EP2292808A1 - Prétraitement métallisant de surfaces en zinc - Google Patents

Prétraitement métallisant de surfaces en zinc Download PDF

Info

Publication number
EP2292808A1
EP2292808A1 EP10187987A EP10187987A EP2292808A1 EP 2292808 A1 EP2292808 A1 EP 2292808A1 EP 10187987 A EP10187987 A EP 10187987A EP 10187987 A EP10187987 A EP 10187987A EP 2292808 A1 EP2292808 A1 EP 2292808A1
Authority
EP
European Patent Office
Prior art keywords
metal
cations
compounds
galvanized
alloy
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP10187987A
Other languages
German (de)
English (en)
Other versions
EP2292808B1 (fr
Inventor
Karsten Hackbarth
Michael Wolpers
Wolfgang Lorenz
Peter Kuhm
Kevin K. Meagher
Christian Rosenkranz
Marcel Roth
Reiner Wark
Guadalupe Sanchis Otero
Eva Wilke
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP2292808A1 publication Critical patent/EP2292808A1/fr
Application granted granted Critical
Publication of EP2292808B1 publication Critical patent/EP2292808B1/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/54—Contact plating, i.e. electroless electrochemical plating
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/48—After-treatment of electroplated surfaces
    • 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
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/26—After-treatment
    • 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
    • C23C22/78—Pretreatment of the material to be coated
    • 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
    • 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
    • C23C28/021—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 including at least one metal alloy 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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12771—Transition metal-base component
    • Y10T428/12785—Group IIB metal-base component
    • Y10T428/12792—Zn-base component
    • Y10T428/12799—Next to Fe-base component [e.g., galvanized]

Definitions

  • the present invention relates to a process for the metallizing pretreatment of galvanized and / or alloy-galvanized steel surfaces or assembled metallic components, which at least partially comprise surfaces of zinc, in a surface treatment comprising a plurality of process steps.
  • metallic layer deposits of in particular not more than 100 mg / m 2 of tin are produced on the treated zinc surfaces.
  • Such metallized zinc surfaces are outstandingly suitable as starting material for subsequent passivation and coating steps ( illustration 1 , Process II-V) and cause a significantly higher efficiency of the anti-corrosion coating, in particular after the pretreatment of galvanized metal surfaces according to the invention.
  • the application of the process on galvanized steel strip prevents corrosive paint infiltration, especially at the cutting edges.
  • the invention therefore comprises an uncoated or subsequently coated metallic component which has been given a metallizing pretreatment according to the invention, as well as the use of such a component in vehicle body construction in automobile manufacturing, shipbuilding, construction and for the production of white goods.
  • the galvanic coupling between the core material and the metallic coating brings about an active, unimpeded local dissolution of the coating material, which in turn constitutes an activation point for the corrosive infiltration of the organic barrier layer.
  • the phenomenon of paint adhesion or "biistering" is especially observed at the cut edges where unimpeded corrosion of the less noble coating material takes place. The same applies in principle to the locations of a component to which different metallic materials are directly connected by joining techniques.
  • An essential strategy is to improve the paint adhesion of the organic barrier layer on the surface-treated steel strip.
  • German Offenlegungsschrift DE19733972 deals with a process for the alkaline passivating pretreatment of galvanized and alloy-galvanized steel surfaces in strip lines.
  • the surface-treated steel strip is brought into contact with an alkaline treatment agent containing magnesium ions, iron (III) ions and a complexing agent.
  • the zinc surface is passivated thereby forming the corrosion protection layer.
  • Such a passivated surface offers according to the teaching of DE19733972 already a paint adhesion, which is comparable to nickel and cobalt-containing processes.
  • this pretreatment can be followed by further treatment steps such as chromium-free post-passivation to improve the corrosion protection before the paint system is applied. Nevertheless, it appears that this pretreatment system can not satisfactorily suppress the paint peeling caused by the corrosion at the cut edges.
  • This object has been achieved by a method for metallizing pretreatment of galvanized and alloy-galvanized steel surfaces, wherein the zinc surface is brought into contact with an aqueous agent (1) whose pH is not greater than 9, characterized in that cations and / or compounds of a metal (A) in the middle (1) are contained, whose redox potential E redox measured at a metal electrode of the metal (A) at a predetermined process temperature and concentration of cations and / or compounds of the metal (A) in the aqueous medium (1) is more anodic than the electrode potential E Zn of the galvanized or alloy-galvanized steel surface in contact with an aqueous agent (2), which differs from the agent (1) only in that it contains no cations and / or compounds of the metal (A), wherein the cations and / or compounds of the metal (A) in the middle (1) are selected from cations and / or compounds of tin in the oxidation states + II and / or + IV.
  • the method according to the invention is suitable for all metal surfaces, for example strip steel, and / or assembled metallic components, which at least partially also consist of zinc surfaces, for example automobile bodies.
  • the material combination of iron-containing surfaces and zinc surfaces is preferred.
  • pretreatment refers to the passivation by means of inorganic barrier layers (eg phosphating, chromating) or a process step preceding the lacquer coating for conditioning the cleaned metallic surface.
  • inorganic barrier layers eg phosphating, chromating
  • Such conditioning of the surface results in an improvement of the corrosion protection and the paint adhesion for the entire layer system resulting at the end of a process chain for corrosion-protecting surface treatment.
  • FIG 1 are typical process chains summarized in the sense of the present invention, which benefit in particular from the pretreatment according to the invention.
  • the specifying designation of the pretreatment as "metallizing” is to be understood as meaning a pretreatment process which directly effects a metallic deposition of metal cations (A) on the zinc surface, with at least 50 at.% Of the element (A) corresponding to after metallizing pretreatment the analytical method defined in the example part of this application on the zinc surface in the metallic state.
  • the method according to the invention is characterized in that a metallizing pretreatment of the zinc surface takes place when the redox potential E redox is more anodic than the electrode potential E Zn . This is the case when E Redox -E Zn > 0.
  • the redox potential E redox of the cations and / or compounds of the metal (A) in the aqueous medium (1) is at least +50 mV, preferably at least +100 mV and particularly preferably at least +300 mV, but at most +800 mV anodic than the electrode potential E Zn of the zinc surface in contact with the aqueous agent (2). If the EMF is less than +50 mV, sufficient metallization of the galvanized surface can not be achieved in technically relevant contact times, so that in a subsequent passivating conversion treatment the metal deposit of the metal (A) is completely removed from the galvanized surface and the effect of the pretreatment therewith will be annulled.
  • an excessively high EMF of more than +800 mV in short times can lead to a complete and massive occupation of the galvanized surface with the metal (A), so that the desired formation of an inorganic corrosion-inhibiting and adhesion-promoting layer does not occur or at least in a subsequent conversion treatment is hindered.
  • metallization is particularly effective when the concentration of cations and / or compounds of the metal (A) is at least 0.001M and preferably at least 0.01M, but does not exceed 0.2M, preferably 0.1M ,
  • those cations and / or compounds of the metal (A) are preferred which on the average (1) fulfill both the condition for the electromotive force (EMF) as described above and have a standard potential E 0 Me of the metal (A), the cathodic is as the normal potential E 0 H2 of the standard hydrogen electrode (SHE), preferably more than 100 mV, more preferably more than 200 mV cathodic than the normal potential E 0 H2 , wherein the standard potential E 0 Me of the metal (A) the reversible redox reaction Me 0 ⁇ Me n + + n e- in an aqueous solution of the metal cation Me n + with the activity 1 at 25 ° C.
  • EMF electromotive force
  • accelerators with a reducing action are oxo acids of phosphorus or nitrogen and their salts in question, wherein at least one phosphorus atom or nitrogen atom must be present in a middle oxidation state.
  • Such accelerators are, for example, hyposalphous acid, hypo nitric acid, nitrous acid, hypophosphoric acid, hypodiphosphonic acid, diphosphorus (III, V) acid, phosphonic acid, diphosphonic acid and particularly preferably phosphinic acid and salts thereof.
  • accelerators known to the person skilled in the art in phosphating have in addition to their reduction properties also depolarizing properties, i. they act as hydrogen scavengers, thus additionally favoring the metallization of the galvanized steel surface.
  • depolarizing properties i. they act as hydrogen scavengers, thus additionally favoring the metallization of the galvanized steel surface.
  • These include hydrazine, hydroxylamine, nitroguanidine, N-methylmorpholine N-oxide, glucoheptonate, ascorbic acid and reducing sugars.
  • the molar ratio of accelerator to the concentration of the cations and / or compounds of the metal (A) in the aqueous medium (1) is preferably not greater than 2: 1, more preferably not greater than 1: 1 and preferably not below 1: 5.
  • the aqueous agent (1) in the process according to the invention additionally contain small amounts of copper (II) cations, which can also be deposited metallically on the galvanized surface simultaneously with the cations and / or compounds of the metal (A).
  • the aqueous agent (1) should additionally contain not more than 50 ppm, preferably not more than 10 ppm, but at least 0.1 ppm of copper (II) cations.
  • the aqueous agent (1) for the metallizing pretreatment may additionally contain surfactants which are able to liberate the metallic surface from impurities without itself inhibiting the surface by forming compact adsorbate layers for the metallization.
  • Nonionic surfactants with average HLB values of at least 8 and at most 14 may be used for this purpose.
  • the pH of the aqueous agent (1) is preferably not smaller than 4, and preferably not larger than 8, more preferably not larger than 6.
  • the application methods customary in strip steel production and strip steel finishing are practicable. These include, in particular, dipping and spraying processes.
  • the contact time or pretreatment time with the aqueous agent (1) should be at least 1 second but not longer than 30 seconds, preferably not longer than 10 seconds.
  • the metallic layer support is defined as the area-related mass fraction of the element (A) on the galvanized or alloy-galvanized steel surface immediately after the pretreatment according to the invention.
  • Both the preferred contact times and layer conditions as well as the preferred application methods also apply to the pretreatment according to the invention of components assembled from a plurality of metallic materials insofar as these at least partially have zinc surfaces.
  • the present invention also includes those combinations of alloy-galvanized steel surfaces and aqueous compositions (1) in which an alloying constituent of the galvanized steel surface is the same element (A) as the metal (A) in the form of its cations and / or compounds in the aqueous medium (1).
  • the pretreatment process according to the invention is adapted to the subsequent process steps of the surface treatment of galvanized and / or alloy-galvanized steel surfaces with regard to optimized corrosion protection and outstanding paint adhesion, especially at cut edges, surface defects and bimetal contacts. Consequently, the present invention encompasses various aftertreatment processes, ie conversion and lacquer coatings, which, in conjunction with the pretreatment described above, provide the desired results in terms of corrosion protection.
  • the illustration 1 illustrates various preferred within the meaning of the present invention process chains for corrosion-protective coating of metallic surfaces in automotive manufacturing, which already started at the steel producer ("Coit Industry") and continued and completed in the paint shop (“Paint Shop”) at the car manufacturer.
  • the invention therefore relates in a further aspect to the production of a passivating conversion coating on the metallized pretreated galvanized and / or alloy-galvanized steel surface with or without intermediate rinsing and / or drying step (US Pat. illustration 1 , Method IIa).
  • a chromium-containing or preferably chromium-free conversion solution can be used.
  • Preferred conversion solutions with which the metal surfaces pretreated according to the present invention can be treated prior to the application of a permanent corrosion-protective organic coating can be used DE-A-199 23 084 and the literature cited herein.
  • a chromium-free aqueous conversion agent besides hexafluoro anions of Ti, Si and / or Zr may contain as further active ingredients: phosphoric acid, one or more compounds of Co, Ni, V, Fe, Mn, Mo or W, a water-soluble or water-dispersible film-forming organic polymer or copolymer and organophosphonic acids that have complexing properties.
  • phosphoric acid one or more compounds of Co, Ni, V, Fe, Mn, Mo or W
  • water-soluble and / or water-dispersible polymeric complexing agents with oxygen and / or nitrogen ligands based on Mannich addition products of polyvinylphenols with formaldehyde and aliphatic amino alcohols may be present.
  • Such polymers are in the patent US 5,298,289 disclosed.
  • the process parameters for a conversion treatment in the context of this invention are to be chosen such that a conversion layer is produced, the per m 2 surface at least 0.05, preferably at least 0.2, but not more than 3, Contains 5, preferably not more than 2.0 and more preferably not more than 1.0 mmol of the metal M, which is the essential component of the conversion solution.
  • metals M are Cr (III), B, Si, Ti, Zr, Hf.
  • the coverage of the zinc surface with the metal M can be determined, for example, by an X-ray fluorescence method.
  • the chromium-free conversion medium additionally contains copper ions.
  • the molar ratio of metal atoms M selected from zirconium and / or titanium to copper atoms in such a conversion agent is preferably chosen such that it produces a conversion layer in which at least 0.1, preferably at least 0.3, but not more than 2 mmol Copper are also included.
  • a method (IIa), in which the metallizing pretreatment is followed by a conversion treatment to form a thin amorphous inorganic coating may also include a method (IIa).
  • the metallizing pretreatment and the subsequent conversion treatment usually follow further process steps for the application of additional layers, in particular organic paints or coating systems ( illustration 1 , Method III-V).
  • Component a) is a fully reacted polycondensation product of epichlorohydrin and a bisphenol. This essentially has no epoxide groups as reactive groups more.
  • the polymer is then in the form of a hydroxyl-containing polyether, which can undergo crosslinking reactions with, for example, polyisocyanates via these hydroxyl groups.
  • the bisphenol component of this polymer can be selected, for example, from bisphenol A and bisphenol F.
  • the average molar mass (according to the manufacturer, for example determinable by gel permeation chromatography) is preferably in the range from 20,000 to 60,000, in particular in the range from 30,000 to 50,000.
  • the OH number is preferably in the range from 170 to 210 and in particular in the range from 180 to 200.
  • polymers are preferred whose hydroxyl content based on the Estherharz in the range of 5 to 7 wt .-%.
  • the aliphatic polyisocyanates b) and c) are preferably based on HDI, in particular on HDI trimer.
  • the customary polyisocyanate blocking agents may be used. Examples which may be mentioned are: butanone oxime, dimethylpyrazole, malonic esters, diisopropylamine / malonic esters, diisopropylamine / triazole and ⁇ -caprolactam.
  • a combination of malonic ester and diisopropylamine is used as the blocking agent.
  • the content of blocked NCO groups of component b) is preferably in the range from 8 to 10% by weight, in particular in the range from 8.5 to 9.5% by weight.
  • the equivalent weight is preferably in the range of 350 to 600, in particular in the range of 450 to 500 g / mol.
  • the non-blocked aliphatic polyisocyanate c) preferably has an equivalent weight in the range of 200 to 250 g / mol and an NCO content in the range of 15 to 23 wt%.
  • an aliphatic polyisocyanate can be selected which has an equivalent weight in the range of 200 to 230 g / mol, in particular in the range of 210 to 220 g / mol and an NCO content in the range of 18 to 22 wt .-%, preferably in the range from 19 to 21% by weight.
  • Another suitable aliphatic polyisocyanate has for example an equivalent weight in the range of 220 to 250 g / mol, in particular in the range of 230 to 240 g / mol and an NCO content in the range of 15 to 20 wt .-%, preferably in the range of 16 , 5 to 19 wt .-%.
  • Each of these aliphatic polyisocyanates mentioned may be component c). However, a mixture of these two polyisocyanates can also be present as component c). If a mixture of the two mentioned polyisocyanates is used, the ratio of the first-mentioned polyisocyanate to the last-mentioned polyisocyanate for component c) is preferably in the range from 1: 1 to 1: 3.
  • Component d) is selected from hydroxyl-containing polyesters and hydroxyl-containing poly (meth) acrylates.
  • a hydroxyl-containing poly (meth) acrylate having an acid number in the range of 3 to 12, in particular in the range of 4 to 9 mg KOH / g can be used.
  • the content of hydroxyl groups is preferably in the range of 1 to 5 and in particular in the range of 2 to 4 wt .-%.
  • the equivalent weight is preferably in the range of 500 to 700, in particular in the range of 550 to 600 g / mol.
  • a hydroxyl-containing polyester is used as component d
  • a branched polyester having an equivalent weight in the range from 200 to 300, in particular in the range from 240 to 280 g / mol can be selected for this purpose.
  • a weakly branched polyester having an equivalent weight in the range of 300 to 500, in particular in the range of 350 to 450 g / mol is suitable.
  • These different types of polyester can each individually or as a mixture form the component d).
  • a mixture of hydroxyl-containing polyesters and hydroxyl-containing poly (meth) acrylates may also be present as component d).
  • the coating composition (1) in process (III) according to the invention thus contains both a blocked aliphatic polyisocyanate b) and an unblocked aliphatic polyisocyanate c).
  • the hydroxyl-containing components a) and d) are available. Possible reaction of each of components a) and d) with each of components b) and c) produces a complex polymer network of polyurethanes during curing of the agent (2).
  • hydroxyl-containing poly (meth) acrylates are used as component d)
  • further crosslinking via the double bonds of these components occur.
  • component d) consists at least partially of hydroxyl-containing poly (meth) acrylates.
  • the coating composition (1) is cured in the process (III) according to the invention, it is to be expected that initially the non-blocked aliphatic polyisocyanate c) reacts with one or both of components a) and d). If the hydroxyl groups of the components d) are more reactive than those of the component a), during curing, first of all, a reaction of the component c) with the component d) occurs.
  • the blocked aliphatic polyisocyanate b) only reacts with one or both of the components a) and d) when the deblocking temperature is reached.
  • the reactants a) and d) available which has the less reactive OH groups.
  • the coating composition (1) contains, in addition to the components a) to d), a conductive pigment or a mixture of conductive pigments. These may have a relatively low density, such as carbon black and graphite, or a relatively high density, such as metallic iron.
  • the absolute content of the coating composition (1) of the conductivity pigments depends on their density, since it depends less on the mass fraction than on the volume fraction of the conductive pigment in the cured coating for the effect as a conductive pigment.
  • the coating composition (1) based on the total mass of the composition, contains (0.8 to 8) .p% by weight of conductive pigment, where ⁇ is the density of the conductive pigment or the average density of the mixture of conductive pigments in g / cm 3 means.
  • the coating composition (1) preferably contains (2 to 6).% By weight of conductive pigment, based on its total mass.
  • the coating composition (1) contains only graphite having a density of 2.2 g / cm 2 as the conductive pigment, then it preferably contains at least 1.76, in particular at least 4.4, and preferably not more than 17 , 6, in particular not more than 13.2 wt .-% graphite.
  • the coating composition (1) based on its total mass, preferably contains at least 6.32, in particular at least 15.8 wt .-% and not more than 63 , 2, in particular not more than 47.4 wt .-% Accordingly, the Gew.-proportions are calculated if, for example, exclusively as MoS 2 as a conductive pigment a density of 4.8 g / cm3, aluminum having a density of 2.7 g / cm 3, or zinc at a density of 7.1 g / cm3 is used.
  • the coating composition (1) contains not only a single conductive pigment but a mixture of at least two conductive pigments, which then differ greatly in their density.
  • a mixture can be used in which the first mixing partner is a light conductive pigment such as carbon black, graphite or aluminum and the second partner of the mixture is a heavy conductive pigment such as zinc or iron.
  • the average density of the mixture is used, which can be calculated from the weight percentages of the components in the mixture and from their respective density.
  • a specific embodiment of a coating agent (1) in process (IIIb) is characterized in that it contains both a conductive pigment having a density of less than 3 g / cm 3 and a conductive pigment having a density of greater than 4 g / cm 3 in which the total amount of conductive pigment, based on the total mass of the agent (2), is (0.8 to 8).% by weight, where ⁇ is the average density of the mixture of conductive pigments in g / cm 3 .
  • the coating agent (1) as a conductive pigment, a mixture of carbon black or graphite on the one hand and iron powder on the other hand.
  • the weight ratios of carbon black and / or graphite on the one hand and iron on the other hand can be in the range from 1: 0.1 to 1:10, in particular in the range from 1: 0.5 to 1: 2.
  • the coating composition (1) may therefore contain aluminum flakes, graphite and / or carbon black as a light electrically conductive pigment.
  • the use of graphite and / or carbon black is preferred.
  • Carbon black, and especially graphite not only provide electrical conductivity of the resultant coating, but also contribute to this layer having a desirable low Mohs hardness of not more than 4 and being readily reshapeable.
  • the lubricating effect of graphite contributes to a reduced wear of the forming tools. This effect can be further promoted by additionally using pigments with a lubricating effect such as molybdenum sulfide with.
  • As another Lubricants or forming aids may contain the coating agent (1) waxes and / or Teflon.
  • the electrically conductive pigment having a specific weight of at most 3 g / cm 3 may be in the form of small spheres or aggregates of such spheres. It is preferred that the balls or the aggregates of these balls have a diameter of less than 2 microns. However, these electrically conductive pigments are preferably in the form of platelets whose thickness is preferably less than 2 ⁇ m.
  • the coating composition (1) in process (III) according to the invention comprises at least the resin components described above and also solvents.
  • the resin components a) to d) are usually present in their commercial form as a solution or dispersion in organic solvents.
  • the coating composition (1) prepared therefrom then also contains these solvents.
  • the electrically conductive pigment such as, for example, graphite and optionally further pigments such as, in particular, anticorrosive pigments to set a viscosity which allows the coating agent (1) to be applied to the substrate in the coil coating process.
  • additional solvent can be added.
  • the chemical nature of the solvents is usually dictated by the choice of raw materials containing the appropriate solvent.
  • solvents cyclohexanone, diacetone alcohol, diethylene glycol monobutyl ether acetate, diethylene glycol, propylene glycol methyl ether, propylene glycol n-butyl ether, methoxypropyl acetate, n-butyl acetate, xylene, glutaric acid dimethyl ester, dimethyl adipate and / or dimethyl succinate.
  • the preferred proportion of solvent, on the one hand, and organic resin components, on the other hand, in the coating agent (1) depends, when expressed in weight percent, on the proportion of conductive pigment in weight percent in the coating agent (1).
  • the preferred weight percent of solvent and Resin components therefore depend on the density ⁇ of the conductivity pigment used or the average density ⁇ of a mixture of conductive pigments.
  • the coating composition (1) in the process (III) according to the invention it is preferable that, based on the total mass of the coating composition (1), [(25 to 60). Adjustment factor] wt%, preferably [(35 to 55). Adjustment factor] wt% organic solvent and [(20 to 45). Adjustment factor] wt%, preferably [(25 to 40). Adjustment factor] wt%, containing organic resin components, wherein the sum of the weight percentages of organic resin component and solvent is not greater than [93. Adjustment factor] wt%, preferably not greater than [87. Adjustment factor] is% by weight and wherein the adjustment factor [100-2.8p] is 93.85 and ⁇ is the density of the conductive pigment or the average density of the mixture of conductive pigments in g / cm 3 .
  • the coating agent (1) based on the total mass of the coating agent (1), be [(2 to 8) ⁇ adjustment factor]% by weight, preferably [(3 to 5) ⁇ adjustment factor] Wt .-% of the resin component a), wherein the adjustment factor [100-2.8p]: 93.85 and ⁇ is the density of the conductive pigment or the average density of the mixture of conductive pigments in g / cm 3 . From the proportion of the resin component a) can be calculated with the above-mentioned preferred ratios of the individual resin components, the preferred proportions of the resin components b) to d) in the coating agent (1).
  • the proportion of components b) in the total mass of the coating composition can be [(2 to 9) adjustment factor] wt%, preferably [(3 to 6) adjustment factor] wt%, the proportion of resin components c) [ (4 to 18) ⁇ Adjustment factor: Wt%, preferably [(6 to 12) ⁇ Adjustment factor] Wt%, and the proportion of resin components d) [(7 to 30) ⁇ Adjustment factor] Wt%, preferably [ (10 to 20) ⁇ Adjustment factor] wt%.
  • the "adaptation factor" has the meaning given above.
  • the layer b) additionally contains corrosion inhibitors and / or anticorrosive pigments.
  • Corrosion inhibitors or anticorrosive pigments which are known in the prior art for this purpose can be used here. Examples include: magnesium oxide pigments, in particular in nanoscale, finely divided and very finely divided barium sulfate or anticorrosive pigments are based on calcium silicate.
  • the preferred weight fraction of the anticorrosion pigments on the total mass of the coating composition (1) in turn depends on the density of the anticorrosion pigments used.
  • the coating composition (1) in the process (III) according to the invention based on the total mass of the coating composition, preferably contains [(5 to 25) adjustment factor]% by weight, in particular [(10 to 20) adjustment factor]% by weight corrosion protection pigment where the adjustment factor is [100-2.8p]: 93.85 and ⁇ is the density of the conductive pigment or the average density of the mixture of conductive pigments in g / cm 3 .
  • the mechanical and chemical properties of the coating obtained after the baking of the coating agent (1) in process (III) according to the invention can be further improved by additionally containing fillers.
  • these may be selected from silicas or silicas (optionally hydrophobed), alumina (including basic alumina), titania and barium sulfate.
  • the coating composition is (1) [(0.1 to 3) adjustment factor]% by weight, preferably [(0.4 to 2) adjustment factor]% by weight filler selected from silicas or Silicon dioxide, aluminum oxide, titanium dioxide and barium sulfate, where the adjustment factor is [100-2.8 p]: 93.85 and ⁇ is the density of the conductive pigment or the average density of the mixture of conductive pigments in g / cm 3 .
  • the coating composition (1) based on its total mass, lubricants or shaping aids, preferably selected from waxes, molybdenum sulphide and Teflon, preferably in an amount of [(0.5 to 20). Adjustment factor], in particular in an amount of [(1 to 10) adjustment factor] wt%, wherein the adjustment factor is [100-2.8p]: 93.85 and ⁇ is the density of the conductive pigment or the average density of the mixture of conductive pigments in g / cm 3 .
  • steps (i-vi) are carried out as a strip treatment method, wherein the liquid coating composition (1) is applied in step (vi) in such an amount that, after curing, the desired layer thickness is in the range from 0.5 to 10 receives ⁇ m.
  • the coating agent (1) is applied in the so-called coil coating process.
  • continuous metal strips are continuously coated.
  • the coating agent (1) can be applied by different methods, which are familiar in the prior art. For example, applicator rolls can be used to directly adjust the desired wet film thickness. Alternatively, one can immerse the metal strip in the coating agent (1) or spray it with the coating agent (1), after which the desired wet film thickness is adjusted by means of squeeze rolls.
  • step (ii) If metal strips coated immediately before with a metal coating, for example with zinc or zinc alloys, electrolytically or by hot dip coating, it is not necessary to clean the metal surfaces prior to performing the metallizing pretreatment (ii). However, if the metal strips have already been stored and in particular provided with corrosion protection oils, a purification step (i) is necessary before carrying out step (ii).
  • the coated sheet is heated to the required drying or crosslinking temperature for the organic coating.
  • the treatment agent can also be brought to the corresponding drying or crosslinking temperature by infrared radiation, in particular by near infrared radiation.
  • Such pre-coated metal sheets are tailored and converted in the automotive production for the production of bodies accordingly.
  • the assembled component or the assembled body shell therefore has unprotected edges, which must be treated in addition corrosion protection.
  • the so-called "paint shop” therefore, there is a further corrosion-protective treatment and, ultimately, the realization of the automobile-typical paint structure.
  • the present invention therefore relates, in a further aspect, to a process (IV) which extends the process chain (i-vi) of process (III), wherein a crystalline phosphate layer is first deposited on the exposed metal surfaces, in particular on the cut edges, in order to subsequently to provide a final corrosion protection by means of dip paint, in particular protection against infiltration of the paint system at the cutting edges.
  • a process (IV) which extends the process chain (i-vi) of process (III), wherein a crystalline phosphate layer is first deposited on the exposed metal surfaces, in particular on the cut edges, in order to subsequently to provide a final corrosion protection by means of dip paint, in particular protection against infiltration of the paint system at the cutting edges.
  • the entire metallic component including the phosphated cut edges and the first-coated surfaces in process (III) can be electrodeposited ( illustration 1 , Method IVb).
  • the initial coating is not sufficiently conductive, only the phosphated cutting edges are electrocoated, without any further coating being applied on the first coated surfaces.
  • the cut edges are not phosphated, but coated with a self-depositing dip (AC) ( illustration 1 , Method IVc).
  • AC self-depositing dip
  • the present invention is distinguished by the fact that the zinc surfaces pretreated in a metallizing manner according to the invention in particular excellently prevent edge corrosion.
  • the present invention relates to the galvanized and / or alloy-galvanized steel surface and the metallic component, which consists at least partially of a zinc surface which has been pretreated by metallizing in accordance with the process according to the invention with the aqueous agent (1) or subsequently this pretreatment with further passivating Conversion layers and / or paints, eg according to the inventive method (II-IV) coated.
  • Such a treated steel surface or treated component is used in body construction in automotive manufacturing, shipbuilding, construction and for the production of white goods.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Mechanical Engineering (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Paints Or Removers (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Coating With Molten Metal (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
  • Chemically Coating (AREA)
EP10187987.2A 2007-05-04 2008-04-30 Prétraitement métallisant de surfaces en zinc Active EP2292808B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102007021364A DE102007021364A1 (de) 2007-05-04 2007-05-04 Metallisierende Vorbehandlung von Zinkoberflächen
EP08749904.2A EP2145031B1 (fr) 2007-05-04 2008-04-30 Prétraitement de métallisation de surfaces de zinc

Related Parent Applications (3)

Application Number Title Priority Date Filing Date
EP08749904.2A Division-Into EP2145031B1 (fr) 2007-05-04 2008-04-30 Prétraitement de métallisation de surfaces de zinc
EP08749904.2A Division EP2145031B1 (fr) 2007-05-04 2008-04-30 Prétraitement de métallisation de surfaces de zinc
EP08749904.2 Division 2008-04-30

Publications (2)

Publication Number Publication Date
EP2292808A1 true EP2292808A1 (fr) 2011-03-09
EP2292808B1 EP2292808B1 (fr) 2016-06-08

Family

ID=39791281

Family Applications (2)

Application Number Title Priority Date Filing Date
EP10187987.2A Active EP2292808B1 (fr) 2007-05-04 2008-04-30 Prétraitement métallisant de surfaces en zinc
EP08749904.2A Active EP2145031B1 (fr) 2007-05-04 2008-04-30 Prétraitement de métallisation de surfaces de zinc

Family Applications After (1)

Application Number Title Priority Date Filing Date
EP08749904.2A Active EP2145031B1 (fr) 2007-05-04 2008-04-30 Prétraitement de métallisation de surfaces de zinc

Country Status (17)

Country Link
US (1) US8293334B2 (fr)
EP (2) EP2292808B1 (fr)
JP (2) JP5917802B2 (fr)
KR (1) KR20100028542A (fr)
CN (1) CN101675181B (fr)
AU (1) AU2008248694B2 (fr)
BR (1) BRPI0811537A2 (fr)
CA (1) CA2686380C (fr)
DE (1) DE102007021364A1 (fr)
ES (2) ES2589380T3 (fr)
HU (2) HUE030515T2 (fr)
MX (1) MX2009011876A (fr)
PL (2) PL2292808T3 (fr)
PT (2) PT2145031E (fr)
RU (1) RU2482220C2 (fr)
WO (1) WO2008135478A2 (fr)
ZA (1) ZA200907724B (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105063696A (zh) * 2015-08-07 2015-11-18 昆山—邦泰汽车零部件制造有限公司 一种耐磨的汽车五金件制造方法

Families Citing this family (32)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102007021364A1 (de) * 2007-05-04 2008-11-06 Henkel Ag & Co. Kgaa Metallisierende Vorbehandlung von Zinkoberflächen
US9574093B2 (en) 2007-09-28 2017-02-21 Ppg Industries Ohio, Inc. Methods for coating a metal substrate and related coated metal substrates
US9234292B2 (en) * 2009-11-18 2016-01-12 Jx Nippon Mining & Metals Corporation Nickel-iron alloy plating solution
DE102009047522A1 (de) * 2009-12-04 2011-06-09 Henkel Ag & Co. Kgaa Mehrstufiges Vorbehandlungsverfahren für metallische Bauteile mit Zink- und Eisenoberflächen
DE102010001686A1 (de) * 2010-02-09 2011-08-11 Henkel AG & Co. KGaA, 40589 Zusammensetzung für die alkalische Passivierung von Zinkoberflächen
KR101262497B1 (ko) * 2011-03-28 2013-05-08 주식회사 노루코일코팅 강판의 흑변 방지용 피막 형성 조성물 및 상기 조성물에 의해 피막이 형성된 강판 및 피막 형성방법
DE102011078258A1 (de) 2011-06-29 2013-01-03 Henkel Ag & Co. Kgaa Elektrolytische Vereisenung von Zinkoberflächen
EP2631333A1 (fr) * 2012-02-24 2013-08-28 Henkel AG & Co. KGaA Prétraitement de surfaces en zinc avant une passivation
WO2013160567A1 (fr) 2012-04-25 2013-10-31 Arcelormittal Investigacion Y Desarrollo, S.L. Procédé de réalisation d'une tôle prélaquée à revêtements znalmg et tôle correspondante.
DE102012212598A1 (de) 2012-07-18 2014-02-20 Henkel Ag & Co. Kgaa Verzinnende Vorbehandlung von verzinktem Stahl in Gegenwart von Pyrophosphat
DE102012111066A1 (de) 2012-11-16 2014-06-05 Salzgitter Flachstahl Gmbh Beschichtetes Stahlblech mit verbesserten Korrosionseigenschaften und Verfahren zur Herstellung eines solchen Bleches
CN104338668A (zh) * 2013-07-30 2015-02-11 比亚迪股份有限公司 一种基材表面自泳涂装的方法以及电子产品外壳
RU2591919C1 (ru) * 2015-04-01 2016-07-20 Российская Федерация, от имени которой выступает Государственная корпорация по атомной энергии "Росатом" Установка диффузионного цинкования металлических деталей
DE102015206812A1 (de) 2015-04-15 2016-10-20 Henkel Ag & Co. Kgaa Polymerhaltige Vorspüle vor einer Konversionsbehandlung
DE102015209910A1 (de) 2015-05-29 2016-12-01 Henkel Ag & Co. Kgaa Vorspüle enthaltend ein quartäres Amin zur Konditionierung vor einer Konversionsbehandlung
DE102015209909A1 (de) 2015-05-29 2016-12-01 Henkel Ag & Co. Kgaa Konditionierung vor einer Konversionsbehandlung von Metalloberflächen
JP7035021B2 (ja) 2016-08-23 2022-03-14 ヘンケル・アクチェンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフト・アウフ・アクチェン ジ－又はポリアミンとα，β－不飽和カルボン酸誘導体との反応生成物として得られる接着促進剤の金属表面処理のための使用
EP3591092B1 (fr) * 2017-03-03 2024-05-01 Nissan Motor Co., Ltd. Élément coulissant de conception élevée
EP3569734A1 (fr) 2018-05-18 2019-11-20 Henkel AG & Co. KGaA Composition de passivation à base de chrome trivalent
CN109267079A (zh) * 2018-11-15 2019-01-25 济南大学 一种中性金属表面除锈清洗剂的制备方法
FI3663435T3 (fi) 2018-12-05 2024-05-24 Henkel Ag & Co Kgaa Fosfori- ja fosfonihappojen seoksiin perustuva passivointikoostumus
EP3771749A1 (fr) * 2019-07-29 2021-02-03 Ewald Dörken Ag Procédé de passivation de substrats métalliques
WO2021114015A1 (fr) * 2019-12-09 2021-06-17 Hewlett-Packard Development Company, L.P. Substrat en alliage métallique revêtu et son procédé de production
CN110923768B (zh) * 2019-12-19 2022-01-25 漳州市福美鑫新材料科技有限公司 一种用于三价铬电镀工件后处理工艺的设备
CN110983220B (zh) * 2019-12-30 2023-08-18 江苏圣大中远电气有限公司 核电产品抗磨耐腐蚀表面处理系统
WO2021139955A1 (fr) 2020-01-06 2021-07-15 Henkel Ag & Co. Kgaa Composition de passivation appropriée pour des surfaces internes de réservoirs d'acier revêtus de zinc stockant des hydrocarbures
EP3872231A1 (fr) * 2020-02-28 2021-09-01 voestalpine Stahl GmbH Procédé de conditionnement de la surface d'un bande métallique revêtu d'une couche de protection contre la corrosion en alliage de zinc
CN116670236A (zh) 2021-01-06 2023-08-29 汉高股份有限及两合公司 用于涂锌铝钢的基于Cr(III)的改善钝化
GB2603194A (en) 2021-02-01 2022-08-03 Henkel Ag & Co Kgaa Improved cr(iii) based dry-in-place coating composition for zinc coated steel
EP4174211A1 (fr) 2021-11-02 2023-05-03 Henkel AG & Co. KGaA Traitement en plusieurs étages permettant d'activer le phosphatation au zinc des composants métalliques pourvus de surfaces en zinc
CN114108043B (zh) * 2021-11-19 2023-08-11 山东省路桥集团有限公司 钢结构桥梁锈蚀区域的修复再生预处理方法
CN115627465B (zh) * 2022-10-26 2024-05-24 国网湖北省电力有限公司电力科学研究院 一种耐盐穴高压气氛防腐镀层的施镀工艺及应用

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS57188663A (en) * 1981-05-13 1982-11-19 Agency Of Ind Science & Technol Improvement for corrosion resistance of zinc plating
JPH0448095A (ja) * 1990-06-15 1992-02-18 Nippon Steel Corp 缶外面の耐錆性と外観に優れた容器用表面処理鋼板の製造法
US5298289A (en) 1987-12-04 1994-03-29 Henkel Corporation Polyphenol compounds and treatment and after-treatment of metal, plastic and painted surfaces therewith
DE19733972A1 (de) 1997-08-06 1999-02-11 Henkel Kgaa Alkalische Bandpassivierung
DE19923084A1 (de) 1999-05-20 2000-11-23 Henkel Kgaa Chromfreies Korrosionsschutzmittel und Korrosionsschutzverfahren
WO2009041616A1 (fr) * 2007-09-27 2009-04-02 Nippon Paint Co., Ltd. Procédé pour produire un matériau métallique traité en surface et procédé pour produire un article revêtu en métal

Family Cites Families (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE171455C (fr)
CH361954A (de) 1953-08-27 1962-05-15 Gen Am Transport Verfahren zur chemischen Vernickelung
NL282799A (fr) * 1961-09-13
DE2103086C3 (de) * 1971-01-23 1979-11-15 Metallgesellschaft Ag, 6000 Frankfurt Verfahren zur Oberflächenbehandlung von Werkstücken aus Eisen und Stahl
JPS5243171B2 (fr) * 1973-01-11 1977-10-28
JPS51135840A (en) * 1975-05-21 1976-11-25 Nippon Packaging Kk Surface treatment process for zinc or zinc alloy
JPS6169978A (ja) * 1984-09-12 1986-04-10 Nisshin Steel Co Ltd 低鉛溶融亜鉛めつき鋼板の塗装前処理方法
JPS62127479A (ja) * 1985-11-26 1987-06-09 Nisshin Steel Co Ltd 亜鉛めつき鋼板の表面処理方法
JPH0331484A (ja) * 1989-06-27 1991-02-12 Nippon Parkerizing Co Ltd 亜鉛または亜鉛系メッキ材料の黒色化処理法
JP2904592B2 (ja) * 1991-01-14 1999-06-14 日本鋼管株式会社 亜鉛又は亜鉛合金のクロメート処理の前処理方法
JP2968147B2 (ja) * 1993-04-07 1999-10-25 日本パーカライジング株式会社 亜鉛含有金属めっき鋼板用酸性置換めっき液組成物
US5449415A (en) * 1993-07-30 1995-09-12 Henkel Corporation Composition and process for treating metals
AU7619094A (en) * 1993-09-17 1995-04-03 Brent International Plc Pre-rinse for phosphating metal surfaces
JP3366724B2 (ja) * 1994-04-20 2003-01-14 日本ペイント株式会社 金属表面用化成処理水溶液
DE19751153A1 (de) * 1997-11-19 1999-05-20 Henkel Kgaa Polymerisierbare chromfreie organische Coilbeschichtungen
DE10010758A1 (de) * 2000-03-04 2001-09-06 Henkel Kgaa Korrosionsschutzverfahren für Metalloberflächen
US6530999B2 (en) * 2000-10-10 2003-03-11 Henkel Corporation Phosphate conversion coating
DE10322446A1 (de) * 2003-05-19 2004-12-09 Henkel Kgaa Vorbehandlung von Metalloberflächen vor einer Lackierung
DE102004041142A1 (de) * 2004-08-24 2006-03-02 Basf Ag Verfahren zum Passivieren von metallischen Oberflächen unter Verwendung von Itaconsäure Homo- oder Copolymeren
JP2007023353A (ja) * 2005-07-19 2007-02-01 Yuken Industry Co Ltd 亜鉛系めっき部材のノンクロム反応型化成処理
DE102007001654A1 (de) 2007-01-04 2008-07-10 Henkel Kgaa Leitfähige, organische Beschichtungen mit optimiertem Polymersystem
DE102007021364A1 (de) * 2007-05-04 2008-11-06 Henkel Ag & Co. Kgaa Metallisierende Vorbehandlung von Zinkoberflächen

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS57188663A (en) * 1981-05-13 1982-11-19 Agency Of Ind Science & Technol Improvement for corrosion resistance of zinc plating
US5298289A (en) 1987-12-04 1994-03-29 Henkel Corporation Polyphenol compounds and treatment and after-treatment of metal, plastic and painted surfaces therewith
JPH0448095A (ja) * 1990-06-15 1992-02-18 Nippon Steel Corp 缶外面の耐錆性と外観に優れた容器用表面処理鋼板の製造法
DE19733972A1 (de) 1997-08-06 1999-02-11 Henkel Kgaa Alkalische Bandpassivierung
DE19923084A1 (de) 1999-05-20 2000-11-23 Henkel Kgaa Chromfreies Korrosionsschutzmittel und Korrosionsschutzverfahren
WO2009041616A1 (fr) * 2007-09-27 2009-04-02 Nippon Paint Co., Ltd. Procédé pour produire un matériau métallique traité en surface et procédé pour produire un article revêtu en métal

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105063696A (zh) * 2015-08-07 2015-11-18 昆山—邦泰汽车零部件制造有限公司 一种耐磨的汽车五金件制造方法

Also Published As

Publication number Publication date
MX2009011876A (es) 2010-02-24
RU2482220C2 (ru) 2013-05-20
EP2145031A2 (fr) 2010-01-20
WO2008135478A3 (fr) 2009-01-08
CN101675181B (zh) 2012-10-24
AU2008248694A1 (en) 2008-11-13
ZA200907724B (en) 2011-04-28
RU2009144881A (ru) 2011-06-10
ES2589380T3 (es) 2016-11-14
HUE028450T2 (en) 2016-12-28
DE102007021364A1 (de) 2008-11-06
EP2145031B1 (fr) 2016-03-16
CA2686380C (fr) 2016-04-05
PL2145031T3 (pl) 2016-09-30
JP2010526206A (ja) 2010-07-29
JP2016074985A (ja) 2016-05-12
US8293334B2 (en) 2012-10-23
KR20100028542A (ko) 2010-03-12
PT2145031E (pt) 2016-06-16
ES2575993T3 (es) 2016-07-04
AU2008248694B2 (en) 2012-10-04
PT2292808T (pt) 2016-09-08
CA2686380A1 (fr) 2008-11-13
US20100209732A1 (en) 2010-08-19
WO2008135478A2 (fr) 2008-11-13
JP5917802B2 (ja) 2016-05-18
EP2292808B1 (fr) 2016-06-08
BRPI0811537A2 (pt) 2014-11-18
PL2292808T3 (pl) 2016-12-30
HUE030515T2 (en) 2017-05-29
CN101675181A (zh) 2010-03-17

Similar Documents

Publication Publication Date Title
EP2292808B1 (fr) Prétraitement métallisant de surfaces en zinc
EP2016138B1 (fr) Système de protection contre la corrosion pour métaux et pigment associé
EP2507408B1 (fr) Procédé de prétraitement à étapes multiples pour des composants métalliques présentant des surfaces en zinc et en fer
EP2817434B1 (fr) Prétraitement de surfaces en zinc avant une passivation
WO2005061761A1 (fr) Traitement de conversion en deux etapes
WO2008080647A1 (fr) Revêtements organiques conducteurs à système polymère optimisé
EP2726650B1 (fr) Placage électrolytique de fer sur des surfaces en zinc
WO2005061570A1 (fr) Resine phenol-aldehyde fonctionnalisee et procede de traitement de surfaces metalliques
DE10353149A1 (de) Ergänzender Korrosionsschutz für Bauteile aus organisch vorbeschichteten Metallblechen
WO2008014885A1 (fr) Couche de protection contre la corrosion présentant des propriétés améliorées
DE102012111066A1 (de) Beschichtetes Stahlblech mit verbesserten Korrosionseigenschaften und Verfahren zur Herstellung eines solchen Bleches

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20101019

AC Divisional application: reference to earlier application

Ref document number: 2145031

Country of ref document: EP

Kind code of ref document: P

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MT NL NO PL PT RO SE SI SK TR

AX Request for extension of the european patent

Extension state: AL BA MK RS

17Q First examination report despatched

Effective date: 20110214

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

INTG Intention to grant announced

Effective date: 20160129

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AC Divisional application: reference to earlier application

Ref document number: 2145031

Country of ref document: EP

Kind code of ref document: P

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MT NL NO PL PT RO SE SI SK TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: LANGUAGE OF EP DOCUMENT: GERMAN

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 805304

Country of ref document: AT

Kind code of ref document: T

Effective date: 20160715

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 502008014296

Country of ref document: DE

REG Reference to a national code

Ref country code: PT

Ref legal event code: SC4A

Ref document number: 2292808

Country of ref document: PT

Date of ref document: 20160908

Kind code of ref document: T

Free format text: AVAILABILITY OF NATIONAL TRANSLATION

Effective date: 20160902

REG Reference to a national code

Ref country code: SE

Ref legal event code: TRGR

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20160608

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160908

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160608

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2589380

Country of ref document: ES

Kind code of ref document: T3

Effective date: 20161114

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160608

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160909

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160608

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20161008

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160608

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160608

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 502008014296

Country of ref document: DE

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 10

26N No opposition filed

Effective date: 20170309

REG Reference to a national code

Ref country code: HU

Ref legal event code: AG4A

Ref document number: E030515

Country of ref document: HU

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160608

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160608

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160608

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170430

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170430

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170430

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 11

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170430

REG Reference to a national code

Ref country code: AT

Ref legal event code: MM01

Ref document number: 805304

Country of ref document: AT

Kind code of ref document: T

Effective date: 20170430

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170430

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160608

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: PL

Payment date: 20190322

Year of fee payment: 12

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SK

Payment date: 20190328

Year of fee payment: 12

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: PT

Payment date: 20190325

Year of fee payment: 12

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160608

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 20190627

Year of fee payment: 10

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20160608

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160608

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160608

REG Reference to a national code

Ref country code: FI

Ref legal event code: MAE

REG Reference to a national code

Ref country code: SK

Ref legal event code: MM4A

Ref document number: E 21933

Country of ref document: SK

Effective date: 20200430

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20200501

Ref country code: FI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20200430

Ref country code: PT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20201102

Ref country code: SE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20200501

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SK

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20200430

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20200430

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20200430

P01 Opt-out of the competence of the unified patent court (upc) registered

Effective date: 20230530

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20230425

Year of fee payment: 16

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 20230419

Year of fee payment: 16

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20240419

Year of fee payment: 17

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20240418

Year of fee payment: 17

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20240524

Year of fee payment: 17

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CZ

Payment date: 20240419

Year of fee payment: 17