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
  • C23C22/07—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
• • 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
• • 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
• • 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
  • C23C22/361—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 titanium, zirconium or hafnium compounds
• • 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

• This invention relates to the field of corrosion protection treatment of metal surfaces.
• One aspect of the invention involves depositing an anticorrosive layer onto the bare metal surface.
• a second aspect of the invention involves enhancing the anticorrosive action of an anticorrosive layer already deposited onto the metal surface.
• a particular feature of the invention is that no toxic heavy metals, such as chromium or nickel, have to be used.
• U.S. Pat. No. 5,129,967 discloses treatment baths for a no-rinse treatment (therein referred to as “dried in place conversion coating”) of aluminum, containing:
• European Pat. No. 8942 discloses treatment solutions, preferably for aluminum cans, containing:
• DE-C-1933013 discloses treatment baths having a pH of above 3.5 which, besides complex fluorides of boron, titanium or zirconium in quantities of 0.1 to 15 g/l, based on the metals, contain in addition 0.5 to 30 g/l oxidizing agent, in particular sodium metanitrobenzenesulfonate.
• DE-C-2433704 describes treatment baths for increasing the coating adhesion and the permanent corrosion protection on, inter alia, aluminum; these baths may contain 0.1 to 5 g/l polyacrylic acid or salts or esters thereof, as well as 0.1 to 3.5 g/l 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 from 6 to 8.
• U.S. Pat. No. 4,992,116 describes treatment baths for the conversion treatment of aluminum having a pH of between about 2.5 and 5, which contain at least three components:
• DE-A-2715292 discloses treatment baths for the chromium-free preliminary treatment of aluminum cans. These baths contain at least 10 ppm titanium and/or zirconium, between 10 and 1000 ppm phosphate and a quantity of fluoride sufficient for the formation of complex fluorides of the titanium and/or zirconium present, but at least 13 ppm, and have a pH of between 1.5 and 4.
• WO 92/07973 discloses a chromium-free treatment process for aluminum which uses from 0.01 to about 18 wt. % H 2 ZrF 6 and from 0.01 to about 10 wt.% of a 3-(N—Cl—4-alkyl-N-2-hydroxyethylaminomethyl)-4-hydroxystyrene polymer as essential components in acidic aqueous solution.
• Optional components are 0.05 to 10 wt. % dispersed SiO 2 ′ 0.06 to 0.6 wt. % of a solubilizer for the polymer as well as a surfactant.
• the metal surface may first of all be subjected to a conversion treatment according to prior art, for example, a phosphating using zinc or iron, a conversion treatment using fluoric acids of metals, for example, of titanium, zirconium or hafnium, or even of boron or silicon, or a treatment using a solution or suspension of an organic polymer which contains no vinylpyrrolidone units.
• a conversion treatment for example, a phosphating using zinc or iron, a conversion treatment using fluoric acids of metals, for example, of titanium, zirconium or hafnium, or even of boron or silicon, or a treatment using a solution or suspension of an organic polymer which contains no vinylpyrrolidone units. Examples of such polymers are given in the literature cited in the introduction.
• An alternative embodiment of the cited invention involves contacting the metal surface with a homo- or copolymer of vinylpyrrolidone at the same time that the metal surface is being subjected to a conversion treatment.
• the homo- or copolymer is therefore present in the treatment solution by means of which a conversion layer is produced on the metal surface.
• the treatment solution for the production of the conversion layer may contain, for example, phosphoric acid or anions thereof. Divalent cations, such as zinc and/or manganese, may also be present in the treatment solution.
• a particular example of such a treatment solution for the production of a conversion layer is a zinc phosphating solution, which produces a crystalline layer of zinc-containing metal phosphates on the metal surface.
• the treatment solution may, however, also contain phosphoric acid and/or anions thereof, but no divalent metals.
• An example of this is an iron phosphating solution, which produces a substantially non-crystalline layer of metal phosphates and/or metal oxides on a metal surface, in particular an iron-containing surface.
• the presence of homo- or copolymers of vinylpyrrolidone in such a treatment solution improves the corrosion protection achieved by the conversion layer. This also applies if the treatment solution, in addition to homo- or copolymers of vinylpyrrolidone, contains fluoric acids and/or complex fluorides of metals and semi-metals, such as boron, silicon, titanium, zirconium and/or hafnium, as components forming the conversion layer.
• the ready-to-use solution for treating metal surfaces preferably contains between 0.05 and 200 g/l of a homo- or copolymer of vinylpyrrolidone.
• the set object of the present invention is to improve on the subject matter of DE 100 05 113 with regard to the efficiency of the chemicals used.
• the present invention relates to an agent for treating metal surfaces, which contains phosphoric acid and/or at least one fluoric acid of one or more elements selected from Zr, Ti, Hf and Si or the respective anions thereof, as well as a homo- or copolymer of vinylpyrrolidone, characterized in that it is in the form of a ready-to-use solution for application, containing
• the agent for treating metal surfaces is a phosphating solution. If this does not contain ions of divalent metals, such as zinc and/or manganese, it is a so-called “non-layer-forming” phosphating solution, for example, it may be in the form of an iron phosphating solution.
• Phosphating solutions containing zinc and/or manganese which contain, for example, 0.3 to 2 g/l zinc ions and, if desired, in addition to or instead of this about the same concentration of manganese ions, are referred to as so-called “layer-forming” phosphating solutions in the field of conversion treatment.
• the treatment solution may also contain one or more fluoric acids of one or more elements selected from Zr, Ti, Hf and Si, together with or instead of phosphoric acid.
• fluoric acids of one or more elements selected from Zr, Ti, Hf and Si
• both phosphoric acid and the above-mentioned fluoric acids are present partly in the form of singly or multiply negatively charged anions.
• the ratio of acidic anions to undissociated acid depends on the protolysis constant of the respective acid and on the pH actually established. This phenomenon is generally known as the acid-base equilibrium.
• the agents contain water and, if desired, other active components or auxiliary substances in order to adjust the pH, increase the anticorrosive action, improve the ease of application and possibly for other purposes.
• the ready-to-use agent can be obtained by diluting a concentrate; this is the subject matter of the previously unpublished German Patent Application DE 100 05 113.
• a concentrate which already contain all the active components are not sufficiently stable in storage for long periods.
• one component of the concentrate may contain at least predominantly the inorganic constituents of the agent, while at least one other component of the concentrate contains the organic polymers.
• the two components of the concentrate may then have different pH values, thus enabling the stability of the concentrate components in storage to be enhanced.
• the individual components of the concentrate are diluted with water to the extent that the active components are present in the required concentration range.
• Preferred concentration ranges for the active components a) and b) in the solution for application are 5 to 20 g/l, in particular 8 to 16 g/l phosphate ions, and in the case of the fluoric acids are a quantity such that Zr, Ti, Hf and/or Si, based on these elements, are present in a concentration within the range of between 20 and 1000 mg/l, in particular 50 to 400 mg/l.
• the concentration of the homo- or copolymers of vinylpyrrolidone in the solution for application is preferably within the range of 20 to 45 mg/l.
• Suitable homo- or copolymers of vinylpyrrolidone are, for example, the polymers listed in Table 1 or polymers of the monomers named therein. TABLE 1 Examples of homo- or copolymers of vinylpyrrolidone Trade Name and Name Manufacturer Vinylpyrrolidone, homopolymer Luviskol ®, BASF/ ISP Vinylpyrrolidone/Vinyl acetate Luviskol ®, BASF/ ISP Vinylpyrrolidone/Vinylcaprolactam Luvitec ®, BASF Vinylpyrrolidone/Vinylimidazole Luvitec ®, BASF Vinylpyrrolidone/Vinylimidazolium methyl Luvitec ®, BASF sulfate Vinylpyrrolidone/Na methacrylate Luvitec ®, BASF Vinylpyrrolidone/olefins ISP ®, Antaron Vinylpyrrolidone/Dimethylaminoethyl ISP ® meth
• the agents according to the invention may contain other transition metal ions, such as ions of the elements zinc, manganese, cerium or vanadium, also hydrofluoric acid or free fluorides.
• transition metal ions such as ions of the elements zinc, manganese, cerium or vanadium
• hydrofluoric acid or free fluorides such as sodium, manganese, cerium or vanadium
• chromium ions or nickel ions may in principle also have advantages. However, for reasons of industrial safety and environmental protection, the addition of chromium ions or nickel ions is preferably avoided. Consequently, in a preferred embodiment of the invention, the agent is free from nickel and chromium. This means that these metals or compounds thereof are not intentionally added to the agent.
• the ready-to-use agent according to the invention has a pH preferably in the range of 1 to 6 and in particular in the range of 2 to 5.5.
• acid-soluble compounds of Zr, Ti, Hf or Si, as well as hydrofluoric acid or soluble fluorides may be added separately, as the fluoro anions of the above-mentioned elements can be formed from these.
• the pH has to be adjusted to the desired range by addition of acid, such as the free fluoric acids of the above-mentioned elements, but even, for example, hydrofluoric acid, sulfuric acid, nitric acid or phosphoric acid or by addition of a base, such as alkali metal carbonate solution, alkali metal hydroxide solution or ammonia.
• acid such as the free fluoric acids of the above-mentioned elements, but even, for example, hydrofluoric acid, sulfuric acid, nitric acid or phosphoric acid
• a base such as alkali metal carbonate solution, alkali metal hydroxide solution or ammonia.
• the agent according to the invention contains homo- or copolymers of vinylpyrrolidone containing caprolactam groups.
• a further aspect of the invention is a process for treating metal surfaces.
• the metal surfaces which, if desired, may already carry an anticorrosive layer, are contacted with the above-mentioned agent.
• the metal surfaces may be selected, for example, from surfaces made of steel, zinc-plated steel (electroplated or hot-dip galvanized), steel coated with zinc alloy, or of aluminum or magnesium.
• the metals aluminum and magnesium are generally not in pure form, but in the form of alloys with other elements, such as lithium, zinc, copper, silicon, magnesium (in the case of aluminum alloys) or aluminum (in the case of magnesium alloys).
• the process is envisaged in particular for the treatment of surfaces made of those metals which are used in the construction of vehicles, in the household appliance industry, or in the field of architecture or furnishings.
• those metal surfaces which as yet have no anticorrosive layer may be treated.
• the treatment process according to the invention then produces an anticorrosive coating, which at the same time improves the adhesion of an organic coating, such as a lacquer, optionally to be applied subsequently.
• those metal surfaces which already have a previously formed anticorrosive layer may also be treated by the process according to the invention. In this case, the anticorrosive action of this previously applied anticorrosive layer is further improved.
• the process according to the invention is suitable for the aftertreatment of metal surfaces which have an X-ray-amorphous or crystalline coating, such as are produced, for example, by a non-layer-forming or a layer-forming phosphating, for instance, a layer-forming zinc phosphating.
• the treatment according to the invention of such pretreated metal surfaces results in the closure of the pores remaining in the initial anticorrosive layer after the pretreatment.
• the metal surfaces may be contacted with the treatment solution, for example, by spraying or dipping.
• the treatment solution be rinsed off with water after a contact time, which may range, for example, from 30 seconds to 5 minutes.
• the treatment solution may be contacted with the metal surface in the so-called no-rinse process.
• the treatment solution is either sprayed onto the metal surface or transferred onto the surface by spreading rollers.
• a contact time which may range, for example, from 2 to 20 seconds
• the treatment solution is then dried without further intermediate rinsing. This may take place, for example, in a heated furnace.
• the treatment solution has a pH preferably in the range of 1 to 6.
• the pH is adjusted preferably to within the range of 2 to 6 for the treatment of bare metal surfaces; in particular to within the range of 2 to 4 for the treatment of aluminum surfaces and in particular to within the range of 3 to 5 for the treatment of steel, zinc or zinc-plated steel.
• Already pretreated metal surfaces having, for example, a phosphate layer, are preferably contacted with a treatment solution having a pH in the range of 3.5 to 5.
• the temperature of the treatment solution in the course of the process according to the invention may generally be between the freezing point and the boiling point of the treatment solution, temperatures in the region of room temperature or above being preferred for practical reasons.
• the temperature of the treatment solution may be within the range of 15 degrees C. to 60 degrees C. and in particular from 20 degrees C. to 45 degrees C.
• the treatment process according to the invention is one step in an otherwise conventional sequence of steps in the field concerned.
• the metal surfaces to be treated are usually cleaned using a conventional cleaning solution prior to the treatment according to the invention.
• the cleaning step may be omitted if, immediately before the treatment according to the invention, the metal surfaces to be treated are coated, for example, zinc-plated, or are subjected to a conversion treatment, for example, a phosphating.
• the metal surfaces are conventionally coated with an organic coating, for instance, a lacquer. This may be a powder coating, for example, or an electrolytically, especially cathodically, precipitable electrophoretic coating.
• a particularly preferred procedure in carrying out the process according to the invention involves treating the metal surface with an aqueous solution of an acid prior to its being contacted with the above-mentioned agent in order to produce a conversion layer, i.e., during a conversion treatment.
• the inserted processing step involving the treatment of the metal surface with an aqueous solution of an acid prior to the conversion treatment, is also referred to in the industry as “acid pickling” or “pickle passivation”. Acids which are conventionally used for acid pickling or pickle passivation can be employed for this purpose in the procedure according to the invention. An example of these is phosphoric acid.
• Hot-dip galvanized steel HDG
• electrolytically galvanized steel EG
• aluminum AC120
• cold-rolled steel CRS
• Galvanized substrates Coating adhesion after storage in salt water
• Aluminum Copper-accelerated salt spray test
• Steel Salt spray test SS DIN 50021, 21 days

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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)
• Preventing Corrosion Or Incrustation Of Metals (AREA)
• Application Of Or Painting With Fluid Materials (AREA)
• Paints Or Removers (AREA)

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• 2001
  • 2001-06-30 DE DE10131723A patent/DE10131723A1/de not_active Withdrawn
• 2002
  • 2002-06-21 RU RU2004102694/02A patent/RU2004102694A/ru not_active Application Discontinuation
  • 2002-06-21 AT AT02780906T patent/ATE294259T1/de not_active IP Right Cessation
  • 2002-06-21 MX MXPA03011369A patent/MXPA03011369A/es unknown
  • 2002-06-21 EP EP02780906A patent/EP1402083B1/de not_active Expired - Lifetime
  • 2002-06-21 CZ CZ20033572A patent/CZ20033572A3/cs unknown
  • 2002-06-21 WO PCT/EP2002/006888 patent/WO2003002781A1/de active IP Right Grant
  • 2002-06-21 BR BR0210725-2A patent/BR0210725A/pt not_active IP Right Cessation
  • 2002-06-21 JP JP2003508743A patent/JP2004533542A/ja active Pending
  • 2002-06-21 ES ES02780906T patent/ES2240824T3/es not_active Expired - Lifetime
  • 2002-06-21 DE DE50202924T patent/DE50202924D1/de not_active Expired - Fee Related
  • 2002-06-21 SK SK1619-2003A patent/SK16192003A3/sk unknown
  • 2002-06-21 CA CA002453138A patent/CA2453138A1/en not_active Abandoned
  • 2002-06-21 KR KR10-2003-7017270A patent/KR20040043135A/ko not_active Application Discontinuation
  • 2002-06-21 CN CNA028132149A patent/CN1527889A/zh active Pending
• 2003
  • 2003-12-11 US US10/734,815 patent/US20040151619A1/en not_active Abandoned

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