EP1571237B1 - Fluide de traitement pour traitement de surface de métal et procédé de traitement de surface - Google Patents

Fluide de traitement pour traitement de surface de métal et procédé de traitement de surface Download PDF

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Publication number
EP1571237B1
EP1571237B1 EP03780727.8A EP03780727A EP1571237B1 EP 1571237 B1 EP1571237 B1 EP 1571237B1 EP 03780727 A EP03780727 A EP 03780727A EP 1571237 B1 EP1571237 B1 EP 1571237B1
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Prior art keywords
surface treatment
compound
metal
ppm
treating solution
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EP03780727.8A
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German (de)
English (en)
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EP1571237A4 (fr
EP1571237A1 (fr
Inventor
Takaomi Nihon Parkerizing Co. Ltd. NAKAYAMA
Hiroyuki Nihon Parkerizing Co. Ltd. SATO
Toshiyuki Nihon Parkerizing Co. Ltd. AISHIMA
Eisaku Toyota Jidosha Kabushiki Kaisha OKADA
Fumiya Daihatsu Motor Co. Ltd. YOSHIDA
Katsuhiro Daihatsu Motor Co. Ltd. SHIOTA
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Nihon Parkerizing Co Ltd
Toyota Motor Corp
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Nihon Parkerizing Co Ltd
Toyota Motor Corp
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Publication of EP1571237A4 publication Critical patent/EP1571237A4/fr
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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
    • C23C22/05—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
    • C23C22/40—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 molybdates, tungstates or vanadates
    • C23C22/44—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 molybdates, tungstates or vanadates containing also 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
    • C23C22/73—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
    • C23C22/76—Applying the liquid by spraying
    • 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
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D9/00—Electrolytic coating other than with metals
    • C25D9/04—Electrolytic coating other than with metals with inorganic materials
    • C25D9/08—Electrolytic coating other than with metals with inorganic materials by cathodic processes

Definitions

  • the present invention relates to a method of surface treatment of metal comprising contacting simultaneously with a treating solution for surface treatment of metal which may deposit a surface treated film having excellent corrosion resistance after being coated on the surface of a metal material of a structural construction such as car body consisting of two or more metal materials selected from the group, consisting of ferriferous material, zinciferous material, aluminiferous material and magnesiferous material in the condition being joined by welding or riveting.
  • a zinc phosphate treatment and a chromate treatment are currently used as ordinary methods.
  • the zinc phosphate treatment it is possible to deposit a film having excellent corrosion resistance on the surface of steel such as cold rolled steel plate, zinc plated steel plate and some of aluminum alloys.
  • the generation of sludge, which is the byproduct of the reaction can not be avoided, and depending on the kind of aluminum alloy, the sufficient corrosion resistance after coated can not be obtained.
  • the chromate treatment which contains harmful hexavalent chrome in the treating solution is more likely to be avoided.
  • various methods have been proposed as described below.
  • JP 2000-204485 A a compound containing nitrogen atom having a lone electron-pair and a non-chrome coating agent for metal surface treatment containing said compound and zirconium compound are suggested.
  • This method may obtain a surface treated film which is excellent in corrosion resistance and adhesiveness after being coated, and yet does not contain harmful hexavalent chrome by coating above mentioned coating agent.
  • the metal material which can be treated is limited to aluminum alloys only, and, it is difficult to be applied to a structural construction having complex structure such as car body, because the surface treated film is formed by coating and drying.
  • metal materials to be treated may include magnesium, magnesium alloy, zinc and zinc plated alloy other than aluminum alloy.
  • a method for metal surface treatment by chrome free coating acid composition by coating aqueous solution containing component which can be a film having excellent corrosion resistance over the surface of metal, then baking and drying without rinsing with water so as the film to be fixed (see JP 5-195244 A ).
  • This method does not involve any chemical reaction to form a film, so this method may form a film on the surface of metal such as zinc plated steel plate, cold rolled steel plate or aluminum alloy.
  • JP 2000-204485 A since the film is formed by coating and drying, it is difficult to form a uniform film on the surface of a structural construction having complex structure such as car body.
  • GB 2 165 165 A , US 4,457,790 A , US 5,380,374 A , EP 0 411 609 A2 , US 4,338,140 A , EP 0 337 075 A2 , EP 0 411 606 A2 , EP 0 774 535 A1 , and EP 1 405 933 A1 (which is a document under Article 54(3) EPC) describe a treating solution for surface treatment of metal and/or a method for surface treatment of metal.
  • the object of the present invention is to provide a method for surface treatment of metal using a treating solution for surface treatment of metal to form a surface treated film having excellent corrosion resistance after coated on the surface of ferriferous material, zinciferous material, aluminiferous material and magnesiferous material, which does not contain harmful component to the environment and does not generate sludge to be wasted, which was not accomplished by the prior arts.
  • the object of the present invention is to provide a method for surface treatment of metal using a treating solution for metal surface treatment to form a surface treated film of a uniform component having excellent corrosion resistance after coated on the surface of a metal material composing a structural construction such as car body consisting of two to four materials selecting from the group consisting of ferriferous material, zinciferous material, aluminiferous material and magnesiferous material by same component simultaneously under a uniform condition.
  • the inventors of the present invention have conducted intensive study to solve the above mentioned problem and have accomplished a method of surface treatment of metal using a treating solution for surface treatment of metal and a method for surface treatment which were not provided by the prior art.
  • the treating solution used in the method for surface treatment of metal contains 5 to 5000 ppm of at least one compound selected from the group consisting of zirconium compound and titanium compound calculated as metal element, at least one compound selected from the group consisting of calcium compound, magnesium compound and strontium compound, wherein concentration of the compound calculated as metal element is 5 to 100 ppm in the case of the calcium compound, 10 to 5000 ppm in the case of the magnesium compound and 10 to 5000 ppm in the case of the strontium compound and 0.1 to 100 ppm of free fluorine ion, and has a pH of 2 to 6. It is desirable that the treating solution for surface treatment of metal further contains 1000 to 50000 ppm of nitrate group.
  • the treating solution for surface treatment of metal further contains at least one oxygen acid and/or salt of oxygen acid selected from the group consisting of HClO 3 , HBrO 3 , HNO 2 , HNO 3 , HMnO 4 , HVO 3 , H 2 O 2 , H 2 WO 4 , H 2 MoO 4 and salts thereof.
  • the treating solution for surface treatment of metal may further contain at least one polymer compound selected from the group consisting of water soluble polymer compounds and water dispersible polymer compounds, and may further contain at least one surface active agent selected from the group consisting of nonionic surface active agents, anionic surface active agents and cationic surface active agents.
  • the present invention is the method for surface treatment of metal according to claim 8.
  • the method for surface treatment after electrolytic treating in the treating solution for surface treatment, it is possible to further contact the two or more metal materials with acidic aqueous solution of compound containing at least one element selected from the group consisting of cobalt, nickel, tin, copper, titanium and zirconium, with or without washing by water, or it is possible to further contact the two or more metal materials with treating solution containing at least one polymer compound selected from water soluble polymer compounds and water dispersible polymer compounds, with or without washing by water.
  • the present invention is the method for surface treatment of metal according to claim 5, wherein the contacting step comprises contacting the two or more metal materials whose surfaces are not degreased and cleaned.
  • the treating solution for surface treatment contains at least one surface active agent selected from the group consisting of the above described nonionic surface active agents, anionic surface active agents and cationic surface active agents.
  • the methods of the present invention can be used to provide a metal material having a surface treated film containing at least one metal element selected from the group consisting of titanium and zirconium formed on a surface of iron metal material by the method for surface treatment, wherein an adhesion amount of the surface treated film calculated as the metal element is 30 mg/m 2 or more; in the case where formed on a surface of zinc metal material, an adhesion amount of the surface treated film calculated as the metal element is 20mg/m 2 or more; in the case where formed on a surface of aluminum metal material, an adhesion amount of the surface treated film calculated as the metal element is 10mg/m 2 or more; and in the case where formed on a surface of magnesium metal material, an adhesion amount of the surface treated film calculated as the metal element is 10mg/m 2 or more.
  • the present invention relates to the art characterizing to deposit a surface treated film having excellent corrosion resistance after coated, by surface treatment on simultaneously two or more metal materials selected from the group consisting of ferriferous material, zinciferous material, aluminiferous material and magnesiferous material.
  • ferriferous material is an iron metal such as cold rolled steel plate, hot rolled steel plate, cast iron or sintered steel.
  • Zinciferous material is a die casting zinc or a zinc containing plating.
  • This zinc containing plating means a metal plating with zinc or zinc alloy composed of zinc and other metals (for example, at least one metal selected from the group consisting of nickel, iron, aluminum, manganese, chromium, magnesium, cobalt, lead or antimony) and inevitable impurities, and the methods for such plating includes hot galvanizing, electric plating and vapor deposition plating, and are not limited to these methods.
  • the aluminiferous material is an aluminum alloy board such as JIS 5000 series aluminum alloy or JIS 6000 series aluminum alloy, or an aluminum alloy die cast represented by ADC-12. Still more, the magnesiferous material is a metal board or a die cast made of magnesium alloy.
  • the present invention can be applied to the structural construction which contains two to four metal materials mentioned above in the composing parts, and it is possible to treat the surfaces of two to four metal materials at the same time.
  • the different metals are in the condition being joined and contacted by means of joining method which is welding or riveting. Another joining method disclosed herein is adhesion.
  • the treating solution for surface treatment of metal used in the present invention contains 5 to 5000 ppm of at least one compound selected from the group consisting of zirconium compound and titanium compound calculated as the metal element.
  • zirconium compound used in the present invention ZrCl 4 , ZrOCl 2 , Zr(SO 4 ) 2 , ZrOSO 4 , Zr(NO 3 ) 4 , ZrO(NO 3 ) 2 , H 2 ZrF 6 , salt of H 2 ZrF 6 , ZrO 2 , ZrOBr 2 and ZrF 4 can be mentioned.
  • titanium compound TiCl 4 , Ti(SO 4 ) 2 , TiOSO 4 , Ti(NO 3 ) 4 , TiO(NO 3 ) 2 , TiO 2 OC 2 O 4 , H 2 TiF 6 , salt of H 2 TiF 6 , TiO 2 and TiF 4 can be mentioned.
  • zirconium compound is desirably used.
  • the concentration of at least one compound selected from the group consisting of zirconium compound and titanium compound is 5 to 5000 ppm calculated as the metal element (that is, as zirconium and/or titanium), and the more desirable concentration is 10 to 3000 ppm.
  • the film obtained by using the treating solution for surface treatment of metal in the method for surface treatment of the present invention is oxide or hydroxide of zirconium or titanium. Therefore, when the concentration of the compound selected from the group consisting of zirconium compound and titanium compound calculated as zirconium and/or titanium is smaller than 5 ppm, it is difficult to obtain sufficient adhesion amount to attain corrosion resistance in a practical period of time for treating, because the concentration of main component of film is too low. On the contrary, when the concentration is larger than 5000 ppm, the sufficient adhesion amount can be obtained, but it is not effective to improve the corrosion resistance and is disadvantageous from the economical view point.
  • the zirconium compound and the titanium compound can be easily dissolved in the acidic solution, but are not stable in the alkaline solution, and easily deposit as the oxide or the hydroxide of zirconium or titanium.
  • the pH of the treating solution for surface treatment of metal of the present invention is pH 2 to 6, more desirably pH 3 to 6.
  • the dissolving reaction of the metal material to be treated occurs.
  • the pH becomes higher at the surface of the metal material to be treated, and the oxide or the hydroxide of zirconium or titanium deposits as a film on the surface of the metal material to be treated.
  • the treating solution for surface treatment of metal of the present invention has free fluorine ion existing therein.
  • the fluorine compound is added into the treating solution for surface treatment of metal.
  • hydrofluoric acid, H 2 ZrF 6 and salt of H 2 ZrF 6 , H 2 TiF 6 , salt of H 2 TiF 6 , H 2 SiF 6 , salt of H 2 SiF 6 , HBF 4 and salt of HBF 4 , NaHF 2 , KHF 2 , NH 4 HF 2 , NaF, KF and NH 4 F can be mentioned.
  • the free fluorine ion has an effect to improve the stability of the zirconium compound and the titanium compound in the treating solution for surface treatment of metal. Further, the free fluorine ion has the function to promote the dissolving reaction of any of ferriferous material, zinciferous material, aluminiferous material and magnesiferous material which are the metal materials to be surface treated in the present invention. Therefore, by allowing free fluorine ion to exist therein by adding fluorine compound, the stability of the treating solution for surface treatment of metal of the present invention is improved, and further the reactivity to the metal material to be treated can be improved.
  • composition for surface treatment and treating solution for surface treatment of metal containing at least one of iron and zinc in WO02/103080 as follows. That is, the composition for surface treatment and treating solution for surface treatment of metal use titanium compound or zirconium compound and fluorine containing compound, wherein the ratio A/B is set within the specific range from 0.06 to 0.18, where A refers to the total mole weight of metal elements in the composition for surface treatment and treating solution for surface treatment of metal and B refers to the mole weight which when total fluorine atom in fluorine containing compound is calculated as HF.
  • the present invention it is possible to perform surface treatment on simultaneously two or more metal materials selected from the group consisting of ferriferous material, zinciferous material, aluminiferous material and magnesiferous material, even if out of above mentioned specific range of the ratio, by regulating the concentration of metal element in the titanium compound and zirconium compound, pH and the concentration of free fluorine ion.
  • the concentration of free fluorine ion means the concentration of fluorine ion measured by an ion electrode which is on the market.
  • the concentration of free fluorine ion in the treating solution for surface treatment of metal used in the method of the present invention is 0.1 to 100 ppm, and more desirably 2 to 70 ppm. In the case where the concentration of free fluorine ion is higher than 100 ppm, the dissolving reaction of the metal material to be treated is promoted.
  • zirconium compound and titanium compound in the treating solution for surface treatment of metal are very stable, even if the pH of the surface of metal material to be treated increases, it becomes difficult to deposit as a film.
  • the concentration of free fluorine ion is lower than 0.1 ppm, the effect for the improvement of the stability of the treating solution for surface treatment of metal and the reactivity thereof is small, and thus, it is no longer advantageous for the treating solution to contain free fluorine ion.
  • the free fluorine ion of the present invention has a role to keep the eluted component by dissolution of the metal material to be treated stable in the treating solution for surface treatment of metal.
  • sludge generates, because, for example, iron ion eluted from iron metal material reacts with phosphoric acid and forms iron phosphate which is an insoluble salt.
  • the treating solution for surface treatment of metal of the present invention may also contain phosphoric acid group, but, if the concentration of phosphoric acid group excesses 1.0g/L, sludge can be generated.
  • one or more compounds selected from the group, for example, consisting of inorganic acid such as sulfuric acid or hydrochloric; organic acid such as acetic acid, oxalic acid, tartaric acid, citric acid, succinic acid, gluconic acid or phthalic acid; and chelating agent which can chelete eluted component, may be added in the treating solution to thereby solubilize the eluted component.
  • the treating solution for surface treatment of metal used in the method of surface treatment of the present invention contains at least one compound selected from the group consisting of calcium compound, magnesium compound and strontium compound.
  • the present invention realizes to perform surface treatment on two or more materials simultaneously selected from the group consisting of ferriferous material, zinciferous material, aluminiferous material and magnesiferous material by regulating the concentration of free fluorine ion in the aqueous solution containing zirconium compound and titanium compound of specific concentration within the specified range.
  • the metal elements (calcium, magnesium or strontium) contained in above mentioned calcium compound, magnesium compound or strontium compound have a function to maintain the concentration of free fluorine ion in aqueous solution to a certain value by generating salt of fluorine and fluorinated compound in the aqueous solution. Due to the function, when the surface of various kinds of metal materials are treated at the same time, the optimum deposit amount of film can be obtained on each metal material to be treated, because certain concentration of free fluorine ion can be maintained regardless of the ratio among the materials used.
  • calcium compound, magnesium compound or strontium compound which can be used in the present invention for example, oxide, hydroxide, chloride, sulfate, nitrate and carbonate of these metal elements can be mentioned. Further, besides calcium compound, magnesium compound and strontium compound, the compound which has a function to maintain the concentration of free fluorine ion constant can be used regardless of whether an organic compound or an inorganic compound.
  • the concentration of the magnesium compound or the strontium compound which are used in the method of surface treatment of the present invention is 10 to 5000 ppm as the metal element, and more desirably is 100 to 3000 ppm.
  • the concentration as calcium is 5 to 100 ppm and more desirable concentration is 5 to 50 ppm, because the solubility of calcium is remarkably small.
  • the concentration of these compounds is higher than the upper limit, the stability of the treating solution for surface treatment of metal may decrease, and the continuous treatment is interrupted. And, when the concentration of these compounds is lower than the lower limit, the deposit amount of film particularly on ferriferous material decreases.
  • Nitric acid group acts as an oxidizing agent, and has a function to promote film depositing reaction of the present invention and a function to improve the solubility of above mentioned calcium compound, magnesium compound or strontium compound in the treating solution for surface treatment of metal. Therefore, even if the concentration of nitric acid group is lower than 1000 ppm, the film having excellent corrosion resistance can be deposited. However, in the case where the concentration of above mentioned calcium compound, magnesium compound or strontium compound is high, the stability of the treating solution for surface treatment of metal may decrease. The concentration of nitric acid group of 50000 ppm is sufficient, and it is disadvantageous to add more nitric acid group from the economical view point.
  • At least one oxygen acid and/or salt of oxygen acid selected from the group consisting of HClO 3 , HBrO 3 , HNO 3 , HNO 2 , HMnO 4 , HVO 3 , H 2 O 2 , H 2 WO 4 , H 2 MoO 4 .
  • Oxygen acid or salt thereof acts as oxidizing agent to the materials to be treated, and promotes the film forming reaction in the present invention.
  • the concentration of these oxygen acid or salts thereof to be added is not restricted, but adding an amount to 10 to 5000 ppm exhibits sufficient effect as the oxidizing agent.
  • At least one polymer compound selected from the group consisting of water soluble polymer compounds and water dispersible polymer compounds may be added.
  • the metal element whose surface is treated by using the treating solution for surface treatment of metal of the present invention has an enough corrosion resistance, but, if additional function such as lubricity is required, it is possible to improve the physical property of the film by adding preferably selected polymer according to the desired function.
  • polymer compounds which are generally used for the surface treatment of metal such as polyvinyl alcohol, poly(metha)acrylic acid, copolymer of acrylic acid and methacrylic acid, copolymer of ethylene with acrylic monomer such as (metha)acrylic acid or (metha)acrylate, copolymer of ethylene and vinyl acetate, polyurethane, amino-modified phenol resin, polyester resin and epoxy resin can be used.
  • metal such as polyvinyl alcohol, poly(metha)acrylic acid, copolymer of acrylic acid and methacrylic acid, copolymer of ethylene with acrylic monomer such as (metha)acrylic acid or (metha)acrylate, copolymer of ethylene and vinyl acetate, polyurethane, amino-modified phenol resin, polyester resin and epoxy resin
  • metal such as polyvinyl alcohol, poly(metha)acrylic acid, copolymer of acrylic acid and methacrylic acid, copolymer of ethylene with acrylic monomer such as (metha)acrylic acid
  • the method for surface treatment of the present invention can be illustrated as follows. Namely, the surface is merely treated by degreasing treatment according to an ordinary method, and the cleaned metal material to be treated is brought into contact with the treating solution for surface treatment of metal. Accordingly, the film composed of oxide and/or hydroxide of a metal element selected from the group consisting of zirconium and titanium is deposited and the surface treated film layer having good adhesiveness and corrosion resistance is formed.
  • any kind of treatment e.g., spraying treatment, immersion treatment or pouring treatment can be used, and the properties of the product will not be influenced by the treating method.
  • the structure of the surface treated layer of the present invention is considered to be a state where oxide and hydroxide are mixed when dried at an ordinary temperature or at a low temperature after surface treatment. And, when dried at a high temperature after surface treatment, the structure of the surface treated layer is considered to be a state of oxide alone or oxide rich.
  • the condition to use the treating solution for surface treatment of metal is not restricted.
  • the reactivity of the treating solution for surface treatment of metal of the present invention can be voluntarily regulated by changing the concentration of zirconium compound or titanium compound and the concentration of free fluorine ion in the treating solution for surface treatment of metal in accordance with claims 1 and 8. Therefore, the treating temperature and treating period of time can be changed voluntarily in combination of the reactivity of the treating bath.
  • At least one surface active agent selected from the group consisting of nonionic surface active agent, anionic surface active agent and cationic surface active agent can be added to the treating solution for surface treatment of metal.
  • this treating solution for surface treatment of a metal can be used also as a surface treating agent and a degreasing agent.
  • the invention provides the method of claim 8 to carry out the electrolysis in the treating solution for surface treatment of metal having two or more metal materials to be simultaneously treated as a cathode.
  • the electrolysis treatment is carried out using the metal material to be treated as a cathode, the reduction occurs at the surface of the cathode and the pH goes up.
  • the stability of zirconium compound and/or titanium compound at the surface of cathode is deteriorated, and the surface treated film is deposited as an oxide or a hydroxide containing water.
  • the effect of the present invention can be improved when, after contacting with treating solution for surface treatment of metal, or after being electrolyzed in the treating solution for surface treatment of metal with or without washed by water, the two or more metal materials are brought into contact with the acidic solution of the compound containing at least one element selected from the group consisting of cobalt, nickel, tin, copper, titanium and zirconium, or with the treating solution containing at least one polymer compound selected from the group consisting of water soluble polymer compound and water dispersible polymer.
  • the surface treated film layer obtained by the method of surface treatment of the present invention is characterized in a thin film and exhibits excellent coating property, but depending on the surface condition of the metal material to be treated, sometimes tiny defects may be formed on the surface treated film layer.
  • the layer in contact with the acidic solution of the compound containing at least one element selected from the group consisting of cobalt, nickel, tin, copper, titanium and zirconium or the treating solution containing at least one polymer compound selected from the group consisting of water soluble polymer compound and water dispersible polymer the tiny defects are covered and the corrosion resistance can be further improved.
  • the compound containing at least one element selected from the group consisting of cobalt, nickel, tin, copper, titanium and zirconium is not restricted, and, it is possible to use oxide, hydroxide, fluoride, complex fluoride, chloride, nitrate, oxynitrate, sulfate, oxysulfate, carbonate, oxycarbonate, phosphate, oxyphosphate, oxalate, oxyoxalate, and organic metal compounds and the like.
  • the pH of acidic solution containing the metal element is 2 to 6, and can be adjusted with acid such as phosphoric acid, nitric acid, sulfuric acid, hydrofluoric acid, hydrochloric acid and organic acid or alkali such as sodium hydroxide, potassium hydroxide, lithium hydroxide, salts of alkali metal, ammonium salt or amines.
  • acid such as phosphoric acid, nitric acid, sulfuric acid, hydrofluoric acid, hydrochloric acid and organic acid or alkali such as sodium hydroxide, potassium hydroxide, lithium hydroxide, salts of alkali metal, ammonium salt or amines.
  • At least one polymer compound selected from above mentioned water soluble polymer compound or water dispersible polymer compound for example, polyvinyl alcohol, poly(metha)acrylic acid, copolymer of acrylic acid and methacrylic acid, copolymer of ethylene with acrylic monomer such as (metha)acrylic acid or (metha)acrylate, copolymer of ethylene and vinyl acetate, polyurethane, amino-modified phenol resin, polyester resin or epoxy resin, tannin and tannic acid and salts thereof, and phytic acid can be used.
  • the present invention may remarkably improve the corrosion resistance of metal material by providing a surface treated film layer composed of oxide and/or hydroxide of metal elements selected from zirconium and/or titanium on the surface of metal material to be treated.
  • the oxide and hydroxide of above mentioned metal elements have a physical property characterized not to be damaged by acid or alkali, and chemically stabilized.
  • the pH becomes lower, while, at the cathode where reduction occurs, the pH becomes higher. Therefore, the surface treated film of less resistant to acid and alkali may be dissolved under the corrosive environment and its effect would be lost. Since the main component of the surface treated film layer of the present invention is resistive to acid or alkali, the excellent effect can be maintained under the corrosive environment.
  • the oxide and hydroxide of above mentioned metal elements form a network structure mediated by metal and oxide, it becomes a very good barrier film.
  • the corrosion of metal material which can be varied depending on the environment for use, generally, is oxygen demanding type corrosion in the atmosphere in which water and oxygen exist, and the speed of corrosion is promoted by the presence of the components such as chloride. Having a barrier effect against water, an acid and a corrosion promoting component, the surface treated film layer of the present invention may exhibit excellent corrosion resistance.
  • the adhesion amount over 30 mg/m 2 calculated as the metal element is necessary, desirably over 40 mg/m 2 and more desirably over 50 mg/m 2 .
  • the adhesion amount over 20 mg/m 2 calculated as the metal element is necessary, desirably over 30 mg/m 2 .
  • the adhesion amount over than 10 mg/m 2 calculated as the metal element is necessary, desirably over 20 mg/m 2 .
  • the adhesion amount over than 10 mg/m 2 calculated as the metal element is necessary, desirably over than 20 mg/m 2 .
  • the adhesion amount there is no upper limit.
  • the desirable upper limit of adhesion amount is 1 g/m 2 , more desirably 800 mg/m 2 .
  • test plates cold rolled steel plates, hot-dip zinc-coated steel plates, aluminum alloy plates and magnesium alloy plates are used in the Examples and Comparative Examples.
  • the abbreviations and specifications of these test plates are shown below.
  • the test plate prepared by joining three metal materials of SPC, GA and Al by a spot welding was used.
  • each test plate of SPC, GA, Al and Mg, and the test plate prepared by joining three metal materials of SPC, GA and Al by a spot welding were used.
  • the coating property the test plate prepared by joining three metal materials of SPC, GA and Al by a spot welding was used and the test from surface treatment, coating and evaluation of coating property were carried out in series.
  • Fig.1 is the plane view of the test plate prepared by joining three metal materials of SPC, GA and Al by a spot welding
  • Fig.2 is an elevation view of it.
  • the numeral 1 indicates a spot welded portion.
  • alkali degreasing was carried out as follows. That is, Fine Cleaner L4460 (Trade Mark: Product of Nihon Parkerizing) was diluted to 2% concentration by city water, and was sprayed to a plate to be treated at 40 °C for 120 sec. Rinsing by water and rinsing by pure water after film formation treatment were performed by spraying water and pure water on the plate to be treated at a room temperature for 30 sec both in Examples and Comparative Examples.
  • Aqueous solution of zirconium with concentration of 200 ppm was prepared using zirconium oxynitrate reagent and nitric acid. After heating the aqueous solution to 45°C, the pH was adjusted to 3.0 using sodium hydroxide reagent and hydrofluoric acid, and the concentration of free fluorine ion measured by a fluorine ion meter (IM-55G; product of Toa Denpa Industries Co., Ltd) was adjusted to 1 ppm, thus obtaining the treating solution for surface treatment of metal. The total fluorine concentration in the treating solution for surface treatment of metal after adjusting free fluorine ion was 50 ppm.
  • test plate rinsed by water after degreasing was immersed into the treating solution for surface treatment of metal for 120 seconds so as to carry out the surface treatment.
  • Aqueous solution of zirconium with concentration of 100 ppm, magnesium with concentration of 5000 ppm, strontium with concentration of 2000 ppm and nitric acid group with concentration of 28470 ppm was prepared using zirconium oxynitrate reagent, magnesium nitrate reagent and strontium nitrate reagent. After heating the aqueous solution to 50°C, the pH was adjusted to 4.0 using ammonium water reagent and hydrofluoric acid, and the concentration of free fluorine ion measured by a fluorine ion meter (IM-55G; product of Toa Denpa Industries Co., Ltd) was adjusted to 80 ppm, thus obtaining the treating solution for surface treatment of metal. The total fluorine concentration in the treating solution for surface treatment of metal after adjusting free fluorine ion was 2000 ppm.
  • IM-55G fluorine ion meter
  • test plate rinsed by water after degreasing was immersed into the treating solution for surface treatment of metal for 60 seconds so as to carry out the surface treatment.
  • Aqueous solution of zirconium with concentration of 1000 ppm, titanium with concentration of 2000 ppm, calcium with concentration of 5 ppm and nitric acid group with concentration of 1000 ppm was prepared using aqueous solution of hexafluorozirconic acid (IV), aqueous solution of titanium sulfate (IV) and calcium sulfate reagent.
  • the pH was adjusted to 5.0 using potassium hydroxide reagent and hydrofluoric acid, and the concentration of free fluorine ion measured by a fluorine ion meter (IM-55G; product of Toa Denpa Industries Co., Ltd) was adjusted to 25 ppm, thus obtaining the treating solution for surface treatment of metal.
  • IM-55G fluorine ion meter
  • the total fluorine concentration in the treating solution for surface treatment of metal after adjusting free fluorine ion was 2250 ppm.
  • test plate rinsed by water after degreasing was immersed into the treating solution for surface treatment of metal for 90 seconds so as to carry out the surface treatment.
  • Aqueous solution of titanium with concentration of 5000 ppm, strontium with concentration of 5000 ppm, nitric acid group with concentration of 7080 ppm and nitrous acid group with concentration of 40 ppm was prepared using aqueous solution of hexafluorotitanium acid (IV), strontium nitrate reagent, and sodium nitrite reagent.
  • the pH was adjusted to 4.0 using triethanol amine reagent and hydrofluoric acid, and the concentration of free fluorine ion measured by a fluorine ion meter (IM-55G; product of Toa Denpa Industries Co., Ltd) was adjusted to 10 ppm, thus obtaining the treating solution for surface treatment of metal.
  • the total fluorine concentration in the treating solution for surface treatment of metal after adjusting free fluorine ion was 11900 ppm.
  • test plate was rinsed by water after degreasing, then the obtained treating solution for surface treatment of metal was sprayed to the surface thereof for 120 sec., thus carrying out the surface treatment.
  • Aqueous solution of zirconium with concentration of 5 ppm, titanium with concentration of 5 ppm, magnesium with concentration of 100 ppm, nitric acid group with concentration of 30520 ppm and chloric acid group with concentration of 100 ppm was prepared using zirconium oxynitrate reagent, aqueous solution of hexafluorotitanic acid (IV), magnesium nitrate reagent, nitric acid and sodium chloric acid reagent.
  • the pH was adjusted to 6.0 using ammonia water reagent and hydrofluoric acid, and the concentration of free fluorine ion measured by a fluorine ion meter (IM-55G; product of Toa Denpa Industries Co., Ltd) was adjusted to 0.5 ppm, thus obtaining the treating solution for surface treatment of metal.
  • IM-55G fluorine ion meter
  • the total fluorine concentration in the treating solution for surface treatment of metal after adjusting free fluorine ion was 12 ppm.
  • test plate was electrolyzed in the treating solution for surface treatment of metal for 5 seconds under the condition of 5A/dm 2 , thus carrying out the surface treatment.
  • Aqueous solution of zirconium with concentration of 150 ppm, magnesium with concentration of 10 ppm, nitric acid group with concentration of 5200 ppm and hydrogen peroxide concentration of 10 ppm was prepared using zirconium oxynitrate reagent, magnesium oxide reagent, nitric acid, and hydrogen peroxide reagent.
  • the pH was adjusted to 5.0 using ammonia water reagent and hydrofluoric acid, the concentration of free fluorine ion measured by a fluorine ion meter (IM-55G; product of Toa Denpa Industries Co., Ltd) was adjusted to 50 ppm and 2 g/L of polyoxyethylenenonylphenylether (ethylene oxide addition mole number: 12 mol), which is nonionic surface active agent, was added, thus obtaining the treating solution for surface treatment of metal.
  • the total fluorine concentration in the treating solution for surface treatment of metal after adjusting free fluorine ion was 170 ppm.
  • Aqueous solution of titanium with concentration of 100 ppm, calcium with concentration of 50 ppm, magnesium with concentration of 5000 ppm, nitric acid group with concentration of 25660 ppm and permanganate with concentration of 10 ppm was prepared using aqueous solution of titanium sulfate (IV), calcium nitrate reagent, magnesium nitrate reagent and potassium permanganate reagent.
  • Water soluble acrylic polymer compound (Jurymer AC-10L: product of Nihon Junyaku Co., Ltd.) was added in the aqueous solution so as the concentration of solid to be 1%, then the aqueous solution was heated to 50°C.
  • the pH was adjusted to 3.0 using sodium hydroxide reagent and hydrofluoric acid, and the total free fluorine ion concentration in the aqueous solution to be measured by a fluorine ion meter (IM-55G; product of Toa Denpa Industries Co., Ltd) was adjusted to 95 ppm, thus obtaining the treating solution for surface treatment of metal.
  • IM-55G fluorine ion meter
  • the total fluorine concentration in the treating solution for surface treatment of metal was 2000 ppm.
  • test plate rinsed by water after degreasing was immersed into the treating solution for surface treatment of metal for 60 seconds so as to carry out the surface treatment.
  • the aqueous solution with 1% of water soluble acrylic polymer compound (Jurymer AC-10L: product of Nihon Junyaku Co., Ltd.) in solid concentration and 2g/L of phosphoric acid reagent as phosphoric acid group was prepared.
  • This aqueous solution was heated to 40°C, then the pH was adjusted to 4.5 using ammonia water reagent, thus obtaining the after treating solution.
  • the test plate on which film formation was carried out by the surface treatment of Example 5 and rinsed by water was dipped into the above mentioned after treating solution for 30 seconds so as to carry out the after treatment.
  • the aqueous solution of zirconium with concentration of 50 ppm and cobalt with concentration of 50 ppm was prepared using aqueous solution of hexafluorozirconic acid (IV) and cobalt nitrate reagent. After heating the aqueous solution to 40°C, the pH was adjusted to 5.0 with ammonia water reagent, thus obtaining the after treating solution.
  • the test plate on which film formation was carried out by the surface treatment of Example 6 and rinsed by water was immersed into the above mentioned after treating solution for 30 seconds so as to carry out the after treatment.
  • the aqueous solution of zirconium with concentration of 500 ppm, magnesium with concentration of 1000 ppm and nitric acid group with concentration of 6780 ppm was prepared using zirconium oxynitrate reagent, magnesium nitrate and nitric acid. After heating the aqueous solution to 45°C, the pH was adjusted to 4.0 with sodium hydroxide solution, thus obtaining the treating solution for surface treatment of metal.
  • the free fluorine ion concentration of the treating solution for surface treatment of metal was measured by a fluorine ion meter on the market (IM-55G; product of Toa Denpa Industries Co., Ltd), and the result was 0 ppm.
  • test plate which was rinsed by water after degreasing was immersed into the above mentioned treating solution for surface treatment of metal for 120 seconds so as to carry out the surface treatment.
  • the aqueous solution of titanium with concentration of 2000 ppm was prepared by using aqueous solution of titanium sulfate (IV). After heating the aqueous solution to 50°C, the pH was adjusted to 3.5 using ammonia water reagent and hydrofluoric acid, and the concentration of free fluorine ion measured by a fluorine ion meter (IM-55G; product of Toa Denpa Industries Co., Ltd) was adjusted to 400 ppm, thus obtaining the treating solution for surface treatment of metal.
  • IM-55G fluorine ion meter
  • test plate which was rinsed by water after degreasing was immersed into the above mentioned treating solution for surface treatment of metal for 90 seconds so as to carry out the surface treatment.
  • Alchrom 713 (Trade Mark, product of Nihon Parkerizing Co., Ltd.), which is the chromic chromate treating agent on the market, was diluted by city water to the concentration of 3.6%, then total acidity and free acid acidity were adjusted to the center value described in the brochure.
  • test plate was rinsed by water after degreasing, then immersed into the chromate treating solution heated to the temperature of 35°C and chromate treatment was carried out for 60 sec.
  • Palcoat 3756 (Trade Mark, product of Nihon Parkerizing Co., Ltd.), which is the chrome free treating agent on the market, was diluted by city water to the concentration of 2%, then total acidity and free acid acidity were adjusted to the center value described in the brochure. The test plate was rinsed by water after degreasing, then immersed into the chrome free treating solution heated to the temperature of 40°C and chrome free treatment was carried out for 60 sec.
  • the test plate was rinsed by water after degreasing, then the solution prepared by diluting Prepalene ZN (Trade Mark, product of Nihon Pakerizing Co., Ltd.), which is a surface conditioning agent, with city water to the concentration of 0.1% was sprayed thereon at the room temperature for 30 sec.
  • Palbond L3020 (Trade Mark, product of Nihon Parkerizing Co., Ltd.) was diluted to the concentration of 4.8% with city water.
  • sodium hydrogen fluoride reagent as fluorine was added into the solution to 200 ppm, and then, total acidity and free acid acidity thereof were adjusted to the center value described in the brochure.
  • the zinc phosphate treating solution was prepared. Above mentioned test plate was immersed into the zinc phosphate chemical treating solution heated to the temperature of 42°C, and zinc phosphate film was deposited.
  • coating was carried out by the following process: cationic electrodeposition coating ⁇ rinsing with pure water ⁇ baking ⁇ surfacer ⁇ baking ⁇ top coating ⁇ baking.
  • the coating property in the Examples and Comparative Examples was evaluated and the results thereof are shown in Table 4 and Table 5. Items evaluated and the abbreviations are described below.
  • the coated film after electrodeposition coating process is called as electrodeposition coated film and the coated film after top coating is called as 3-coats film.
  • the electrodeposition coated plate was soaked into aqueous solution of 5 wt% of NaCl at 50°C for 840 hours. After soaking, the test plate washed with city water and dried at the room temperature. The whole surface of the test plate was peeled off using an adhesive tape, and the removed area of coated film on each metal material was evaluated by inspector's eye.
  • Example 4 The results for evaluation of coating property of the electrodeposition coated film are summarized in Table 4. Examples showed good corrosive resistance on all test plates. On the contrary, in Comparative Example 1, since free fluorine ions were not contained in the treating solution for surface treatment of metal at all, the deposition of surface treated film was not sufficient and thus the corrosion resistance was not so good. Further, in Comparative Example 2, since the concentration of free fluorine ion in the treating solution for surface treatment of metal was high, especially, the adhesion amount of film on SPC was small and the corrosion resistance was not so good. The coating properties of Examples 5 and 6 were superior to those of Comparative Examples, but when compared with other Examples, corrosive resistances after electrodeposition coating was inferior to those of other Examples. However, as shown in Examples 8 and 9, the corrosive resistance was further improved by carrying out the after treatment.
  • Comparative Example 3 Because in Comparative Example 3, a chromate treating agent for aluminum alloy was used and in Comparative Example 4, a chrome free treating agent for aluminum alloy was used, the corrosion resistance of Al was good, but the corrosion resistance of other test plates were obviously inferior to those of Examples.
  • Comparative Example 5 a zinc phosphate treating agent, which is now usually used as the base for coating was used. However, Comparative Example 5, in the condition where each of the test plates was joined by welding, showed the test results inferior to those of Examples.
  • Table 5 shows the evaluation results of adhesion of a 3-coats plate. Examples showed good adhesion to all test plates. Regarding to 1st ADH, good results were obtained in all Comparative Examples. However, regarding to 2nd ADH, Comparative Examples did not show the good level of adhesion to all test plates same as the corrosive resistance of the electrodeposition coating. Further, in Comparative Example 5, the generation of sludge, which is the by-product of zinc phosphate treatment, was observed in the treating bath after surface treatment. However, in Examples of the present invention, the generation of sludge was not observed.
  • the treating solution for metal surface treatment and the method for surface treatment of the present invention it is possible to deposit a surface treated film having excellent corrosion resistance after coating on the surface of a metal made of two or more of ferriferous material, zinciferous material, aluminiferous material and magnesiferous material in the treating bath containing no harmful component to the environment and without generating sludge, which have never been achieved in the prior art. Further, since the present invention does not need a process for surface conditioning on the metal material to be treated, it is possible to shorten the treatment time and to reduce space for the treatment.

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Claims (11)

  1. Procédé de traitement de surface de métal comprenant la mise en contact avec une solution traitante pour traitement de surface simultanément de deux matériaux métalliques ou plus choisis dans le groupe constitué de matériau ferrifère, de matériau zincifère, de matériau aluminifère et de matériau magnésifère dans l'état joint par soudage ou rivetage, la solution traitante comprenant 5 à 5000 ppm d'au moins un composé choisi dans le groupe constitué de composé de zirconium et de composé de titane calculés en tant qu'élément métallique, au moins un composé choisi dans le groupe constitué de composé de calcium, de composé de magnésium et de composé de strontium, dans lequel la concentration du composé calculé en tant qu'élément métallique est de 5 à 100 ppm dans le cas du composé de calcium, de 10 à 5000 ppm dans le cas du composé de magnésium et de 10 à 5000 ppm dans le cas du composé de strontium et de 0,1 à 100 ppm d'ion de fluorure libre, et ayant un pH allant de 2 à 6.
  2. Procédé de traitement de surface selon la revendication 1, dans lequel la solution traitante comprend en outre 1000 à 50 000 ppm de groupe nitrate.
  3. Procédé de traitement de surface selon la revendication 1 ou 2, dans lequel la solution traitante comprend en outre au moins un acide d'oxygène et/ou sel d'acide d'oxygène choisi dans le groupe constitué de HClO3, HBrO3, HNO2, HNO3, HMnO4, HVO3, H2O2, H2WO4, H2MoO4 et des sels de ceux-ci.
  4. Procédé de traitement de surface selon l'une quelconque des revendications 1 à 3, dans lequel la solution traitante comprend en outre au moins un composé polymère choisi dans le groupe constitué de composés polymères hydrosolubles et de composés polymères hydrodispersables.
  5. Procédé de traitement de surface selon l'une quelconque des revendications 1 à 4, dans lequel la solution traitante comprend en outre au moins un agent de surface choisi dans le groupe constitué d'agents de surface non ioniques, d'agents de surface anioniques et d'agents de surface cationiques.
  6. Procédé de traitement de surface selon l'une quelconque des revendications 1 à 5, comprenant en outre la mise en contact des deux matériaux métalliques ou plus avec une solution aqueuse acide d'un composé contenant au moins un élément choisi dans le groupe constitué de cobalt, nickel, étain, cuivre, titane et zirconium, après mise en contact avec la solution traitante pour traitement de surface, avec ou sans lavage à l'eau.
  7. Procédé de traitement de surface selon l'une quelconque des revendications 1 à 6, comprenant en outre la mise en contact des deux matériaux métalliques ou plus avec la solution traitante contenant au moins un composé polymère choisi parmi des composés polymères hydrosolubles et des composés polymères hydrodispersables, après mise en contact avec la solution traitante pour traitement de surface, avec ou sans lavage à l'eau.
  8. Procédé de traitement de surface de métal comprenant le traitement électrolytique dans une solution traitante pour traitement de surface, dans lequel simultanément deux matériaux métalliques ou plus choisis dans le groupe constitué de matériau ferrifère, de matériau zincifère, de matériau aluminifère et de matériau magnésifère dans l'état étant joint par soudage ou rivetage sont une cathode, la solution traitante comprenant 5 à 5000 ppm d'au moins un composé choisi dans le groupe constitué de composé de zirconium et de composé de titane calculés en tant qu'élément métallique, au moins un composé choisi dans le groupe constitué de composé de calcium, de composé de magnésium et de composé de strontium, dans lequel la concentration du composé calculé en tant qu'élément métallique est de 5 à 100 ppm dans le cas du composé de calcium, de 10 à 5000 ppm dans le cas du composé de magnésium et de 10 à 5000 ppm dans le cas du composé de strontium et de 0,1 à 100 ppm d'ion de fluorure libre, et ayant un pH allant de 2 à 6.
  9. Procédé de traitement de surface de métal selon la revendication 8, comprenant en outre la mise en contact des deux matériaux métalliques ou plus avec une solution aqueuse acide de composé contenant au moins un élément choisi dans le groupe constitué de cobalt, nickel, étain, cuivre, titane et zirconium, après traitement électrolytique dans la solution traitante pour traitement de surface, avec ou sans lavage à l'eau.
  10. Procédé de traitement de surface de métal selon la revendication 9, comprenant en outre la mise en contact des deux matériaux métalliques ou plus avec une solution traitante contenant au moins un composé polymère choisi parmi des composés polymères hydrosolubles et des composés polymères hydrodispersables, après traitement électrolytique dans la solution traitante pour traitement de surface, avec ou sans lavage à l'eau.
  11. Procédé de traitement de surface selon la revendication 5, dans lequel l'étape de mise en contact comprend la mise en contact des deux matériaux métalliques ou plus, dont la surface n'est ni dégraissée ni nettoyée.
EP03780727.8A 2002-12-13 2003-12-11 Fluide de traitement pour traitement de surface de métal et procédé de traitement de surface Expired - Lifetime EP1571237B1 (fr)

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Families Citing this family (98)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7578921B2 (en) 2001-10-02 2009-08-25 Henkel Kgaa Process for anodically coating aluminum and/or titanium with ceramic oxides
US7569132B2 (en) 2001-10-02 2009-08-04 Henkel Kgaa Process for anodically coating an aluminum substrate with ceramic oxides prior to polytetrafluoroethylene or silicone coating
US7452454B2 (en) 2001-10-02 2008-11-18 Henkel Kgaa Anodized coating over aluminum and aluminum alloy coated substrates
JP4205939B2 (ja) * 2002-12-13 2009-01-07 日本パーカライジング株式会社 金属の表面処理方法
EP1433875B1 (fr) * 2002-12-24 2013-11-27 Chemetall GmbH Agent de revêtement de conversion chimique et surfaces métalliques revêtues
JP4067103B2 (ja) * 2002-12-24 2008-03-26 日本ペイント株式会社 脱脂兼化成処理剤及び表面処理金属
ITMO20040169A1 (it) * 2004-07-02 2004-10-02 Italtecno S R L 'bagno per il rivestimento di conversione di manufatti in allluminio e sue leghe e relativo procedimenti'.
BRPI0606329A2 (pt) * 2005-01-14 2009-01-27 Henkel Kgaa composiÇço utilizÁvel para passivaÇço de uma superfÍcie de metal, processo de tratar um substrato de metal ferrÍfero, aluminÍfero e zincÍfero, e, artigo de fabricaÇço
DE102005005858A1 (de) * 2005-02-08 2006-08-17 Henkel Kgaa Verfahren zur Beschichtung von Metallblech, insbesondere Zinkblech
JP2006241579A (ja) * 2005-03-07 2006-09-14 Nippon Paint Co Ltd 化成処理剤及び表面処理金属
JP4510079B2 (ja) * 2005-03-16 2010-07-21 日本パーカライジング株式会社 表面処理金属材料
DE102005023728A1 (de) 2005-05-23 2006-11-30 Basf Coatings Ag Lackschichtbildendes Korrosionsschutzmittel und Verfahren zu dessen stromfreier Applikation
DE102005059314B4 (de) 2005-12-09 2018-11-22 Henkel Ag & Co. Kgaa Saure, chromfreie wässrige Lösung, deren Konzentrat, und ein Verfahren zur Korrosionsschutzbehandlung von Metalloberflächen
JP4748384B2 (ja) * 2005-09-21 2011-08-17 日立金属株式会社 サドル型継手
US7815751B2 (en) * 2005-09-28 2010-10-19 Coral Chemical Company Zirconium-vanadium conversion coating compositions for ferrous metals and a method for providing conversion coatings
JP5023468B2 (ja) * 2005-10-28 2012-09-12 Ｊｆｅスチール株式会社 缶又は缶蓋用表面処理金属板およびその製造方法、ならびに缶又は缶蓋用樹脂被覆金属板、金属缶および缶蓋
WO2007061011A1 (fr) * 2005-11-22 2007-05-31 Nihon Parkerizing Co., Ltd. Plaque metallique enduite d'une couche de conversion chimique et son procede de fabrication
TWI340770B (en) 2005-12-06 2011-04-21 Nippon Steel Corp Composite coated metal sheet, treatment agent and method of manufacturing composite coated metal sheet
JP2007182626A (ja) * 2005-12-06 2007-07-19 Nippon Steel Corp 複合被覆金属板、複合被覆処理剤、及び複合被覆金属板の製造方法
JP2007262577A (ja) * 2006-03-01 2007-10-11 Nippon Paint Co Ltd 金属表面処理用組成物、金属表面処理方法、及び金属材料
JP5092332B2 (ja) * 2006-03-22 2012-12-05 Ｊｆｅスチール株式会社 表面処理鋼板およびその製造方法
EP2014783B1 (fr) * 2006-05-02 2013-01-16 JFE Steel Corporation Tole d'acier zinguee trempee a chaud et alliee et son procede de production
MY148014A (en) * 2006-09-07 2013-02-28 Jfe Steel Corp Surface-treated steel shee t
ES2659926T3 (es) 2006-09-08 2018-03-20 Chemetall Gmbh Método de tratamiento superficial de metal base, material metálico tratado por el método de tratamiento superficial y método de recubrimiento del material metálico
CA2662865C (fr) 2006-09-08 2016-07-05 Nippon Paint Co., Ltd. Procede de traitement de surface d'une base metallique, materiau metallique traite au moyen de ce procede de traitement de surface, et procede de revetement de materiau metallique
DE102006053291A1 (de) 2006-11-13 2008-05-15 Basf Coatings Ag Lackschichtbildendes Korrosionsschutzmittel mit guter Haftung und Verfahren zu dessen stromfreier Applikation
ES2391870T3 (es) * 2007-02-12 2012-11-30 Henkel Ag & Co. Kgaa Procedimiento para tratar superficies metálicas
DE102007012406A1 (de) * 2007-03-15 2008-09-18 Basf Coatings Ag Verfahren zur Korrosionsschutzausrüstung metallischer Substrate
EP1978131B2 (fr) * 2007-03-29 2019-03-06 ATOTECH Deutschland GmbH Moyen de fabrication de couche anti-corrosion sur des surfaces métalliques
JP5571277B2 (ja) 2007-04-13 2014-08-13 日本パーカライジング株式会社 亜鉛系金属材料用表面処理液および亜鉛系金属材料の表面処理方法
US8673091B2 (en) * 2007-08-03 2014-03-18 Ppg Industries Ohio, Inc Pretreatment compositions and methods for coating a metal substrate
US9428410B2 (en) 2007-09-28 2016-08-30 Ppg Industries Ohio, Inc. Methods for treating a ferrous metal substrate
US8097093B2 (en) 2007-09-28 2012-01-17 Ppg Industries Ohio, Inc Methods for treating a ferrous metal substrate
US9574093B2 (en) * 2007-09-28 2017-02-21 Ppg Industries Ohio, Inc. Methods for coating a metal substrate and related coated metal substrates
JP5470751B2 (ja) * 2008-02-13 2014-04-16 Ｔｄｋ株式会社 活物質及び電極の製造方法、活物質及び電極
BRPI0909501B1 (pt) * 2008-03-17 2019-03-26 Henkel Ag & Co. Kgaa Método
DE102008014465B4 (de) 2008-03-17 2010-05-12 Henkel Ag & Co. Kgaa Mittel zur optimierten Passivierung auf Ti-/Zr-Basis für Metalloberflächen und Verfahren zur Konversionsbehandlung
KR20110020237A (ko) * 2008-04-25 2011-03-02 헨켈 아게 운트 코 카게아아 아연 도금 강을 처리하기 위한 3가 크롬 부동태화제
CN101629299B (zh) * 2008-07-16 2011-03-30 宝山钢铁股份有限公司 用于二次冷轧材的电镀脱脂剂
JP5338195B2 (ja) * 2008-08-20 2013-11-13 新日鐵住金株式会社 表面処理亜鉛系めっき鋼板及びその製造方法
JP5463652B2 (ja) * 2008-11-14 2014-04-09 Ｔｄｋ株式会社 活物質及び電極の製造方法
EP2186928A1 (fr) * 2008-11-14 2010-05-19 Enthone, Inc. Procédé pour le post-traitement des couches métalliques
JP5407062B2 (ja) * 2008-11-17 2014-02-05 Ｔｄｋ株式会社 活物質及び電極の製造方法、活物質、電極及びリチウムイオン二次電池
US8282801B2 (en) * 2008-12-18 2012-10-09 Ppg Industries Ohio, Inc. Methods for passivating a metal substrate and related coated metal substrates
JP5347522B2 (ja) 2009-01-20 2013-11-20 Ｔｄｋ株式会社 活物質及び電極の製造方法、活物質及び電極
DE102009007632A1 (de) 2009-02-05 2010-08-12 Basf Coatings Ag Beschichtungsmittel für korrosionsstabile Lackierungen
US9701177B2 (en) 2009-04-02 2017-07-11 Henkel Ag & Co. Kgaa Ceramic coated automotive heat exchanger components
JP5434278B2 (ja) * 2009-05-29 2014-03-05 Ｔｄｋ株式会社 活物質及び電極の製造方法、活物質及び電極
US20100316881A1 (en) * 2009-06-16 2010-12-16 Kaylo Alan J Method of reducing mapping of an electrodepositable coating layer
ES2748850T3 (es) 2009-07-02 2020-03-18 Henkel Ag & Co Kgaa Solución de tratamiento de superficies metálicas por conversión química exenta de cromo y flúor, método de tratamiento de superficie metálica, y método de revestimiento de superficie metálica
DE102009028025A1 (de) 2009-07-27 2011-02-03 Henkel Ag & Co. Kgaa Mehrstufiges Verfahren zur Behandlung von Metalloberflächen vor einer Tauchlackierung
CN101603174B (zh) * 2009-07-28 2010-12-08 武汉钢铁(集团)公司 彩色涂层钢板用无铬预处理剂
FR2948690B1 (fr) * 2009-07-30 2013-03-08 Snecma Piece comportant un substrat portant une couche de revetement ceramique
WO2011090691A2 (fr) 2009-12-28 2011-07-28 Henkel Ag & Co. Kgaa Composition de prétraitement d'un métal contenant du zirconium, du cuivre, du zinc et un nitrate, et revêtements correspondants appliqués sur des substrats métalliques
JP4920800B2 (ja) * 2010-03-23 2012-04-18 新日本製鐵株式会社 容器用鋼板の製造方法
TW201139736A (en) * 2010-05-13 2011-11-16 Zen Material Technologies Inc Color whitening processing method for stainless steel surface and processing liquid used thereby
WO2011149047A1 (fr) 2010-05-28 2011-12-01 東洋製罐株式会社 Bain de traitement de surface, procédé de fabrication de plaque en acier traitée en surface au moyen du bain de traitement de surface, et plaque en acier traitée en surface formée suivant ledit procédé de fabrication
JP5861249B2 (ja) * 2010-09-15 2016-02-16 Ｊｆｅスチール株式会社 容器用鋼板の製造方法
MX361013B (es) * 2011-02-08 2018-11-26 Henkel Ag & Co Kgaa Procesos y composiciones para mejorar el desempeño anti-corrosión de superficies de zinc pretratadas con óxido de zirconio.
CN103608491B (zh) * 2011-03-25 2016-06-15 日涂表面处理化工有限公司 表面处理剂组合物、表面处理钢板的制造方法、表面处理钢板、有机被覆表面处理钢板、罐盖、罐体以及无缝罐
JP5894576B2 (ja) 2011-03-25 2016-03-30 日本ペイント・サーフケミカルズ株式会社 錫めっき鋼材用表面処理剤組成物及び表面処理された錫めっき鋼材
JP5750013B2 (ja) * 2011-09-07 2015-07-15 日本ペイント株式会社 電着塗料組成物および化成処理を施していない被塗物に電着塗膜を形成する方法
JP6055263B2 (ja) * 2011-10-14 2016-12-27 日本ペイント・サーフケミカルズ株式会社 自動車部品の製造方法
WO2013080325A1 (fr) * 2011-11-30 2013-06-06 日本パーカライジング株式会社 Supplément et procédé de production de tôle en acier traitée en surface
WO2013089292A1 (fr) * 2011-12-15 2013-06-20 대영엔지니어링 주식회사 Procédé de revêtement par dépôt électrolytique destiné à un matériau en acier de magnésium
RU2611610C2 (ru) 2012-08-29 2017-02-28 Ппг Индастриз Огайо, Инк. Циркониевые композиции предварительной обработки, содержащие молибден, соответствующие способы обработки металлических субстратов и соответствующие металлические субстраты с покрытиями
MX2015002603A (es) 2012-08-29 2015-10-08 Ppg Ind Ohio Inc Composiciones de pretratamiento de zirconio que contienen litio, metodos asociados para tratar sustratos metalicos y sustratos metalicos revestidos relacionados.
US9273399B2 (en) 2013-03-15 2016-03-01 Ppg Industries Ohio, Inc. Pretreatment compositions and methods for coating a battery electrode
EP3051006B1 (fr) 2013-09-25 2019-06-19 Toyo Kohan Co., Ltd. Procédé de production d'une tôle d'acier traitée en surface
CN103526250A (zh) * 2013-09-27 2014-01-22 宁波金恒机械制造有限公司 一种铸铁表面处理剂及处理方法
CN103540919A (zh) * 2013-09-27 2014-01-29 宁波金恒机械制造有限公司 一种铸铁表面防腐处理剂及处理方法
CN103540918A (zh) * 2013-09-27 2014-01-29 宁波金恒机械制造有限公司 一种铸铁表面防腐处理剂
CN104549944B (zh) 2013-10-16 2019-06-18 涂料外国Ip有限公司 制备多层涂层的方法
JP6220226B2 (ja) 2013-10-31 2017-10-25 東洋鋼鈑株式会社 表面処理鋼板の製造方法、表面処理鋼板、および有機樹脂被覆金属容器
KR20150058859A (ko) * 2013-11-21 2015-05-29 삼성전자주식회사 금속 대상체의 피막 형성 조성물, 피막 및 이의 제조방법.
JP6530885B2 (ja) 2013-12-18 2019-06-12 東洋製罐株式会社 表面処理鋼板、有機樹脂被覆金属容器、及び表面処理鋼板の製造方法
JP5886919B1 (ja) 2014-09-12 2016-03-16 東洋製罐株式会社 表面処理鋼板及びその製造方法並びに樹脂被覆表面処理鋼板
US9631281B2 (en) 2014-12-04 2017-04-25 Axalta Coating Systems Ip Co., Llc Processes for producing a multilayer coating
DE102014225237B3 (de) * 2014-12-09 2016-04-28 Henkel Ag & Co. Kgaa Verfahren zur nasschemischen Vorbehandlung einer Vielzahl von Eisen- und Aluminiumbauteilen in Serie
PL3031951T3 (pl) 2014-12-12 2018-03-30 Henkel Ag & Co. Kgaa Zoptymalizowane prowadzenie procesu w antykorozyjnej obróbce wstępnej metali w oparciu o kąpiele zawierające fluorki
CN104532225A (zh) * 2014-12-15 2015-04-22 镁联科技（芜湖）有限公司 铝合金钝化剂及其制备方法和铝合金的钝化方法
CN104532221B (zh) * 2014-12-15 2017-10-17 镁联科技（芜湖）有限公司 无铬铝合金钝化剂及其制备方法和铝合金的钝化方法
CN104532224A (zh) * 2014-12-15 2015-04-22 镁联科技（芜湖）有限公司 无铬铝合金钝化剂及其制备方法和铝合金的钝化方法
JP6495702B2 (ja) * 2015-03-19 2019-04-03 株式会社神戸製鋼所 表面処理方法および表面処理装置
CA3034712C (fr) 2016-08-24 2021-10-12 Ppg Industries Ohio, Inc. Composition alcaline destine au traitement de substrats metalliques
KR102451532B1 (ko) * 2017-11-24 2022-10-06 닛폰세이테츠 가부시키가이샤 화성 처리 합금재의 제조 방법 및 화성 처리 합금재의 제조 방법에 사용하는 화성 처리액 재생 장치
CN111886363A (zh) * 2018-02-09 2020-11-03 Ppg工业俄亥俄公司 用于处理金属基底的系统
CN108796578A (zh) * 2018-05-30 2018-11-13 江苏寅凯照明科技有限公司 一种替代铝合金路灯杆阳极氧化的配方及工艺
KR20210126674A (ko) * 2019-02-11 2021-10-20 피피지 인더스트리즈 오하이오 인코포레이티드 금속 기재의 처리를 위한 시스템
CN110424039B (zh) * 2019-09-16 2021-08-10 东北大学 基于水滑石纳米缓蚀微胶囊的镁合金耐蚀自修复微弧氧化涂层的制备方法
TW202134364A (zh) * 2020-01-31 2021-09-16 美商恩特葛瑞斯股份有限公司 用於研磨硬質材料之化學機械研磨(cmp)組合物
KR102176895B1 (ko) * 2020-07-28 2020-11-10 주식회사 성진케미칼 금속면에 페인트 접착력이 우수한 금속산화막을 형성시키기 위한 화학조성물 및 그의 사용방법
JP7438078B2 (ja) 2020-10-20 2024-02-26 日本ペイント・サーフケミカルズ株式会社 鋼材用水性被覆剤、被膜、鋼材の被覆方法、及び鋼材
CN112899664B (zh) * 2021-01-27 2022-08-02 太原科技大学 一种镁合金表面氧化锆基膜层及制备方法
CN113046813B (zh) * 2021-02-19 2022-04-19 赣州有色冶金研究所有限公司 镁合金材料及其制备方法和焊接方法
KR20230052550A (ko) 2021-10-13 2023-04-20 주식회사 성진케미칼 금속표면에 페인트 접착력이 우수한 금속산화막을 형성시키기 위한 친환경성 화학조성물 및 그 사용방법
TWI812437B (zh) * 2022-08-30 2023-08-11 中國鋼鐵股份有限公司 快速辨識熱浸鍍鋅鋼材缺陷黑化的方法
CN116791072B (zh) * 2023-08-14 2024-02-23 广东宏泰节能环保工程有限公司 一种金属表面处理钝化剂及其制备方法与应用

Family Cites Families (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1586975A (en) * 1976-07-05 1981-03-25 Kansai Paint Co Ltd Surface treatment of metals
FR2417537A1 (fr) * 1978-02-21 1979-09-14 Parker Ste Continentale Composition a base d'hafnium pour inhiber la corrosion des metaux
US4273592A (en) * 1979-12-26 1981-06-16 Amchem Products, Inc. Coating solution for metal surfaces
US4313769A (en) * 1980-07-03 1982-02-02 Amchem Products, Inc. Coating solution for metal surfaces
US4457790A (en) * 1983-05-09 1984-07-03 Parker Chemical Company Treatment of metal with group IV B metal ion and derivative of polyalkenylphenol
AU4751885A (en) * 1984-10-09 1986-04-17 Parker Chemical Company Treating extruded aluminium metal surfaces
CA1333043C (fr) * 1988-02-15 1994-11-15 Nippon Paint Co., Ltd. Produit chimique et bain pour le traitement de surface de l'aluminium et de ses alliages
JPH0364485A (ja) * 1989-08-01 1991-03-19 Nippon Paint Co Ltd アルミニウム又はその合金の表面処理剤及び処理浴
JPH0364484A (ja) * 1989-08-01 1991-03-19 Nippon Paint Co Ltd アルミニウム又はその合金の表面処理剤及び処理浴
AU662758B2 (en) * 1991-08-30 1995-09-14 Henkel Corporation Process for treating metal with aqueous acidic composition that is substantially free from chromium (VI)
US5143562A (en) * 1991-11-01 1992-09-01 Henkel Corporation Broadly applicable phosphate conversion coating composition and process
JP3105322B2 (ja) * 1991-12-27 2000-10-30 日産自動車株式会社 光輝性アルミホイールの無色クロメート皮膜形成方法
DE4317217A1 (de) * 1993-05-24 1994-12-01 Henkel Kgaa Chromfreie Konversionsbehandlung von Aluminium
US5380374A (en) * 1993-10-15 1995-01-10 Circle-Prosco, Inc. Conversion coatings for metal surfaces
DE4401566A1 (de) * 1994-01-20 1995-07-27 Henkel Kgaa Verfahren zur gemeinsamen Vorbehandlung von Stahl, verzinktem Stahl, Magnesium und Aluminium vor der Verbindung mit Gummi
US6059896A (en) * 1995-07-21 2000-05-09 Henkel Corporation Composition and process for treating the surface of aluminiferous metals
JPH0982495A (ja) * 1995-09-18 1997-03-28 Toshiba Corp プラズマ生成装置およびプラズマ生成方法
US5935348A (en) * 1995-11-14 1999-08-10 Henkel Kommanditgesellschaft Auf Aktien Composition and process for preventing corrosion and reducing friction on metallic surfaces
JP3437023B2 (ja) * 1995-11-20 2003-08-18 日本ペイント株式会社 アルミニウム系金属表面処理浴及び処理方法
US6361833B1 (en) * 1998-10-28 2002-03-26 Henkel Corporation Composition and process for treating metal surfaces
DE19857799A1 (de) * 1998-12-15 2000-06-21 Henkel Kgaa Verfahren zum Steuern einer Behandlungslinie
JP4099307B2 (ja) * 2000-04-20 2008-06-11 日本ペイント株式会社 アルミニウム用ノンクロム防錆処理剤、防錆処理方法および防錆処理されたアルミニウム製品
WO2002024344A2 (fr) * 2000-09-25 2002-03-28 Chemetall Gmbh Procede de pretraitement et d'enduction de surfaces metalliques, avant leur façonnage, au moyen d'un revetement ressemblant a de la peinture, et utilisation de substrats ainsi enduits
TWI268965B (en) * 2001-06-15 2006-12-21 Nihon Parkerizing Treating solution for surface treatment of metal and surface treatment method
JP3820165B2 (ja) * 2002-03-04 2006-09-13 日本ペイント株式会社 金属表面処理用組成物
JP2003313678A (ja) * 2002-04-23 2003-11-06 Nippon Paint Co Ltd ノンクロム金属表面処理剤、ノンクロム金属表面処理方法、及び、アルミニウム又はアルミニウム合金
JP4205939B2 (ja) * 2002-12-13 2009-01-07 日本パーカライジング株式会社 金属の表面処理方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

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CN101487115B (zh) 2013-05-22
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US20060185769A1 (en) 2006-08-24
WO2004055237A1 (fr) 2004-07-01
CN101487115A (zh) 2009-07-22
AU2003289323A1 (en) 2004-07-09
JP4205939B2 (ja) 2009-01-07
EP1571237A4 (fr) 2007-11-21
AU2003289323A8 (en) 2004-07-09
EP1571237A1 (fr) 2005-09-07
KR100674778B1 (ko) 2007-01-25
CN100537845C (zh) 2009-09-09
CA2509772A1 (fr) 2004-07-01
MXPA05006156A (es) 2005-12-05
KR20050097916A (ko) 2005-10-10

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