values in the range from about 3.5 to about 4.8 and contain about 250 to about 1500 mg/l of organic polymers.
• these polymer solutions or dispersions may additionally contain hexafluorotitanates, hexafluorozirconates and/or hexafluorosilicates.
• a process sequence according to the invention was tested on sample metal sheets of cold rolled steel (hereinafter usually abbreviated as "CRS”), electrolytically galvanized steel (hereinafter usually abbreviated as “ZE”), electrolytically zinc-iron-coated steel (hereinafter usually abbreviated as “ZFE”) and on aluminum 6111.
• CRS cold rolled steel
• ZE electrolytically galvanized steel
• ZFE electrolytically zinc-iron-coated steel
• aluminum 6111 aluminum 6111.
• these metal sheets were first of all cleaned with alkali and activated with an activating solution containing titanium phosphate. The sheets were then dipped for 3 minutes in a phosphating bath at a temperature of 48 °C having the following composition:
• the corrosion resistance tests were carried out according to the GM9540P-B process cycle of General Motors, which consists of the following steps:
• Table 1 shows the compositions of the three post-rinse solutions, and Tables 2 and 3 show the zinc phosphate coating etch amounts and the average paint creepages at the scribe (full scribe width) respectively.
• Table 1 POST-RINSE COMPOSITIONS Ingredient Comparison Amount of Ingredient in: comparison Post-rinse Post-rinse soln.(b), Post-rinse soln.(c), soln.(a), pH 3.5 pH 2.9 pH 2.7 Polymer* 0.453 g/l 0.451 g/l 0.113 g/l Phosphate 0.957 g/l 0.955 g/l 0.239 g/l Hexafluortitanate 1 g/l 1 g/l 0.25 g/l Mn(II) 0.39 g/l 0.39 g/l 0.1 g/l * Poly(5-vinyl-2-hydroxy-N-benzyl)-N-methylglucamine Table 2: ZINC PHOSPHATE

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• 1998
  • 1998-09-04 CN CNB988099438A patent/CN1157263C/zh not_active Expired - Lifetime
  • 1998-09-04 TR TR2000/00657T patent/TR200000657T2/xx unknown
  • 1998-09-04 PL PL98339252A patent/PL339252A1/xx unknown
  • 1998-09-04 JP JP2000510539A patent/JP2001515959A/ja active Pending
  • 1998-09-04 ES ES98946801T patent/ES2316169T3/es not_active Expired - Lifetime
  • 1998-09-04 CA CA002303183A patent/CA2303183C/en not_active Expired - Lifetime
  • 1998-09-04 BR BR9812069-7A patent/BR9812069A/pt not_active IP Right Cessation
  • 1998-09-04 DE DE69840270T patent/DE69840270C5/de not_active Expired - Lifetime
  • 1998-09-04 EP EP98946801A patent/EP1027170B1/en not_active Expired - Lifetime
  • 1998-09-04 KR KR1020007002586A patent/KR20010023902A/ko not_active Application Discontinuation
  • 1998-09-04 AU AU93738/98A patent/AU756876B2/en not_active Ceased
  • 1998-09-04 WO PCT/US1998/018001 patent/WO1999012661A1/en not_active Application Discontinuation
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