EP3475464A1 - Procédé amélioré de prétraitement de protection anticorrosion d'une surface métallique qui contient de l'acier, de l'acier galvanisé, de l'aluminium, du magnésium et/ou un alliage de zinc et de magnésium - Google Patents

Procédé amélioré de prétraitement de protection anticorrosion d'une surface métallique qui contient de l'acier, de l'acier galvanisé, de l'aluminium, du magnésium et/ou un alliage de zinc et de magnésium

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Publication number
EP3475464A1
EP3475464A1 EP17731571.0A EP17731571A EP3475464A1 EP 3475464 A1 EP3475464 A1 EP 3475464A1 EP 17731571 A EP17731571 A EP 17731571A EP 3475464 A1 EP3475464 A1 EP 3475464A1
Authority
EP
European Patent Office
Prior art keywords
composition
group
metallic surface
magnesium
zinc
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
EP17731571.0A
Other languages
German (de)
English (en)
Other versions
EP3475464B1 (fr
Inventor
Stefan Birkenheuer
Carina HECKER
Oliver Sauer
Daniel SCHATZ
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.)
Chemetall GmbH
Original Assignee
Chemetall GmbH
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 Chemetall GmbH filed Critical Chemetall GmbH
Priority to PL17731571T priority Critical patent/PL3475464T3/pl
Publication of EP3475464A1 publication Critical patent/EP3475464A1/fr
Application granted granted Critical
Publication of EP3475464B1 publication Critical patent/EP3475464B1/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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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
    • C23C22/78—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
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
    • C23C22/36—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/73—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals characterised by the process
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/82—After-treatment
    • C23C22/83—Chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
    • C23C2222/20—Use of solutions containing silanes

Definitions

  • Magnesium and / or a zinc-magnesium alloy contains
  • the present invention relates to an improved method for anticorrosive pretreatment of a metallic surface containing steel, galvanized steel, aluminum, magnesium and / or a zinc-magnesium alloy. It also relates to a composition for improving the corrosion-protective pretreatment of such a metallic surface, a concentrate for producing this composition, a correspondingly coated metallic surface and the use of a correspondingly coated metallic substrate.
  • the coating of metallic surfaces with an aqueous composition containing organoalkoxysilanes, their hydrolysis and / or condensation products and other components is known.
  • the coatings formed can be used to achieve corrosion protection for the treated metal substrates as well as a certain improvement in the adhesion of further layers such as paints.
  • the prior art also includes the addition of certain acid-stable polymers to said compositions. In this way, the properties of the layers formed can be improved.
  • the object of the present invention is to overcome the disadvantages of the prior art, and for metallic surfaces containing steel, galvanized steel, aluminum, magnesium and / or a zinc-magnesium alloy, a to provide an improved process for corrosion-protective pretreatment, with which in particular the corrosion protection on steel substrates can be improved with at the same time good adhesion.
  • the object is achieved by a method according to claim 1, an aqueous composition according to claim 18, a concentrate according to claim 19, a metallic surface according to claim 20 and the use of a metallic substrate according to claim 21.
  • the metallic surface is brought into contact with an aqueous composition A, the
  • Copolymer comprising, in an alternating configuration, i) monomer units containing at least one carboxylic acid group, phosphonic acid group and / or
  • Titanium, zirconium and hafnium compounds Titanium, zirconium and hafnium compounds
  • composition A is brought into contact simultaneously with the composition A and the composition B.
  • aqueous composition is also to be understood as meaning, in addition to water as solvent / dispersant, still less than 50% by weight, based on the total amount of solvent / dispersant, of other organic solvents / dispersants.
  • composition B is to be understood as the fiction that all of the molecules of component b1) in composition B are hexafluorozirconic acid molecules, ie H 2 ZrF 6 .
  • complex fluorides are meant in addition to the deprotonated forms, the respective mono- or multi-protonated forms.
  • the metallic surface is sequentially contacted with a first composition, A, with a composition B and with a second composition A, wherein the first and second compositions A may also be chemically identical.
  • the metallic surface preferably contains steel or galvanized steel, more preferably galvanized steel, and most preferably hot-dip galvanized steel. Especially with these materials, problems have occurred with respect to the corrosive infiltration, but which could be satisfactorily solved by the present invention.
  • the at least one copolymer a) in the composition A is preferably stable at least at a partial range of the pH below 6. This is necessary if the metallic surface is to be contacted with a single composition, as described above, which is an acidic aqueous composition containing all components a), b1) and optionally b2).
  • the properties of the coatings formed, in particular the corrosion protection, can be significantly improved.
  • the copolymers used according to the invention contain acid groups which at least partially dissociate at the increased pH at the surface. This leads to negative charges on the copolymer, which in turn lead to an electrostatic attachment of the copolymer to the metallic surface and / or to the metal oxides - from component b1) and optionally at component b2) and optionally at component b3).
  • the thus-attached copolymer increases the barrier effect of the deposited layers against the diffusion or migration of corrosive salts to the metallic surface. The properties of the coatings formed are thereby improved.
  • the monomer units i) of the at least one copolymer a) in composition A which contain at least one carboxylic acid group, phosphonic acid group and / or sulfonic acid group, are for example, (meth) acrylic acid, vinylacetic acid, itaconic acid, maleic acid, vinylphosphonic acid and / or vinylsulphonic acid.
  • these monomer units each have at least one carboxylic acid group. More preferably, they each have at least two carboxylic acid groups. Particularly preferably, they each have exactly two carboxylic acid groups. Especially preferred here is maleic acid.
  • the at least one copolymer a) in the composition A comprises maleic acid as the monomer unit, this may be present partly in the form of the anhydride. This is the case when the copolymer added to the composition A or the concentrate for the preparation of this composition comprises maleic anhydride and in the composition A or in the concentrate no complete hydrolysis to maleic acid has yet taken place.
  • the monomer units ii) of the at least one copolymer a) in the composition A, which contain no acid group, can either be non-polar or polar.
  • the at least one copolymer a) may also have, as monomer units which do not contain an acid group, a mixture of nonpolar and polar monomer units.
  • Suitable nonpolar monomer units are in particular alkylenes, such as, for example, ethylene, propylene and / or butylene, and / or styrene.
  • a polar monomer units are in particular vinyl alcohol and / or vinyl acetate and / or vinyl ethers, such as methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether and / or butyl vinyl ether, and / or alkylene oxides such as ethylene oxide, propylene oxide and / or butylene oxide, and / or ethyleneimine and / or ( Meth) acrylic acid esters and / or (meth) acrylamide into consideration.
  • the length of the hydrocarbon chains in the monomer units ii), which contain no acid group, is only due to the resulting hydrophobicity of these Monomers and thus limited by the water solubility of the resulting copolymer.
  • the monomer units ii) which do not contain an acid group are vinyl ethers.
  • the monomer units ii) which do not contain an acid group are vinyl ethers.
  • the composition A contains as copolymer a) poly (methyl vinyl ether-a / f-maleic acid).
  • the at least one copolymer a) in composition A preferably has a degree of polymerization based on two monomer units in an alternating configuration of from 25 to 5700, more preferably from 85 to 1750, more preferably from 170 to 1300 and most preferably from 225 to 525. Its number-average molecular weight is preferably 5,000 to 1,000,000 g / mol, more preferably 15,000 to 300,000 g / mol, more preferably 30,000 to 225,000 g / mol, and most preferably 40,000 to 90,000 g / mol.
  • the composition A contains as the at least one copolymer a) poly (methylvinyl ether-a / f-maleic acid) having a number average molecular weight in the range from 40,000 to 60,000 g / mol, preferably from about 48,000 g / mol.
  • the composition A contains as the at least one copolymer a) poly (methyl vinyl ether-a / f-maleic acid) having a number average molecular weight in the range from 70,000 to 90,000 g / mol, preferably from about 80,000 g / mol ,
  • the metallic surface i) is contacted first with the composition A and then with the composition B, the concentration of the at least one copolymer a) in the composition A being in the range from 0.01 to 0.5 g / l, preferably from 0.05 to 0.3 g / l (calculated as solid additive).
  • the metallic surface iii) is brought into contact simultaneously with the composition A and the composition B, wherein the concentration of the at least one copolymer a) in the composition A in the range of 10 to 500 mg / l, preferably from 20 to 200 mg / l, more preferably from 20 to 150 mg / l, more preferably from 30 to 100 mg / l and most preferably from 40 to 60 mg / l (calculated as solid additive).
  • the composition B preferably has a pH in the range from 0.5 to 5.5, more preferably from 2 to 5.5, particularly preferably from 3.5 to 5.3 and very particularly preferably from 4.0 to 5, 0 on.
  • the pH is preferably adjusted with nitric acid, ammonium and / or sodium carbonate.
  • the composition B additionally comprises b2) at least one compound selected from the group consisting of organoalkoxysilanes, organosilanols, polyorganosilanols, organosiloxanes and polyorganosiloxanes.
  • organic is meant at least one organic group which is directly attached via a carbon atom to a silicon atom and, consequently, is not hydrolytically cleaved therefrom.
  • polyorganosiloxanes are understood as meaning those compounds which can be condensed from at least two organosilanols and form no polydimethylsiloxane.
  • concentration of b2) is preferably in the range of 1 to 200 mg / l, more preferably 5 to 100 mg / l, particularly preferably 20 to 50 mg / l and most preferably 25 to 45 mg / l (calculated as silicon).
  • the concentration of b1) is preferably in the range of 0.05 to 4 g / l, more preferably 0.1 to 1.5 g / l, more preferably 0.15 to 0.57 g / l preferably 0.20 to 0.40 g / l and most preferably about 0.25 g / l (calculated as hexafluorozirconic acid).
  • the contents of the components b1), b2) and b3) can be monitored photometrically during the treatment of the metallic surfaces by ICP-OES (optical emission spectrometry with inductively coupled plasma) or, if appropriate, a subsequent dosing of individual or several components can be.
  • ICP-OES optical emission spectrometry with inductively coupled plasma
  • the composition B contains as component b2) at least one organoalkoxysilane, organosilanol, polyorganosilanol, organosiloxane and / or polyorganosiloxane having in each case at least one amino group, urea group, imido group, imino group and / or ureido group per organoalkoxysilane / Organosilanolappel.
  • Component b2) is more preferably at least one organoalkoxysilane, organosilanol, polyorganosilanol, organosiloxane and / or polyorganosiloxane having in each case at least one, in particular one to two, amino groups per organoalkoxysilane / organosilanol unit.
  • composition B preferably contains as component b1) at least one complex fluoride selected from the group consisting of the complex fluorides of titanium, zirconium and hafnium.
  • zirconium complex fluoride Zirconium may also be added as zirconyl nitrate, zirconium carbonate, zirconyl acetate or zirconium nitrate, preferably as zirconyl nitrate. This applies accordingly for titanium and hafnium.
  • the content of the at least one complex fluoride is preferably in the range of 0.05 to 4 g / l, preferably 0.1 to 1.5 g / l and particularly preferably about 0.25 g / l (calculated as hexafluorozirconic acid).
  • the composition B contains as component b1) at least two different complex fluorides, in particular complex fluorides of two different metal cations and more preferably complex fluorides of titanium and zirconium.
  • the composition B additionally comprises a component b3), which is at least one kind of cation selected from the group consisting of cations of metals of the 1. to 3rd and 5th to 8th subgroup including lanthanides and the 2nd main group of the Periodic Table of the Elements as well as lithium, bismuth and tin and / or at least one corresponding compound.
  • a component b3) which is at least one kind of cation selected from the group consisting of cations of metals of the 1. to 3rd and 5th to 8th subgroup including lanthanides and the 2nd main group of the Periodic Table of the Elements as well as lithium, bismuth and tin and / or at least one corresponding compound.
  • the component b3) is preferably at least one type of cation selected from the group consisting of the cations of cerium and other lanthanides, chromium, iron, calcium, cobalt, copper, magnesium, manganese, molybdenum, nickel, niobium, tantalum, yttrium, Vanadium, lithium, bismuth, zinc and tin and / or at least one corresponding compound. More preferably, composition B comprises as component b3) zinc cations, copper cations and / or cations and / or at least one molybdenum compound. With particular preference, composition B comprises, as component b3), zinc cations, very particularly preferably zinc cations and copper cations.
  • composition B concentrations in composition B are preferably the following:
  • Molybdenum compound 10 to 100 mg / l (calculated as molybdenum).
  • composition B - depending on specific requirements or circumstances - additionally contains a component b4).
  • This is at least one compound selected from the group consisting of pH-affecting substances, organic solvents, water-soluble fluorine compounds and colloids.
  • composition B preferably has a content in the range from 0.1 to 20 g / l for component b4).
  • the pH-influencing substances are preferably selected from the group consisting of nitric acid, sulfuric acid, methanesulfonic acid, acetic acid, hydrofluoric acid, ammonium / ammonia, sodium carbonate and sodium hydroxide solution. Further preferred here is nitric acid, ammonium and / or sodium carbonate.
  • the organic solvents are preferably selected from the group consisting of methanol and ethanol. Thus, in practice, methanol and / or ethanol are present as reaction products of the organoalkoxysilane hydrolysis in the treatment baths.
  • the water-soluble fluorine compounds are preferably selected from the group consisting of fluoride-containing compound and fluoride anions.
  • the content of free fluoride in the composition B is preferably in the range of 0.015 to 0.15 g / l, more preferably 0.025 to 0.1 g / l, and particularly preferably in the range of 0.03 to 0.05 g / l.
  • the colloids are preferably metal oxide particles, more preferably metal oxide particles selected from the group consisting of ZnO, S1O2, CeO2, ZrO2 and ⁇ 2.
  • the composition B contains at least one kind of cation selected from the group consisting of alkali metal ions, ammonium ions and corresponding compounds. It particularly preferably contains sodium ions and / or ammonium ions.
  • Composition B may also contain phosphorus- and oxygen-containing compounds such as phosphates and / or phosphonates. In addition, it may have nitrate.
  • the content of sulfur-containing compounds should preferably be kept as low as possible.
  • the content of sulfur-containing compounds is more preferably less than 100 mg / l calculated as sulfur.
  • the metallic surface to be treated which has optionally been previously cleaned and / or pickled, can be sprayed, dipped or flooded with the composition A and / or with the composition B in each case. It is also possible to apply the respective composition manually by wiping or brushing or with rollers or rollers (coil coating method) on the metallic surface to be treated. Also possible is an electrolytic deposition of the respective composition on the metallic surface to be treated.
  • the treatment time in the parts treatment is preferably in the range of 15 seconds to 20 minutes, more preferably 30 seconds to 10 minutes, and particularly preferably in the range of 45 seconds to 5 minutes.
  • the Treatment temperature is preferably in the range of 5 to 50 ° C, more preferably 15 to 40 ° C and particularly preferably in the range of 25 to 35 ° C.
  • the method according to the invention is also suitable for the coating of strips (coils).
  • the duration of treatment is preferably in the range of a few seconds to a few minutes, for example in the range of 1 to 1000 seconds.
  • the metallic surface to be treated contains steel, galvanized steel, aluminum, magnesium and / or a zinc-magnesium alloy, more preferably it contains steel and / or galvanized steel, most preferably it contains steel.
  • the present invention also relates to an aqueous composition A for improving the anticorrosion pretreatment of a metallic surface containing steel, galvanized steel, aluminum, magnesium and / or a zinc-magnesium alloy, as described above.
  • the invention relates to a concentrate from which a composition A according to the invention can be prepared by dilution with water and optionally adjusting the pH.
  • the treatment bath with composition A according to the invention can be prepared by diluting the concentrate with water and / or an aqueous solution preferably by the factor 1: 5,000 to 1:10, more preferably 1: 1, 000 to 1: 10, more preferably 1: 300 to 1:10, and most preferably by a factor of about 1: 100 are obtained.
  • the present invention relates to a metallic surface, which contains steel, galvanized steel, aluminum, magnesium and / or a zinc-magnesium alloy, and has been coated by the method according to the invention and the coating formed has a determined by RFA (X-ray fluorescence analysis) layer weight of :
  • ii) 0.5 to 50 mg / m 2 , preferably 1 to 30 and particularly preferably 2 to 10 mg / m 2, based only on component b2) (calculated as silicon).
  • the coatings produced by the process according to the invention serve as corrosion protection and adhesion promoters for further coatings.
  • they can easily be further coated with at least one primer, lacquer, adhesive and / or a lacquer-like organic composition.
  • at least one of these further coatings can be cured by heating and / or irradiation.
  • the coatings produced by the process according to the invention are preferably rinsed before further treatment in order to remove excess polymer and interfering ions from the metallic surface.
  • the first additional coating can be applied in the wet-on-wet process.
  • the paint used is preferably a cathodic electrodeposition paint (KTL) based on epoxides and / or (meth) acrylates.
  • KTL cathodic electrodeposition paint
  • the present invention finally also relates to the use of a metallic substrate coated by the process according to the invention in the automotive industry, for rail vehicles, in the aerospace industry, in the Apparatus construction, in engineering, in the construction industry, in the furniture industry, for the production of crash barriers, lamps, profiles, panels or small parts, for the production of bodies or body parts, of individual components, pre-assembled or connected elements, preferably in the automotive or aerospace industry , for the manufacture of equipment or installations, in particular household appliances, control equipment, test equipment or construction elements.
  • KTL cathodic electrodeposition paint
  • Gardoclean ® S 5176 (Chemetall;. Contains phosphate, borate and surfactant) is used.
  • 15 g / l were set in a 50 l bath, heated to 60 ° C and the substrates in the spray for 3 min. at a pH between 10.0 and 1 1, 0 cleaned. Subsequently, the substrates were rinsed with city water and deionized water.
  • the pre-rinse of the substrates was carried out for 120 sec. At 20 ° C with moderate agitation.
  • the layer weights (SG) in mg / m 2 on the pretreated substrates were determined by X-ray fluorescence analysis (RFA). The circulation of zirconium was measured. Lackierunp
  • the pretreated substrates were KTL-coated.
  • Cathoguard ® 800 Fa. BASF
  • a bodywork was applied. This one was Daimler Black.
  • the thickness of the lacquer layer was determined by means of a layer thickness gauge according to DIN EN ISO 2808 (version 2007). It was in the range of 90 to 1 10 ⁇ .
  • the layer thickness of the KTLs was between 20 and 25 ⁇ m.
  • Tab. 1 shows that when poly (methylvinylether-a / f-maleic acid) is used in the conversion bath, better corrosion protection results can be achieved than when used in the pre-rinse (B2 compared to B1 and B4 in comparison to B3). Nevertheless, the results in the case of the pre-rinse according to the invention are still satisfactory.

Abstract

L'invention concerne un procédé amélioré de prétraitement de protection anticorrosion d'une surface métallique qui contient de l'acier, de l'acier galvanisé, de l'aluminium, du magnésium et/ou un alliage de zinc et de magnésium, selon lequel la surface métallique est mise en contact avec une composition aqueuse (A) qui comprend a) 0,01 à 0,5 g/l (calculé en tant qu'additif solide) d'au moins un copolymère qui comprend dans une configuration proposée en variante i) des motifs monomères qui contiennent au moins un groupe acide carboxylique, un groupe acide phosphonique et/ou un groupe acide sulfonique, et ii) des motifs monomères qui ne contiennent aucun groupe acide, et selon lequel la surface métallique est mise en contact avec une composition aqueuse acide (B) qui comprend au moins b1) un composé sélectionné parmi le groupe constitué par des composés titane, zirconium et hafnium, la surface métallique étant mise en contact i) tout d'abord avec la composition (A) puis avec la composition (B), ii) simultanément avec la composition (A) et avec la composition (B). L'invention concerne par ailleurs une composition aqueuse (A) correspondante, un concentré aqueux utilisé pour produire ladite composition, une surface métallique revêtue de manière correspondante, ainsi que l'utilisation d'un substrat métallique revêtu de manière correspondante.
EP17731571.0A 2016-06-22 2017-06-21 Procédé amélioré de prétraitement de protection anticorrosion d'une surface métallique qui contient de l'acier, de l'acier galvanisé, de l'aluminium, du magnésium et/ou un alliage de zinc et de magnésium Active EP3475464B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PL17731571T PL3475464T3 (pl) 2016-06-22 2017-06-21 Ulepszony sposób obróbki wstępnej chroniącej przed korozją powierzchni metalowej zawierającej stal, ocynkowaną stal, aluminium, magnez i/lub stop cynkowo-magnezowy

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102016211152 2016-06-22
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EP3475464B1 (fr) 2016-06-22 2020-08-19 Chemetall GmbH Procédé amélioré de prétraitement de protection anticorrosion d'une surface métallique qui contient de l'acier, de l'acier galvanisé, de l'aluminium, du magnésium et/ou un alliage de zinc et de magnésium
JP2022501520A (ja) * 2018-07-05 2022-01-06 ケメタル ゲゼルシャフト ミット ベシュレンクテル ハフツング 金属表面を酸性水性組成物および後リンス組成物で処理して腐食抵抗性を改善する方法
BR112020026213A8 (pt) * 2018-07-05 2021-04-06 Chemetall Gmbh método para tratar uma superfície metálica, composição aquosa ácida, mistura padrão, uso da composição aquosa ácida, e, substrato
CN109371389A (zh) * 2018-12-14 2019-02-22 惠州市四维化工有限公司 一种环保铝及铝合金的钝化方法
DE102019202889A1 (de) * 2019-03-04 2020-09-10 Atlas Elektronik Gmbh Haftvermittler für Piezokeramisches Hydrophon
KR20210149116A (ko) * 2019-04-04 2021-12-08 케메탈 게엠베하 감소된 피클링 침식을 갖는 금속 표면을 위한 포스페이트-무함유 세정제
EP3956406A1 (fr) * 2019-04-15 2022-02-23 BASF Coatings GmbH Composition aqueuse de revêtement destinée au revêtement par immersion de substrats électroconducteurs, contenant du bismuth ainsi que du lithium
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CN109312469A (zh) 2019-02-05
ZA201900292B (en) 2020-10-28
RU2019100885A3 (fr) 2020-10-19
US11441226B2 (en) 2022-09-13
BR112018075600A2 (pt) 2019-03-26
DE102017210358A1 (de) 2017-12-28
PL3475464T3 (pl) 2021-02-08
KR20190021341A (ko) 2019-03-05
ES2832626T3 (es) 2021-06-10
EP3475464B1 (fr) 2020-08-19
JP7195937B2 (ja) 2022-12-26
US20190330745A1 (en) 2019-10-31
RU2748887C2 (ru) 2021-06-01
CN117702097A (zh) 2024-03-15
JP2019518874A (ja) 2019-07-04
MX2018016254A (es) 2019-04-22
RU2019100885A (ru) 2020-07-23
KR102494315B1 (ko) 2023-02-02
WO2017220632A1 (fr) 2017-12-28

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