[go: up one dir, main page]

WO2000071626A1 - Agent anticorrosif depourvu de chrome et procede de protection contre la corrosion - Google Patents

Agent anticorrosif depourvu de chrome et procede de protection contre la corrosion Download PDF

Info

Publication number
WO2000071626A1
WO2000071626A1 PCT/EP2000/004267 EP0004267W WO0071626A1 WO 2000071626 A1 WO2000071626 A1 WO 2000071626A1 EP 0004267 W EP0004267 W EP 0004267W WO 0071626 A1 WO0071626 A1 WO 0071626A1
Authority
WO
WIPO (PCT)
Prior art keywords
acid
diphosphonic acid
corrosion protection
corrosion
coating
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.)
Ceased
Application number
PCT/EP2000/004267
Other languages
German (de)
English (en)
Inventor
Stefan Küpper
Jörg Sander
Karsten Hackbarth
Christina Hirsch
Veit Lachmann
Petra Reessing
Reinhard Seidel
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
Priority to EP00935006A priority Critical patent/EP1187883A1/fr
Priority to AU50656/00A priority patent/AU780777B2/en
Priority to CA002374539A priority patent/CA2374539A1/fr
Publication of WO2000071626A1 publication Critical patent/WO2000071626A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
    • C23C22/36—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates
    • C23C22/364—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates containing also manganese cations
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • C09D5/082—Anti-corrosive paints characterised by the anti-corrosive pigment
    • C09D5/084—Inorganic compounds
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
    • C23C22/36—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates
    • C23C22/361—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates containing titanium, zirconium or hafnium compounds
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
    • C23C22/36—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates
    • C23C22/364—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates containing also manganese cations
    • C23C22/365—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates containing also manganese cations containing also zinc and nickel cations

Definitions

  • the present invention relates to a chromium-free organic / inorganic corrosion protection agent and a corrosion protection method for the treatment of surfaces made of steel, which are optionally provided with a metallic coating of zinc, aluminum, copper, nickel, etc., or of aluminum and its alloys. It is particularly suitable for top surface treatment in coil systems (coil coating) for the use of these substrates in the household and architecture sector and in the automotive industry.
  • phosphating is very complex in terms of plant technology, since depending on the substrate material it requires an additional activation step and, as a rule, a passivation step after phosphating.
  • the inorganic Coating adheres well to the primer applied to it.
  • the primer in turn not only has a favorable effect on the corrosion protection effect of the inorganic conversion layer, the primer layer in turn offers the top coat a good basis for adhesion.
  • sheet finishers are also supplying sheets with a functional pre-coating that facilitate mechanical processing such as punching, drilling, folding, profiling and / or deep drawing. Only after the final assembly of the workpiece is it finally provided with a top coat. In addition to the corrosion-inhibiting properties, the functional pre-coating must also give the sheet mechanical properties. Methods for the production of these layers are known on the basis of chromium-containing inorganic / organic compositions and chromium-free, exclusively organic preparations, the latter having only a limited corrosion protection effect.
  • the organic films In the automotive industry, galvanized steel sheet pre-coated with thin organic films is increasingly used. This substrate ensures good protection against corrosion, even in areas of the body that are difficult or impossible to access in the normal painting process. By using such precoated materials, cost-intensive secondary corrosion protection measures such as cavity sealing and seam sealing can be reduced or saved entirely.
  • the organic films often also contain pigments and fillers which increase the electrical conductivity. Such materials are known for example under the names Durasteel TM, Bonazinc TM, Durazinc TM or Granocoat TM.
  • Materials coated in this way have a thin organic coating over a conversion layer, for example a chromating or phosphating layer, which consists, for example, of binders on epoxy or polyurethane resins, polyamides or polyacrylates.
  • the organic layers are generally applied in a thickness of approximately 0.3 to approximately 5 ⁇ m.
  • This coating of the metal strips is generally carried out in a two-stage process which is complex in terms of plant technology, in which the inorganic conversion layer is first produced and then the organic polymer film is applied in a second treatment stage.
  • US-A-5 344 504 describes a coating process for galvanized steel, in which the substrate is brought into contact with a treatment solution having the following composition: 0.1 to 10 g / l of a tetrabz. Hexafluoro acid of boron, silicon, titanium and zircon or hydrofluoric acid, about 0.015 to about 6 g / l cations of cobalt, copper, iron, manganese, nickel, strontium or zinc and optionally up to about 3 g / l of a polymer selected from polyacrylic acid, Polymethacrylic acid and its esters.
  • the pH of this treatment solution is in the range from about 4 to about 5.
  • WO 95/14117 also describes a method for treating surfaces made of zinc or aluminum or their alloys.
  • the surfaces are brought into contact with a treatment solution with a pH value below 3, which contains a complex between a metal oxoion and a heteroion.
  • the metal oxoion is selected from molybdate, tungstate and vanadate.
  • the heteroion is selected from phosphorus, aluminum, silicon, manganese, magnesium, zirconium, titanium, tin, cerium and nickel.
  • the treatment solution also contains an organic film former which is compatible with the other components of the solution.
  • EP-A-694 593 recommends treating the metal surfaces with a treatment solution which contains the following components: an organic polymer or copolymer in which 0.5 to 8% of the monomers carry groups which can form compounds with metal ions, complex cations or Anions of aluminum, calcium, cerium, cobalt, molybdenum, silicon, vanadium, zircon, titanium, trivalent chromium and zinc, an oxidizing agent such as nitric acid, perchloric acid or hydrogen peroxide and an acid such as oxalic acid, acetic acid, boric acid, phosphoric acid, sulfuric acid, nitric acid or Hydrochloric acid.
  • a treatment solution which contains the following components: an organic polymer or copolymer in which 0.5 to 8% of the monomers carry groups which can form compounds with metal ions, complex cations or Anions of aluminum, calcium, cerium, cobalt, molybdenum, silicon, vanadium, zircon, titanium, trivalent chromium and zinc
  • WO 95/04169 teaches the treatment of metal surfaces with a treatment solution which contains at least the following components: fluorocomplexes of titanium, zirconium, hafnium, silicon, aluminum and boron, metal ions selected from cobalt, magnesium, manganese, zinc, nickel, tin, copper , Zircon, iron and strontium, phosphates or phosphonates and water-soluble or water-dispersible organic film formers.
  • EP-A-792 922 describes a chromium-free corrosion-inhibiting coating composition for aluminum or aluminum alloys which contains a film-forming organic polymer and (i) a salt selected from esters of rare earth metals, alkali or alkaline earth metal adadate and furthermore (ii) a borate salt of an alkaline earth metal.
  • a film-forming organic polymer and (i) a salt selected from esters of rare earth metals, alkali or alkaline earth metal adadate and furthermore (ii) a borate salt of an alkaline earth metal.
  • preferred polymers are epoxides, including polyimide-based epoxies, polyurethanes, acrylic polymers and alkyd-based systems.
  • this coating composition must therefore contain at least one borate and a further component, which can be a vanadate.
  • EP-A-685534 describes a method for protecting a steel substrate by means of a thin film of an organic-inorganic hybrid polymer based on an alkoxysilane, another condensable one Organometallic compound of the formula M (OR) 4 and (meth) acrylic acid and a polymerization initiator described.
  • the coating is effected by thermal or photopolymerization.
  • Zircon and titanium are mentioned as metals for the organometallic compound.
  • Such a film is said to protect steel substrates from corrosion and oxidation, and also to protect the substrate from shock and other effects.
  • WO 98/47631 describes a method for repairing defective pretreated metal surfaces.
  • an aqueous acidic solution containing fluorometalate anions, divalent or tetravalent cations of cobalt, magnesium, manganese, zinc, nickel, tin, copper, zirconium, iron and strontium is applied to the defective metal surfaces; Phosphorus-containing inorganic oxo anions and phosphonate anions and a water-soluble and / or water-dispersible organic polymer and / or a polymer-forming resin.
  • the document makes no statement as to whether such compositions are also suitable for the first coating of non-precoated metal strip.
  • the as yet unpublished DE-A-1 9754108.9 describes a chrome-free aqueous corrosion protection agent for the treatment of surfaces made of galvanized or alloy-galvanized steel and aluminum.
  • it contains hexafluoro anions of titanium and / or zirconium, vanadium ions, cobalt ions, phosphoric acid and preferably also an organic film former, in particular based on polyacrylate.
  • This anti-corrosion agent is particularly suitable for the anti-corrosion treatment of metal strips.
  • DE-A-4412138 describes a process for producing chromium-free conversion layers on the surface of aluminum and its alloys in the no-rinse process.
  • aqueous solutions which contain titanium and / or zirconium as well as a Orthophosphate, fluorides and 0.15 to 1.5 g / l of a water-soluble or homogeneously dispersible organic film former.
  • a solid film with a mass per unit area of about 50 to 350 mg / m 2 remains on the metal surface. Larger layer thicknesses, in particular with a predominant proportion of organic film-forming agents, are not disclosed.
  • US-A-5449415 describes a chrome-free conversion coating especially for cold-rolled steel, which contains a component made of titanium, zirconium, hafnium, silicon and boron anions and a cation component made of cobalt, magnesium, manganese and similar heavy metals and a sufficient one Amount of free acid to ensure a pH in the range between 0.5 and 5.0. Furthermore, these compositions contain inorganic phosphorus-containing oxyanions or phosphonate anions and a small proportion of water-soluble or water-dispersible organic polymers and polymer-forming resins. The ratio of the polymers or polymer-forming resins to the inorganic anions of the coating should be in the range 1: 2 to 3: 1. Coating thicknesses between 5 and 500 mg / m 2 (area-related mass of the dry film) can be achieved in this way. Larger layer thicknesses cannot be achieved with this coating composition.
  • US-A-5427632 describes very similar compositions to the aforementioned, with the difference that they still contain a dissolved oxidizing agent and can contain anti-settling agents. Even after the teaching of this document, no higher layer thicknesses of the coating are disclosed.
  • aqueous solutions for treating metallic surfaces and processes for their use.
  • This aqueous solution should contain one or more compounds of the type XYZ, where Y is an organic group with up to 50 C atoms and X is a carboxylic acid, sulfone, sulfate, phosphonate or phosphate group and Z is a functional group such as OH , SH-, NH 2 - the CN group.
  • Such connections are ' also referred to as SAM compounds (Seif Assembling Molecule). They only allow very thin layer thicknesses of the coatings in the practically monomolecular range, that is to say layer thicknesses of 5 to 10 nm are typically achieved in this way.
  • the treatment process should be able to be carried out without the use of chromium compounds and, if possible, with the exclusion of organic solvents.
  • the main fields of application are the household appliance and architecture industries mentioned above, as well as the automotive industry.
  • Vanadium, iron, manganese, molybdenum or tungsten d.) 0.5 to 30% by weight of at least one water-soluble or water-dispersible film-forming organic polymer or copolymer (based on active substance), e.) 0.1 to 10% by weight of an organophosphonic acid f.) optionally further auxiliaries and additives .
  • the invention further relates to a method for the corrosion-protecting treatment of steel, which is optionally provided with a metallic coating of zinc, aluminum, copper, nickel or similar metals, or aluminum or its alloys, which includes the following essential process steps:
  • the surface of the substrate is brought into contact with a corrosion protection agent of the type mentioned above for a period of time between 0.5 and 60 seconds at a treatment temperature between 10 and 50 ° C, preferably 15 and 35 ° C;
  • the treatment temperature can be set by supplying heat via the workpiece or the treatment solution,
  • the excess anticorrosive agent is removed from the surface, if necessary, and
  • c) is heated for a period of 1 to 120 seconds by suitable supply of heat, with peak metal temperatures between 50 ° C and 150 ° C should be reached, at the same time a crosslinking of the polymeric film and its anchoring on the metal surface takes place.
  • the anti-corrosion agent is preferably applied to the workpiece, preferably metal strip surface, by flooding / squeezing, spraying / squeezing, suitable scraper or roller applications.
  • Corrosion protection agents are: a) 5-50 g / l hexafluoro anions of titanium (IV), silicon (IV) and / or zircon (IV), b) 0-50 g / l phosphoric acid, c) 0-40 g / l ions of cobalt, nickel, vanadium, iron, manganese, molybdenum, tungsten, d) 5-30% by weight of one or more film-forming organic polymers or copolymers (based on the active substance) e) 0.1-10% by weight of an organophosphonic acid.
  • concentration ranges of components a) to e) should preferably be chosen so that the ratio of polymer component d) to inorganic anion component a) is greater than 3.1. This enables “thick layers”, the majority of the layer obtained being the organic polymer. “Thick layers” in the sense of this invention have area-based masses of the coating after drying of between 0.1 and 5 g / m 2 .
  • the pH of the anticorrosive agent is in the range from 0.5 to 4.0, preferably in the range from 0.7 to 2.5.
  • Such an acidic agent dissolves the metal surfaces to be treated, so that a treatment bath which has been in use for some time can additionally contain cations which originate from the treated metallic substrates. Examples include zinc, aluminum, iron, nickel, silicon, lead and copper.
  • a large number of compounds are suitable as film-forming organic polymers or copolymers, but they must satisfy two essential selection criteria: firstly, they must be present in the strongly acidic aqueous solution, the also contains polyvalent inorganic ions, be soluble or dispersible in sufficient concentration without coagulation and / or precipitation of the polymeric constituents. On the other hand, they must contain at least partially crosslinkable groups which allow the polymer layer to be sufficiently crosslinked in a short time by the application of heat and to be adhesively bonded to the substrate.
  • film-forming polymers are epoxy resins, aminoplast resins (e.g. melamine-formaldehyde resins, urea
  • Formaldehyde resins can contain crosslinkable comonomers known per se.
  • Examples include acrylic acid, methacrylic acid, glycidyl (meth) acrylate, acrylamide, N-methylolacrylamide, N, N-bis-alkoxymethyl (meth) acrylamide and similar thermally crosslinkable groups, where the alkoxy group can have 1 to 4 carbon atoms.
  • Crosslinkers known per se can also be used in the form of epoxy resins, urea derivatives, or (blocked) polyisocyanates or their oligomeric derivatives.
  • Self-crosslinking or externally crosslinkable (meth) acrylate dispersions or emulsions or their combination with epoxy resins and / or copolymers of 4-hydroxystyrene are particularly preferred.
  • the latter copolymers can be represented by the following general formula: y- (R 1 -NR 2 - aminomethyl) -4-hydroxystyrene, where y 2, 3, 5 or 6 and R 1 is an alkyl group with 1 to 4 carbon atoms , preferably a methyl group and R 2 can be represented by the following general formula: H (CHOH) n CH 2 -, where n is an integer between 1 and 7, preferably between 3 and 5.
  • the Average molecular weight of the aforementioned polymers is usually in the range between 600 and 20,000, preferably between 800 and 6,000.
  • the molecular weights of water-soluble polymers are more likely to be found in the lower range, while the molecular weights of water-dispersible polymers are generally found in the middle to upper range.
  • Further suitable film-forming organic (co) polymers are mentioned in T. Brock, M. Groteklaes, P. Miscke, "Textbook of coating technology", Vincentz-Verlag, 1998 in chapter 2.1.4 and chapter 3.5. The binders mentioned there are express Part of this registration.
  • organophosphonic acids Another important component of the compositions are organophosphonic acids, specific examples are the following phosphonic acids and diphosphonic acids:
  • N, N '- dimethylureidomethane diphosphonic acid N- (2-hydroxyethyl) ethylenediamine -N.N'.N'- trismethylenephosphonic acid
  • compositions according to the invention may contain, as further additives, conductivity pigments or conductive fillers, such as iron phosphide (Ferrophos), vanadium carbide, titanium nitride, carbon black, graphite, molybdenum disulfide or barium sulfate doped with tin or antimony. Iron phosphide is particularly preferred.
  • the conductivity pigments or fillers are added to improve the weldability or to improve the coating with electrocoat materials.
  • silica suspensions can be used - especially when using the anti-corrosion agents for aluminum substrates.
  • auxiliaries should be in finely divided form, that is to say their average particle diameter is between 0.005 and 5 ⁇ m, preferably between 0.05 and 2.5 ⁇ m.
  • the auxiliaries are used in proportions between 0.1 and 30% by weight.
  • the compositions may contain additives to improve the forming behavior, for example wax-based derivatives based on natural or synthetic waxes, for example polyethylene, polytetrafluoroethylene (PTFE) waxes or wax derivatives.
  • PTFE polytetrafluoroethylene
  • the pH of the application solutions - i.e. the original composition or a variant further diluted with water - is between 0.5 and 4.0, preferably between 0.7 and 2.5.
  • the application solution is applied in a manner known per se by roller application (chem coating), stripping, dipping / squeezing or spraying / squeezing onto a steel strip or (alloyed) aluminum strip, which may have a metallic coating. They are used at temperatures between 10 and 50 ° C, preferably between 15 and 35 ° C. The temperature can be adjusted by supplying heat via the workpiece or the treatment solution.
  • the layers produced in this way can be coated with the paint systems customary in the household appliance and / or architecture industry, i.e. a liquid primer with subsequent coating with a liquid topcoat can be used, and powder coating with a single-layer paint can also be carried out .
  • the corrosion protection layer according to the invention can be used immediately, that is without Primer treatment, to be coated with typical tape top coats.
  • the layers created in this way protect the sheet and provide adequate protection against corrosion.
  • a salt spray test in accordance with DIN 50021 SS can withstand more than 250 hours.
  • a salt spray test of more than 250 hours according to DIN 50021 ESS has also been successfully passed for (alloyed) aluminum.
  • a climatic test according to DIN 50017 KK for (alloy) galvanized steel is passed more than 3 weeks without white rust formation.
  • the corrosion resistance of materials which have been treated with the corrosion protection composition according to the invention, with or without a primer coating reaches the values which can be achieved with a conventional treatment.
  • the reshaping behavior is improved compared to substrates not coated according to the invention; furthermore, the substrates coated according to the invention can be cataphoretically coated under the same conditions and with the same result as the material that is typically phosphated in automobiles.
  • the method according to the invention can also take the place of conventional chromating and phosphating methods if subsequently a coating with a further corrosion protection layer such as Granocoat TM and the like is to take place.
  • the strips can be brought into contact with the treatment solution or dispersion according to the invention without prior cleaning.
  • the metal strips to be treated were stored and / or transported before the coating according to the invention, they are usually provided with anti-corrosion oils or at least so far soiled that cleaning before the coating according to the invention is necessary. This can be done with common weakly to strongly alkaline cleaners, with aluminum and its alloys also with acidic cleaners.
  • the corrosion protection composition according to the invention may also contain very low concentrations of organophosphonic acid and may be free of organophosphonic acids.
  • Demineralized water 73.5 62.4 50.6 74.6 75.8 53.0 53.6 62.0 52.6 62.0 52.7 53.2 52.6 52.0 74.5
  • Wax emulsion based on polyethylene and paraffins approx. 40% solids
  • organophosphonic acids used were, for example: 1,2-diaminopropane tetrakis (methylenephosphonic acid), diethylenetriaminepentakis (methylenephosphonic acid),
  • Ethylenediamine tetrakis (methylenephosphonic acid), N-carboxy methane-1-aminoethane-1,1-diphosphonic acid 8.) Test according to DIN 50021 SS, white rust attack ⁇ 5 area% after 100 h 9.) Additional coating with PUR / PA coil -Coating top coat, 20 ⁇ m, test according to DIN 50021 ESS, infiltration at the test scratch in mm
  • Examples 1 to 3 and 6 and 7 listed in Table 1 are not according to the invention, they already show significant white rust attack on galvanized steel in the test according to DIN 50021 SS after about 100 hours.
  • Examples 4, 5 and 15 show good results of corrosion protection on aluminum,
  • Examples 8 to 14 show good results of corrosion protection on galvanized steel.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Metallurgy (AREA)
  • Mechanical Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)

Abstract

Cette invention concerne agent anticorrosif aqueux dépourvu de chrome, convenant à la réalisation de fines couches organiques sur des surfaces en acier, en acier recouvert de métal (par exemple de zinc ou d'un alliage au zinc) et en aluminium. Cet agent anticorrosif comprend principalement les éléments suivants: a) 0,5 à 100 g/l d'anions hexafluoro du titane (IV), silicium (IV) et/ou zircon (IV); b) 20 à 100 g/l d'acide phosphorique; c) 0 à 100 g/l d'un ou plusieurs composés du cobalt, nickel, vanadium, fer, manganèse, molybdène ou tungstène; d) 0,5 à 30 % en poids d'au moins un polymère ou copolymère organique filmogène soluble ou dispersable dans l'eau; e) 0,1 à 10 % en poids d'un acide organophosphonique; f) éventuellement un ou plusieurs auxiliaires ou additifs. Les compositions conviennent particulièrement au traitement anticorrosif de bandes de métal et sont de préférence appliquées de manière à former sur la surface une couche sèche de masse surfacique comprise entre 0,1 et 5 g/m<2>.
PCT/EP2000/004267 1999-05-20 2000-05-11 Agent anticorrosif depourvu de chrome et procede de protection contre la corrosion Ceased WO2000071626A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP00935006A EP1187883A1 (fr) 1999-05-20 2000-05-11 Agent anticorrosif depourvu de chrome et procede de protection contre la corrosion
AU50656/00A AU780777B2 (en) 1999-05-20 2000-05-11 Chromium-free anticorrosive and anticorrosive method
CA002374539A CA2374539A1 (fr) 1999-05-20 2000-05-11 Agent anticorrosif depourvu de chrome et procede de protection contre la corrosion

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19923084.6 1999-05-20
DE1999123084 DE19923084A1 (de) 1999-05-20 1999-05-20 Chromfreies Korrosionsschutzmittel und Korrosionsschutzverfahren

Publications (1)

Publication Number Publication Date
WO2000071626A1 true WO2000071626A1 (fr) 2000-11-30

Family

ID=7908575

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2000/004267 Ceased WO2000071626A1 (fr) 1999-05-20 2000-05-11 Agent anticorrosif depourvu de chrome et procede de protection contre la corrosion

Country Status (5)

Country Link
EP (1) EP1187883A1 (fr)
AU (1) AU780777B2 (fr)
CA (1) CA2374539A1 (fr)
DE (1) DE19923084A1 (fr)
WO (1) WO2000071626A1 (fr)

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001066827A1 (fr) * 2000-03-04 2001-09-13 Henkel Kommanditgesellschaft Auf Aktien Procede pour proteger des surfaces metalliques contre la corrosion
WO2002077323A3 (fr) * 2001-03-27 2003-10-23 Henkel Kgaa Primaire pour peintures et adhesifs sur metaux
WO2005021834A1 (fr) * 2003-08-26 2005-03-10 Henkel Kommanditgesellschaft Auf Aktien Couches de conversion colorées sur des surfaces métalliques
CN100339507C (zh) * 2003-06-20 2007-09-26 联合工艺公司 用于镁合金的抗腐蚀、无铬酸盐转化涂层
WO2008022819A1 (fr) * 2006-08-24 2008-02-28 Henkel Ag & Co. Kgaa agent anti-corrosion thermiquement durcissable exempt de chrome
WO2008034449A1 (fr) * 2006-09-18 2008-03-27 Henkel Ag & Co. Kgaa Revêtement hybride organique-inorganique mince sans chrome sur des métaux zincifères
WO2008092528A1 (fr) * 2007-02-01 2008-08-07 Henkel Ag & Co. Kgaa Prétraitement pour métaux contenant des pigments luminescents
US7491274B2 (en) 2004-10-29 2009-02-17 Chemetall Corp. Non-chrome metal treatment composition
WO2013000674A1 (fr) * 2011-06-29 2013-01-03 Henkel Ag & Co. Kgaa Dépôt électrolytique de fer sur des surfaces galvanisées
WO2014072443A1 (fr) * 2012-11-08 2014-05-15 Henkel Ag & Co. Kgaa Prétraitement de boîtes pour une meilleure adhérence de vernis
EP2255025B1 (fr) 2008-03-11 2015-06-17 Chemetall GmbH Procédé d enduction de surfaces métalliques avec un agent de passivation
JP2016501986A (ja) * 2014-01-08 2016-01-21 日本パーカライジング株式会社 塗膜接着性を向上させるための缶の前処理方法
US9771493B2 (en) 2012-11-08 2017-09-26 Henkel Ag & Co. Kgaa Can pretreatment for improved coating adhesion
US10125424B2 (en) 2012-08-29 2018-11-13 Ppg Industries Ohio, Inc. Zirconium pretreatment compositions containing molybdenum, associated methods for treating metal substrates, and related coated metal substrates
US10400337B2 (en) 2012-08-29 2019-09-03 Ppg Industries Ohio, Inc. Zirconium pretreatment compositions containing lithium, associated methods for treating metal substrates, and related coated metal substrates
US11518960B2 (en) 2016-08-24 2022-12-06 Ppg Industries Ohio, Inc. Alkaline molybdenum cation and phosphonate-containing cleaning composition
DE102014203412B4 (de) 2013-02-25 2025-08-21 Zschimmer & Schwarz Mohsdorf GmbH & Co. KG. Verfahren, Formulierung und Verwendung der Formulierung zur gleichzeitigen Entschichtung und Passivierung von Edelstahloberflächen

Families Citing this family (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7294211B2 (en) 2002-01-04 2007-11-13 University Of Dayton Non-toxic corrosion-protection conversion coats based on cobalt
EP1504743B1 (fr) * 2002-03-28 2013-05-08 Shiseido Company, Ltd. Poudre insoluble, poudre restaurant la fonction barriere de la peau, poudre empechant/moderant les gercures de la peau et preparation a usage externe contenant cette poudre
DE10349728A1 (de) 2003-10-23 2005-05-25 Basf Ag Im wesentlichen Chrom-freies Verfahren zum Passivieren von metallischen Oberflächen aus Zn, Zn-Legierungen, AI oder AI-Legierungen
JP2006161115A (ja) * 2004-12-08 2006-06-22 Nippon Paint Co Ltd 化成処理剤及び表面処理金属
EP1836330A1 (fr) * 2005-01-14 2007-09-26 Henkel Kommanditgesellschaft Auf Aktien Formulations passivees organiques a film mince stables sans chrome
US8273412B2 (en) 2005-01-28 2012-09-25 Basf Aktiengesellschaft Method for applying corrosion protection layers comprising thioamides to metallic surfaces
DE102005005858A1 (de) 2005-02-08 2006-08-17 Henkel Kgaa Verfahren zur Beschichtung von Metallblech, insbesondere Zinkblech
EP1851276B1 (fr) 2005-02-10 2017-01-25 BASF Coatings GmbH Un procédé pour appliquer des couches de protection contre la corrosion depourvues de chrome comprenant d'acides dithiophosphiniques et/ou de leurs sels
DE102007021364A1 (de) 2007-05-04 2008-11-06 Henkel Ag & Co. Kgaa Metallisierende Vorbehandlung von Zinkoberflächen
WO2009072905A2 (fr) * 2007-12-04 2009-06-11 Katja Products Limited Revêtement de surface
DE102007061109B4 (de) 2007-12-19 2013-01-17 Henkel Ag & Co. Kgaa Behandlungslösung zum Beschichten eines Stahlbandes, ein Verfahren zum Aufbringen derselben sowie ein Stahlband mit einer Beschichtung erhalten aus der Behandlungslösung zur Verbesserung des Umformverhaltens
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.
WO2013160568A1 (fr) 2012-04-25 2013-10-31 Arcelormittal Investigacion Y Desarrollo, S.L. Procédé de réalisation d'une tôle à revêtements ZnAlMg comprenant l'application d'une solution acide et tôle correspondante.
DE102012021241A1 (de) 2012-10-29 2014-04-30 Airbus Operations Gmbh Zusammensetzung für die lokale Applikation von chemischen Konversionsschichten
EP2733179A1 (fr) * 2012-11-19 2014-05-21 Basf Se Mélanges pour le revêtement de surfaces métalliques comprenant des inhibiteurs de corrosion organiques
JP7463379B2 (ja) 2019-01-02 2024-04-08 ノベリス・インコーポレイテッド 缶エンドストックをラミネート加工するためのシステム及び方法
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
CN115161628B (zh) * 2021-04-07 2023-10-13 中南大学 一种电解锰的钝化剂及钝化方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4992116A (en) * 1989-04-21 1991-02-12 Henkel Corporation Method and composition for coating aluminum
US5427632A (en) * 1993-07-30 1995-06-27 Henkel Corporation Composition and process for treating metals
US5858282A (en) * 1997-11-21 1999-01-12 Ppg Industries, Inc. Aqueous amine fluoride neutralizing composition for metal pretreatments containing organic resin and method

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5449415A (en) * 1993-07-30 1995-09-12 Henkel Corporation Composition and process for treating metals
DE4412138A1 (de) * 1994-04-08 1995-10-12 Henkel Kgaa Chromfreies Verfahren zur No-Rinse Behandlung von Aluminium und seinen Legierungen sowie hierfür geeignete wäßrige Badlösungen
DE19654642C2 (de) * 1996-12-28 2003-01-16 Chemetall Gmbh Verfahren zur Behandlung metallischer Oberflächen mit einer wässerigen Lösung

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4992116A (en) * 1989-04-21 1991-02-12 Henkel Corporation Method and composition for coating aluminum
US5427632A (en) * 1993-07-30 1995-06-27 Henkel Corporation Composition and process for treating metals
US5858282A (en) * 1997-11-21 1999-01-12 Ppg Industries, Inc. Aqueous amine fluoride neutralizing composition for metal pretreatments containing organic resin and method

Cited By (31)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001066827A1 (fr) * 2000-03-04 2001-09-13 Henkel Kommanditgesellschaft Auf Aktien Procede pour proteger des surfaces metalliques contre la corrosion
KR100757723B1 (ko) 2000-03-04 2007-09-11 니혼 파커라이징 가부시키가이샤 금속 표면의 부식 방지 방법
WO2002077323A3 (fr) * 2001-03-27 2003-10-23 Henkel Kgaa Primaire pour peintures et adhesifs sur metaux
CN100339507C (zh) * 2003-06-20 2007-09-26 联合工艺公司 用于镁合金的抗腐蚀、无铬酸盐转化涂层
WO2005021834A1 (fr) * 2003-08-26 2005-03-10 Henkel Kommanditgesellschaft Auf Aktien Couches de conversion colorées sur des surfaces métalliques
US8293029B2 (en) 2003-08-26 2012-10-23 Henkel Ag & Co. Kgaa Colored conversion layers on metal surfaces
US7491274B2 (en) 2004-10-29 2009-02-17 Chemetall Corp. Non-chrome metal treatment composition
WO2008022819A1 (fr) * 2006-08-24 2008-02-28 Henkel Ag & Co. Kgaa agent anti-corrosion thermiquement durcissable exempt de chrome
RU2454486C2 (ru) * 2006-08-24 2012-06-27 Хенкель Аг Унд Ко. Кгаа Не содержащее хром термически отверждаемое противокоррозионное средство
AU2007287782B2 (en) * 2006-08-24 2011-06-30 Henkel Ag & Co. Kgaa Chromium-free, thermally curable corrosion protection composition
CN101506405B (zh) * 2006-08-24 2011-07-06 汉高两合股份公司 无铬的、可热硬化的防腐蚀剂
WO2008034449A1 (fr) * 2006-09-18 2008-03-27 Henkel Ag & Co. Kgaa Revêtement hybride organique-inorganique mince sans chrome sur des métaux zincifères
CN101512044A (zh) * 2006-09-18 2009-08-19 汉高两合股份公司 在含锌的金属上的非铬的薄有机-无机混合涂层
WO2008092528A1 (fr) * 2007-02-01 2008-08-07 Henkel Ag & Co. Kgaa Prétraitement pour métaux contenant des pigments luminescents
DE102007005943A1 (de) 2007-02-01 2008-08-07 Henkel Ag & Co. Kgaa Metall-Vorbehandlung mit lumineszierenden Pigmenten
EP2255025B2 (fr) † 2008-03-11 2018-07-18 Chemetall GmbH Procédé d enduction de surfaces métalliques avec un agent de passivation
EP2255025B1 (fr) 2008-03-11 2015-06-17 Chemetall GmbH Procédé d enduction de surfaces métalliques avec un agent de passivation
WO2013000674A1 (fr) * 2011-06-29 2013-01-03 Henkel Ag & Co. Kgaa Dépôt électrolytique de fer sur des surfaces galvanisées
US9309602B2 (en) 2011-06-29 2016-04-12 Henkel Ag & Co. Kgaa Electrolytic iron metallizing of zinc surfaces
US10920324B2 (en) 2012-08-29 2021-02-16 Ppg Industries Ohio, Inc. Zirconium pretreatment compositions containing molybdenum, associated methods for treating metal substrates, and related coated metal substrates
US10400337B2 (en) 2012-08-29 2019-09-03 Ppg Industries Ohio, Inc. Zirconium pretreatment compositions containing lithium, associated methods for treating metal substrates, and related coated metal substrates
US10125424B2 (en) 2012-08-29 2018-11-13 Ppg Industries Ohio, Inc. Zirconium pretreatment compositions containing molybdenum, associated methods for treating metal substrates, and related coated metal substrates
CN104769158A (zh) * 2012-11-08 2015-07-08 汉高股份有限及两合公司 用于改善涂层粘合性的罐预处理
US9771493B2 (en) 2012-11-08 2017-09-26 Henkel Ag & Co. Kgaa Can pretreatment for improved coating adhesion
US9512524B2 (en) 2012-11-08 2016-12-06 Henkel Ag & Co. Kgaa Can pretreatment for improved coat adhesion
JP2016505707A (ja) * 2012-11-08 2016-02-25 日本パーカライジング株式会社 塗膜密着性を向上させるための缶の前処理方法
US10870923B2 (en) 2012-11-08 2020-12-22 Henkel Ag & Co. Kgaa Can pretreatment for improved coat adhesion
WO2014072443A1 (fr) * 2012-11-08 2014-05-15 Henkel Ag & Co. Kgaa Prétraitement de boîtes pour une meilleure adhérence de vernis
DE102014203412B4 (de) 2013-02-25 2025-08-21 Zschimmer & Schwarz Mohsdorf GmbH & Co. KG. Verfahren, Formulierung und Verwendung der Formulierung zur gleichzeitigen Entschichtung und Passivierung von Edelstahloberflächen
JP2016501986A (ja) * 2014-01-08 2016-01-21 日本パーカライジング株式会社 塗膜接着性を向上させるための缶の前処理方法
US11518960B2 (en) 2016-08-24 2022-12-06 Ppg Industries Ohio, Inc. Alkaline molybdenum cation and phosphonate-containing cleaning composition

Also Published As

Publication number Publication date
AU5065600A (en) 2000-12-12
AU780777B2 (en) 2005-04-14
DE19923084A1 (de) 2000-11-23
CA2374539A1 (fr) 2000-11-30
EP1187883A1 (fr) 2002-03-20

Similar Documents

Publication Publication Date Title
EP1187883A1 (fr) Agent anticorrosif depourvu de chrome et procede de protection contre la corrosion
EP1517955B1 (fr) Polymeres contenant du carboxylate pour le traitement de surfaces metalliques
EP2449149B1 (fr) Traitement de protection anticorrosion pour des surfaces à base de zinc et d&#39;alliages de zinc
EP2057303B1 (fr) Agent anti-corrosion thermiquement durcissable exempt de chrome
DE19754108A1 (de) Chromfreies Korrosionsschutzmittel und Korrosionsschutzverfahren
DE10310972A1 (de) Stickstoffhaltige Polymere für die Metalloberflächenbehandlung
EP2145031A2 (fr) Prétraitement de métallisation de surfaces de zinc
WO2002031064A1 (fr) Procede de pretraitement et / ou d&#39;enduction de surfaces metalliques avant le formage a l&#39;aide d&#39;une couche de type peinture et utilisation des substrats ainsi recouverts
DE102004028764A1 (de) Strahlungshärtbares elektrisch leitfähiges Beschichtungsgemisch
EP1692325A1 (fr) Traitement de conversion en deux etapes
US20060169363A1 (en) Stable, non-chrome, thin-film organic passivates
EP2215285B1 (fr) Phosphatation au zirconium de pièces métalliques, en particulier en fer
EP1570109B1 (fr) Procede pour revetir des substrats metalliques avec un agent de revetement polymerisable par polymerisation radicalaire, et substrats ainsi revetus
US20090297843A1 (en) Non-chrome thin organic-inorganic hybrid coating on zinciferous metals
EP1292719A1 (fr) Agent adhesif dans des solutions pour conversion
EP1531012A2 (fr) Protection supplémentaire contre la corrosion pour des piéces de tôle métallique disposant déjà d&#39;un revêtement organique
WO2005061570A1 (fr) Resine phenol-aldehyde fonctionnalisee et procede de traitement de surfaces metalliques
DE19745801A1 (de) Verfahren zum Beschichten von Metallen und hiermit beschichtetes Metall
JPS60110899A (ja) Ζｎ系金属粉体を含有させた電着塗膜を得る塗装方法

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AU BR CA CN KR PL RU SK US ZA

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: 2000935006

Country of ref document: EP

ENP Entry into the national phase

Ref document number: 2374539

Country of ref document: CA

Ref country code: CA

Ref document number: 2374539

Kind code of ref document: A

Format of ref document f/p: F

WWE Wipo information: entry into national phase

Ref document number: 50656/00

Country of ref document: AU

WWE Wipo information: entry into national phase

Ref document number: 09979261

Country of ref document: US

WWP Wipo information: published in national office

Ref document number: 2000935006

Country of ref document: EP

WWW Wipo information: withdrawn in national office

Ref document number: 2000935006

Country of ref document: EP

WWG Wipo information: grant in national office

Ref document number: 50656/00

Country of ref document: AU