EP1484432B1 - Solution de traitement pour la formation d'un revetement chimique exempt de chrome hexavalent noir sur un substrat recouvert de zinc ou d'alliage de zinc, et procede de formation de revetement chimique exempt de chrome hexavalent noir sur un substrat recouvert de zinc ou d'alliage de zinc - Google Patents

Solution de traitement pour la formation d'un revetement chimique exempt de chrome hexavalent noir sur un substrat recouvert de zinc ou d'alliage de zinc, et procede de formation de revetement chimique exempt de chrome hexavalent noir sur un substrat recouvert de zinc ou d'alliage de zinc Download PDF

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Publication number
EP1484432B1
EP1484432B1 EP03708593A EP03708593A EP1484432B1 EP 1484432 B1 EP1484432 B1 EP 1484432B1 EP 03708593 A EP03708593 A EP 03708593A EP 03708593 A EP03708593 A EP 03708593A EP 1484432 B1 EP1484432 B1 EP 1484432B1
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Prior art keywords
zinc
processing solution
ions
hexavalent chromium
chromium
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EP1484432A1 (fr
EP1484432A4 (fr
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Manabu Dipsol Chemicals Co. Ltd. INOUE
Ryo Dipsol Chemicals Co. Ltd. NAKAJIMA
Kazuhiro Dipsol Chemicals Co. Ltd. WATANABE
Kimitaka Dipsol Chemicals Co. Ltd. WATANABE
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Dipsol Chemicals Co Ltd
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Dipsol Chemicals Co Ltd
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    • 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
    • C23C22/74—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 for obtaining burned-in conversion coatings
    • 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
    • C23C22/10—Orthophosphates containing oxidants
    • 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
    • C23C22/46—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 oxalates
    • 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
    • C23C22/46—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 oxalates
    • C23C22/47—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 oxalates 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
    • C23C22/48—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 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
    • C23C22/53—Treatment of zinc or alloys based thereon
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
    • C23C28/023—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material only coatings of metal elements only
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
    • C23C28/023—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material only coatings of metal elements only
    • C23C28/025—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material only coatings of metal elements only with at least one zinc-based layer
    • 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
    • C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
    • C23C2222/10—Use of solutions containing trivalent chromium but free of hexavalent chromium

Definitions

  • the present invention relates to a processing solution for forming a hexavalent chromium free, black conversion film on zinc or zinc alloy plating layers, and a method for forming the hexavalent chromium free, black conversion film on zinc or zinc alloy plating layers.
  • J.P. KOKOKU Japanese Examined Patent Publication
  • Sho 63-015991 discloses a method, which comprises the step of treating the surface of a metal with a bath containing a mixture of trivalent chromium and a fluoride, an organic acid, an inorganic acid and/or a metal salt such as cobalt sulfate.
  • a fluoride is used in this plating bath and therefore, a problem of environmental pollution would arise.
  • Hei 03-010714 discloses a method, which makes use of a plating bath comprising a mixture of trivalent chromium and an oxidizing agent, an organic acid, an inorganic acid and/or a metal salt such as a cerium salt.
  • this method makes use of an oxidizing agent and cerium and therefore, the trivalent chromium may possibly be oxidized into hexavalent chromium, during the processing and/or the storage of the bath.
  • J.P. KOKAI Japanese Un-Examined Patent Publication
  • No. Hei 10-183364 discloses a method which comprises the step of treating the surface of a metal with a bath containing a phosphoric acid, a salt of metal such as Mo, Cr 3+ and Ti, and an oxidizing agent to provide the surface with a hexavalent chromium free, corrosion resistant conversion film.
  • This method uses a large quantity of the oxidizing agent and therefore, the trivalent chromium may possibly be oxidized into a hexavalent chromium, during the processing and/or the storage of the bath.
  • J.P. KOKAI No. 2000-54157 discloses a method which comprises the step of chemical conversion treating the surface of a metal with a bath containing phosphorus, a metal such as Mo, and trivalent chromium, but no fluoride.
  • a metal such as Mo
  • trivalent chromium but no fluoride.
  • J.P. KOKAI No. 2000-509434 discloses a method, which comprises the step of treating the surface of a metal using a plating bath comprising 5 to 100 g/L of trivalent chromium and nitrate residues, an organic acid and/or a metal salt such as a cobalt salt.
  • This method uses, for instance, trivalent chromium in a high concentration and the plating operation is carried out at a high temperature. Therefore, this method is advantageous in that it can form a thick film and ensure good corrosion resistance.
  • the method suffers from a problem in that it is difficult to stably form a dense film and that the method cannot ensure the stable corrosion resistance of the resulting film.
  • the processing bath contains trivalent chromium in a high concentration and also contains a large amount of an organic acid. This makes the post-treatment of the waste water difficult and results in the formation of a vast quantity of sludge after the processing.
  • the method suffers from a serious problem in that it may give a new burden to the environment such that the method generates a vast quantity of waste.
  • U.S. Patent No. 5415702 discloses a method which comprises the step of treating the surface of a metal with an acidic bath containing a phosphate compound and trivalent chromium. Also, with regard to a chemical conversion interference color film containing a trivalent chromium on zinc-nickel alloy plating layers (containing 8% or more of nickel in the layers), U.S. Patent No.
  • 5407749 discloses a method, which comprises the step of treating the surface of a metal with an acidic bath similar to that disclosed in U.S. Patent No. 5415702 containing a phosphorus compound, trivalent chromium and oxy-halogen acid ions.
  • a Ni eutectoid rate in zinc-nickel alloy plating layers actually produced is less than 8%, and thus it is difficult to obtain a black feature from a practical standpoint. Furthermore, the black conversion film on zinc-iron alloy plating layers does not have enough corrosion resistivity.
  • Another object of the present invention is to provide a method for forming such a hexavalent chromium free, black conversion film.
  • the present invention has been completed on the basis of such finding that the foregoing problems associated with the conventional techniques can effectively be solved by depositing a zinc or zinc alloy plating layer(s) on a substrate and then subjecting the plating layer to a trivalent chromate treatment using a processing solution having a specific composition, i.e. containing a low concentration of nitrate ions, cobalt ions and nickel ions.
  • a processing solution for forming a hexavalent chromium free, black conversion film on zinc or zinc alloy plating layers comprises:
  • a method for forming a hexavalent chromium free, black conversion film which comprises the step of bringing zinc or zinc alloy plating into contact with the foregoing processing solution.
  • the substrates used in the present invention may be a variety of metals such as iron, nickel and copper, alloys thereof and metals or alloys such as aluminum, which have been subjected to zincate treatment and the substrate may have a variety of shapes such as plate-like, rectangular prism-like, column-like, cylindrical and spherical shapes.
  • the foregoing substrate is plated with zinc or a zinc alloy according to the usual method.
  • the zinc-plating layer may be deposited on the substrate using either, for instance, acidic baths such as a sulfuric acid bath, an ammonium chloride bath or a potassium chloride bath, and alkaline baths such as an alkaline non-cyanide bath and an alkaline cyanide bath, but an alkaline non-cyanide bath (NZ-98 available from Dipsol Chemicals Co., Ltd.) is preferable.
  • examples of zinc alloy plating are zinc-iron alloy plating, zinc-nickel alloy plating having a rate of nickel-co-deposition ranging from 5 to 20% by mass, zinc-cobalt alloy plating and tin-zinc alloy plating.
  • the thickness of the zinc or zinc alloy plating to be deposited on the substrate may arbitrarily be selected, but it is desirably not less than 1 ⁇ m and preferably 5 to 25 ⁇ m.
  • the plated substrate is water-rinsed or subjected to nitrate activation processing after being water-rinsed, and then brought into contact with a processing solution for forming a hexavalent chromium free, black conversion film according to the present invention.
  • a processing solution for forming a hexavalent chromium free, black conversion film for instance, the zinc or zinc alloy plating subjected to a dipping treatment using this processing solution.
  • the source of the trivalent chromium may be any chromium compound containing trivalent chromium, but preferred examples thereof usable herein are trivalent chromium salts such as chromium chloride, chromium sulfate, chromium nitrate, chromium phosphate and chromium acetate or it is also possible to reduce hexavalent chromium such as chromic acid or dichromic acid into trivalent chromium using a reducing agent.
  • Particularly preferable trivalent chromium source is chromium phosphate (Cr(H n PO 4 ) (3/3 ⁇ n)) ).
  • trivalent chromium may be used alone or in any combination of at least two of them.
  • the trivalent chromium concentration in the processing solution is not limited. It is preferably as low as possible from the viewpoint of the easiness of the wastewater treatment, but it is preferably 0.5 to 10 g/L and most preferably 0.8 to 5 g/L, while taking into account the corrosion resistance.
  • the use of trivalent chromium in such a low concentration falling within the range specified above is also quite advantageous from the viewpoint of the wastewater treatment and the processing cost.
  • the processing solution of the present invention comprises nitrate ions in a mole ratio of nitrate ions to a trivalent chromium (NO 3- /Cr 3+ ) of less than 0.5/1, and preferably in a range of from 0.02/1 to 0.25/1.
  • the nitrate ion concentration in the processing solution preferably ranges from 0.1 to 1 g/L.
  • the nitrate ion source include nitric acid or a salt thereof.
  • the chelating agent used in the processing solution of the present invention examples include a hydroxycarboxylic acid such as tartaric acid and malic acid, a monocarboxylic acid, a polyvalent carboxylic acid such as a dicarboxylic acid such as oxalic acid, malonic acid, succinic acid, citric acid and adipic acid, or a tricarboxylic acid, aminocarboxylic acid such as glysinic acid.
  • the chelating agent may be used alone or in any combination of at least two of these acids or salts thereof (e.g. salt of sodium, potassium, ammonium or the like).
  • the chelating agent concentration in the processing solution preferably ranges from 1 to 40 g/L, and more preferably 5 to 35 g/L in total.
  • the molar ratio of the chelating agent to the trivalent chromium (the chelating agent / Cr 3+ ) present in the processing solution of the present invention preferably ranges from 0.2 / 1 to 4/1 and more preferably 1/1 to 4 /1.
  • the processing solution of the present invention comprises cobalt ions and / or nickel ions.
  • the sources of the cobalt ions and / or nickel ions there may be used any metallic compounds containing either of these metals.
  • One of these metallic compounds or any combination of at least two of them may be used, but one or more of each of metal salt, cobalt and nickel, is preferably used.
  • the metallic salt concentration in the processing solution preferably ranges from 0.1 to 2 g/L, and more preferably 0.5 to 1.5 g/L in total.
  • the processing solution of the present invention may comprise monovalent to hexavalent metal ions, for example silicon, iron, titan, zirconium, tungsten, vanadium, molybdenum, strontium, niobium, tantalum, manganese, calcium, barium, magnesium, aluminum and the like.
  • Said metal ions may be added alone or in any combination of at least two of them to the processing solution of the present invention.
  • the sources of said metal ions there may be used any metallic compounds containing either of these metals, but nitrate, sulfate or chloride are preferably used. These metallic compounds may be used alone or in any combination of at least two of them.
  • the concentration in the processing solution preferably ranges from 0.05 to 3.0 g/L, and more preferably 0.1 to 2.0 g/L in total.
  • the trivalent chromium and a chelating agent such as oxalic acid should be present in the processing solution in the form of a stable water-soluble complex formed therebetween, which is supposed to have a structure represented by the following general formula, while the metal ions such as cobalt ions should stably exist in the solution without causing any precipitation by forming a hardly soluble metal salt with the chelating agent.
  • [(Cr) 1 • (A) m ] +3l-mn wherein A represents a chelating agent, and n represents a valence of the chelating agent.
  • the molar ratio of the chelating agent to the trivalent chromium (m/l) in the processing solution of the present invention preferably ranges from 0.2/1 to 4/1.
  • the sources of phosphate ions include oxyacid of phosphorus such as phosphoric acid or phosphorous acid and a salt thereof. One of these sources or any combination of at least two of them may be used.
  • the concentration of phosphate ions in the processing solution preferably ranges from 0.1 to 50 g/L, and more preferably 5 to 25 g/L.
  • sulfate ions may be added to the foregoing processing solution.
  • sources of these ions include sulfuric acid, hydrochloric acid, boric acid and an inorganic salt thereof and the like.
  • concentration of ions of these inorganic acids in the processing solution preferably ranges from 1 to 50 g/L, and more preferably 1 to 20 g/L in total.
  • the pH value of the processing solution of the present invention is preferably adjusted to the range of 0.5 to 4 and more preferably 2 to 3.
  • ions of the foregoing inorganic acids or an alkaline agent such as an alkali hydroxide or aqueous ammonia in order to adjust the pH value thereof to the range specified above.
  • the rest (balance) of the processing solution used in the present invention is water.
  • the method for bringing the zinc or zinc alloy plating into contact with the foregoing processing solution it is usual to immerse an article plated with zinc or zinc alloy in the foregoing processing solution.
  • an article is immersed in the solution maintained at a temperature ranging from 10 to 80°C and more preferably 40 to 60°C for preferably 5 to 600 seconds and more preferably 30 to 120 seconds.
  • the subject to be treated may be immersed in a dilute nitric acid solution in order to activate the surface of the zinc or zinc alloy plating layers, before it is subjected to the trivalent chromate treatment.
  • aging treatment heat treatment
  • the aging treatment is conducted at 100 to 250°C for 10 to 300 minutes, preferably at 150 to 200°C for 10 to 300 minutes, and more preferably at 200°C for 4 hours.
  • a topcoat film may be applied onto the hexavalent chromium free, black conversion film and this would permit the further improvement of the corrosion resistance of the film.
  • this is a quite effective means for imparting more excellent corrosion resistance to the film.
  • the zinc or zinc alloy plating is first subjected to the foregoing trivalent chromate treatment, followed by washing the plating with water, subjecting the plating to immersion or electrolyzation in a topcoating solution and then drying the processed article.
  • the article is subjected to immersion or electrolyzation in a topcoating solution after the trivalent chromate treatment and the subsequent drying treatment, and then dried.
  • topcoat effectively used herein means not only an inorganic film of, for instance, a silicate or a phosphoric acid salt, but also an organic film of, for instance, polyethylene, polyvinyl chloride, polystyrene, polypropylene, methacrylic resin, polycarbonate, polyamide, polyacetal, fluorine plastic, urea resin, phenolic resin, unsaturated polyester resin, polyurethane, alkyd resin, epoxy resin or melamine resin.
  • topcoating liquids for forming such an topcoat film usable herein may be, for instance, DIPCOAT W or CC445 available from Dipsol Chemicals Co., Ltd..
  • the thickness of the topcoat film may arbitrarily be selected, but it desirably ranges from 0.1 to 30 ⁇ m.
  • reaction mechanism of the hexavalent chromium free, black conversion film-formation according to the present invention can be supposed to be as follows:
  • the black conversion film is a composite film of (iii), (iv) and (v).
  • Cr 3+ sources used were CrCl 3 (in Examples 1, 2, 3 and 5), CrPO 4 (in Examples 4 and 6) and Cr(NO 3 ) 3 (in Example 5).
  • the concentrations of NO 3. were adjusted by Cr(NO 3 ) 3 (in Example 5) or by adding HNO 3 (in Examples 1, 2 and 3) or NaNO 3 (in Examples 4 and 6).
  • the SO 4 2- source used was Na 2 SO 4 and the PO 4 3- source used was NaH 2 PO 4 .
  • the balance of each processing solution was water.
  • the metallic salts used such as Co and Ni were its sulfate (in Examples 1, 4 and 6) and chloride (in Examples 2, 3 and 5).
  • the Si source used was colloidal silica and the Ti source used was titanium trichloride.
  • the concentration of metal ions other than Co and Ni was 1g/L.
  • the pH value of each solution was adjusted using NaOH.
  • the Cr 3+ sources used were CrCl 3 (in Example 8) and CrPO 4 (in Examples 7, 9 and 10).
  • the concentrations of NO 3 were adjusted by adding HNO 3 (in Example 8) or_NaNO 3 (in Examples 7, 9 and 10). Further, the SO 4 2- source used was Na 2 SO 4 and the PO 4 3- source used was NaH 2 PO 4 . The balance of each processing solution was water. The metal salts used such as Co and Ni were its sulfate (in Examples 7 and 9) and chloride (in Example 8). The Si source used was colloidal silica and the concentration thereof was 1g/L. The pH value of each solution was adjusted using NaOH.
  • the hexavalent chromate bath used herein was ZB-535A (200 mL/L) and ZB-535B (10 mL/L) available from Dipsol Chemicals Co., Ltd.
  • the processing was carried out at 30°C for 40 seconds.
  • the present invention permits the formation of a hexavalent chromium free, black conversion film directly on zinc or zinc alloy plating layers.
  • the plated article obtained according to this method has not only the corrosion resistance due to the zinc or zinc alloy plating as such, but also the excellent corrosion resistance due to the presence of the trivalent chromate film.
  • the processing solution used in the present invention comprises trivalent chromium in a low concentration and therefore, the present invention is quite advantageous from the viewpoint of the wastewater treatment and production and processing cost.
  • the film obtained by directly forming trivalent chromate on the plating possesses not only corrosion resistance, resistance to salt water and after heating resistance identical or superior to those observed for the conventional hexavalent chromium-containing film, but also expresses a black feature, and therefore, the film of the present invention can widely be used in a variety of fields in the future.

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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Paints Or Removers (AREA)

Claims (13)

  1. Solution de traitement pour la formation d'un film de conversion noir exempt de chrome hexavalent sur une/des couche (s) de placage au zinc ou en alliage de zinc, la solution de traitement comprenant :
    des ions nitrate et du chrome trivalent en un rapport molaire (NO3/Cr3+) inférieur à 0,5/1, où le chrome trivalent est présent sous la forme d'un complexe soluble dans l'eau avec un chélateur ; et
    des ions cobalt et/ou des ions nickel, où les ions cobalt et/ou les ions nickel sont présents de manière stable dans la solution de traitement sans entraîner de précipitation en formant un sel métallique à peine soluble avec le chélateur ; où la solution réagit avec du zinc lorsqu'elle est mise en contact avec le placage de zinc ou en alliage de zinc pour former un film de conversion noir exempt de chrome hexavalent contenant du zinc, du chrome, du cobalt et/ou du nickel, et le chélateur sur la/les couche(s) de placage.
  2. Solution de traitement selon la revendication 1 où la concentration de chrome trivalent se trouve dans la plage de 0,5 à 10 g/L et un rapport molaire du chélateur rapporté au chrome trivalent (le chélateur/Cr3+) se trouve dans la plage de 0,2/1 à 4/1.
  3. Solution de traitement selon la revendication 1 ou 2 où la source de chrome trivalent est du phosphate de chrome (Cr(HnPO4)3/(3-n))).
  4. Solution de traitement selon l'une quelconque des revendications 1 à 3 où le chélateur est un élément ou plusieurs éléments sélectionnés du groupe constitué d'acides monocarboxyliques, d'acides dicarboxyliques; d'acides tricarboxyliques, d'acides hydrocarboxyliques, d'acides aminocarboxyliques et de leurs sels.
  5. Solution de traitement selon l'une quelconque des revendications 1 à 4 où le chélateur est un élément ou plusieurs éléments sélectionnés du groupe constitué d'acide oxalique, d'acide malonique, d'acide succinique et de leur sel.
  6. Solution de traitement selon l'une quelconque des revendications 1 à 5 qui comprend en outre un ou plusieurs ions métalliques sélectionnés du groupe constitué de silicium, de fer, de titane, de zirconium, de tungstène, de vanadium, de molybdène, de strontium, de niobium, de tantale, de manganèse, de calcium, de baryum, de magnésium et d'aluminium.
  7. Solution de traitement selon l'une quelconque des revendications 1 à 6 où la concentration en ions nitrate se trouve dans la plage de 0,1 à 1 g/L.
  8. Solution de traitement selon l'une quelconque des revendications 1 à 7, qui comprend en outre des ions phosphate.
  9. Solution de traitement selon l'une quelconque des revendications 1 à 8, qui comprend en outre un ou plusieurs ions sélectionnés du groupe constitué d'un ion sulfate, d'un ion halogène et d'un ion borate.
  10. Procédé de formation d'un film de conversion noir exempt de chrome hexavalent, qui comprend l'étape consistant à mettre en contact une/des couche(s) de placage au zinc ou en alliage de zinc avec la solution de traitement de l'une quelconque des revendications 1 à 9.
  11. Procédé selon la revendication 10, qui comprend en outre l'étape consistant à soumettre un film de conversion noir exempt de chrome hexavalent à un traitement de vieillissement à 100 jusqu'à 250°C pendant 30 à 300 minutes.
  12. Procédé selon la revendication 11 où le traitement de vieillissement est appliqué à 200°C pendant 60 à 300 minutes.
  13. Procédé de protection contre la rouille d'un placage au zinc ou en alliage de zinc, qui comprend l'étape consistant à soumettre un film de conversion noir exempt de chrome hexavalent formé par le procédé selon l'une quelconque des revendications 10 à 12 à un traitement de revêtement.
EP03708593A 2002-03-14 2003-03-13 Solution de traitement pour la formation d'un revetement chimique exempt de chrome hexavalent noir sur un substrat recouvert de zinc ou d'alliage de zinc, et procede de formation de revetement chimique exempt de chrome hexavalent noir sur un substrat recouvert de zinc ou d'alliage de zinc Expired - Lifetime EP1484432B1 (fr)

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JP2002070175 2002-03-14
JP2002070175A JP3774415B2 (ja) 2002-03-14 2002-03-14 亜鉛及び亜鉛合金めっき上に黒色の六価クロムフリー化成皮膜を形成するための処理溶液及び亜鉛及び亜鉛合金めっき上に黒色の六価クロムフリー化成皮膜を形成する方法。
PCT/JP2003/002994 WO2003076686A1 (fr) 2002-03-14 2003-03-13 Solution de traitement pour la formation d'un revetement chimique exempt de chrome hexavalent noir sur un substrat recouvert de zinc ou d'alliage de zinc, et procede de formation de revetement chimique exempt de chrome hexavalent noir sur un substrat recouvert de zinc ou d'alliage de zinc

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AU (1) AU2003213350A1 (fr)
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EP1484432A4 (fr) 2009-12-30
JP3774415B2 (ja) 2006-05-17
AU2003213350A1 (en) 2003-09-22
KR20040101294A (ko) 2004-12-02
WO2003076686A1 (fr) 2003-09-18
KR100627029B1 (ko) 2006-09-21
ATE478976T1 (de) 2010-09-15
JP2003268562A (ja) 2003-09-25
CN100457969C (zh) 2009-02-04
CN1729311A (zh) 2006-02-01
DE60333904D1 (de) 2010-10-07

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