EP1330499A2 - Procede de pretraitement et d'enduction subsequente de surfaces metalliques avant le formage a l'aide d'une couche de type peinture et utilisation des substrats ainsi recouverts - Google Patents

Procede de pretraitement et d'enduction subsequente de surfaces metalliques avant le formage a l'aide d'une couche de type peinture et utilisation des substrats ainsi recouverts

Info

Publication number
EP1330499A2
EP1330499A2 EP01986707A EP01986707A EP1330499A2 EP 1330499 A2 EP1330499 A2 EP 1330499A2 EP 01986707 A EP01986707 A EP 01986707A EP 01986707 A EP01986707 A EP 01986707A EP 1330499 A2 EP1330499 A2 EP 1330499A2
Authority
EP
European Patent Office
Prior art keywords
layers
lacquer
polymer
corrosion protection
suspension
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.)
Withdrawn
Application number
EP01986707A
Other languages
German (de)
English (en)
Inventor
Toshiaki Shimakura
Klaus Bittner
Heribert Domes
Hardy Wietzoreck
Christian Jung
Marcus Schinzel
Norbert Maurus
Thomas Kolberg
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.)
Chemteall GmbH
Chemetall GmbH
Original Assignee
Chemteall GmbH
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 Chemteall GmbH, Chemetall GmbH filed Critical Chemteall GmbH
Publication of EP1330499A2 publication Critical patent/EP1330499A2/fr
Withdrawn legal-status Critical Current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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
    • B05D7/16—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies using synthetic lacquers or varnishes
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2701/00—Coatings being able to withstand changes in the shape of the substrate or to withstand welding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/06—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation
    • B05D3/061—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation using U.V.
    • B05D3/065—After-treatment
    • B05D3/067—Curing or cross-linking the coating
    • 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
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T50/00—Aeronautics or air transport
    • Y02T50/60—Efficient propulsion technologies, e.g. for aircraft

Definitions

  • the invention relates to a method for coating metallic surfaces and to the use of the coated substrates produced by the method according to the invention, in particular in vehicle construction, in particular in automobile series production, and for the production of components or body parts or preassembled elements in vehicle and aviation - or space industry.
  • it relates to new possibilities for the preparation and assembly of motor vehicles in that the various parts of the body are no longer assembled, cleaned, phosphated and only then painted with the entire paint system, as is customary today.
  • the anticorrosive layer (s) should be easily formable together with the paint or a paint-like layer and should also have good corrosion protection and good paint adhesion even after the shaping. In addition, depending on the joining process, it may be necessary for these layers to be easy to clinch without being more prone to corrosion.
  • the base coat (base coat) for architectural sheets on the outside often contains chromate today in order to achieve increased corrosion resistance with a relatively small layer thickness; a top coat with a thickness in the range of 10 to 20 ⁇ m is usually applied to this.
  • the same or similar base coats are often applied as on the front as a back coat with a thickness in the range of 6 to 15 ⁇ m as the only coat of paint. So far, as far as the applicant is aware, no UV-hardened lacquers have yet been used in the household appliance and architecture sector for coil coating.
  • the belt system used in each case can be a galvanizing line, a coil coating line and / or a different type of coating line such as e.g. a painting line, for example in an automobile plant, on which cut strip is coated with a lacquer or / and with a coating similar to a lacquer, which was previously pretreated on a belt system.
  • a galvanizing line e.g. a coil coating line and / or a different type of coating line
  • a different type of coating line such as e.g. a painting line, for example in an automobile plant, on which cut strip is coated with a lacquer or / and with a coating similar to a lacquer, which was previously pretreated on a belt system.
  • Prephosphating is understood to mean temporary protection of metallic surfaces, the substrates coated in this way then optionally oiled, temporarily stored, reshaped, after deoiling, for example by clinching, Gluing or welding can be joined and / or pretreated again, for example with phosphate, before the coating system is applied.
  • the pretreatment before painting is done today, especially in the European Aut ⁇ mobi.in ustr.e, partly without deliberate addition of chrome and partly with addition of chrome.
  • a chromium additive has a particularly protective effect against corrosion because a self-healing effect can occur in an injured area.
  • the pretreatment solutions are also preferably poor or free of cobalt, copper, nickel and / or other heavy metals. But in particular levels of nickel are still particularly advantageous and therefore practically always e.g. included in phosphating.
  • the pre-treatment solutions can be applied either in the rinse or the no-rinse process.
  • the solution is rinsed after the solution has been applied, which can be done in particular by spraying and / or dipping, the pretreatment layer being formed.
  • the solution is e.g. applied with a roll coater and dried immediately without rinsing.
  • a base coat is understood to mean a lacquer or a lacquer-like coating which replaces the cathodic immersion lacquer (KTL; electrodeposition lacquer) that is normally used in body construction.
  • This can be a primer, in particular a sliding, welding or pretreatment primer, or a different type of coating e.g. based on silane / siloxane.
  • the filler is usually followed by at least one clear coat, which enhances the brilliance and is also referred to as a top coat.
  • the coating which is formed with a sliding primer, can be used due to the good sliding properties, its low friction and its flexibility. particularly well and easily formed.
  • a welding primer and the coating produced from it contain such a high proportion of electrically conductive substance, in particular of electrically conductive particles, that welding two sheets together is possible without significantly increased effort, even if two lacquer-like layers have to be contacted.
  • a pretreatment primer is a primer or a corresponding coating that can also replace the anti-corrosion properties of a pretreatment layer. These are all paint-like coatings.
  • Resin mixtures are known in which resins are mixed with inorganic acids in order to achieve pickling attack and thus better contact of the resin layer directly with the metallic surface.
  • These compositions have the disadvantage that, due to the pickling attack, the contamination occurs during the contacting of the treatment liquid (dispersion) with the substrate. This leads to the accumulation of metals in the treatment liquid and, as a result, to the permanent change in the chemical composition of the treatment liquid, as a result of which the corrosion protection is significantly impaired.
  • These metals are removed from the metallic surface of the substrates to be treated by the pickling attack.
  • Another disadvantage is that, especially in the case of aluminum or alloys containing aluminum, the surfaces turn dark, possibly dark gray to anthracite in color. The dark discolored metal surfaces cannot be used for decorative applications because the discoloration is undesirable even for aesthetic reasons. Depending on the thickness of the layer overlay, the darkening is visible with different intensities.
  • EP-A-0 713 540 describes an acidic, aqueous composition for the treatment of metal surfaces which contains complex fluoride based on Ti, Zr, Hf, Si, Al or / and B, cations of Co, Mg, Mn, Zn, Ni, Contains Sn, Cu, Zr, Fe or / and Sr, inorganic phosphates or phosphonates and polymers in a ratio of polymers to complex fluorides in the range from 1: 2 to 3: 1.
  • this publication describes an addition of phosphate or phosphonate in each example.
  • EP-A-0 181 377 and WO 85/05131 lists aqueous compositions based on a) complex fluoride of B, Si, Ti or Zr, hydrofluoric acid and / or fluoride, b) salts of Co, Cu, Fe, Mn, Ni, Sr or / and Zn, c) a sequestering agent selected from nitrilotriacetic acid NTA, ethylenediaminetetraacetic acid EDTA, gluconic acid, citric acid or its derivatives or alkali metal or ammonium salts and d) a polymer made from polyacrylic acid, polymethacrylic acid or their C, - to C 8 ⁇ alkanol esters.
  • WO-A-93/20260 relates to a method for producing a coating for an aluminum-rich metallic surface with an aqueous mixture without separation of phases, the complex fluoride based on Ti, Zr, Hf, Si, Ge, Sn or / and B and a dissolved or / and dispersed compound based on Ti, Zr, Hf, Al, Si, Ge, Sn or / and B.
  • the specific polymer added is based on 4-hydroxostyrene and phenolic resin and is yellowish and may have a toxic effect. It serves as a film former and adhesion promoter.
  • aqueous compositions containing hexafluorotitanic acid, SiO 2 particles and this polymer in a range from 5.775 to 8.008% by weight In addition, this publication protects a process for coating a metallic surface with this aqueous mixture only by contacting and drying and then briefly contacting it with such a mixture at temperatures in the range from 25 to 90 ° C. No layer thickness of the coating applied with this aqueous composition is mentioned. However, this can be stated from the layer coatings of titanium indicated, which are 22 to 87 mg / m 2 and are roughly about ten times as strong as in the examples according to the invention of this application.
  • Hexafluorozirconic acid 0.01 to 10% by weight of a specific polymer based on 4-hydroxystyrene and phenolic resin (see also WO-A-93/20260), 0.05 to 10 wt .-% Si0 2 particles, optionally a solvent for dissolving 4-hydroxystyrene phenolic resin below 50 ° C and optionally contains a surfactant, the aqueous composition being applied in the drying process without subsequent rinsing.
  • WO96 / 07772 describes a process for the conversion treatment of metallic surfaces with an aqueous composition containing (A) complex fluorides based on Ti, Zr, Hf, Si, Al or / and B of at least 0.15 M / kg, (B) cations selected from Co, Cu, Fe, Mg, Mn, Ni, Sn, Sr, Zn or / and Zr with a molar ratio of (B) to (A) in the range from 1: 5 to 3; 1, (C) at least 0J5 M p / kg of phosphorus-containing oxyanions and / or phosphonates, (D) at least 1% of water-soluble and water-dispersible polymers or of polymer-forming resins, and (E) sufficient free acid to the aqueous To impart composition pH in the range of 0.5 to 5.
  • A complex fluorides based on Ti, Zr, Hf, Si, Al or / and B of at least 0.15 M / kg
  • B cations
  • the object of the invention is to overcome the disadvantages of the prior art and, in particular, to propose a method for coating metallic surfaces which is also suitable for high coating speeds, such as are used for strips, which is largely or completely free of chromium (VI) compounds is applicable and can be used on an industrial scale.
  • a method for coating metallic surfaces which is also suitable for high coating speeds, such as are used for strips, which is largely or completely free of chromium (VI) compounds is applicable and can be used on an industrial scale.
  • the object of the invention is to propose a method for coating metallic substrates which is also suitable for coating on fast-moving belts, in which at least one organic, sufficiently flexible and at the same time sufficiently corrosion-resistant coating can subsequently be applied (base coat).
  • the coating sequence should be sufficiently corrosion-resistant even after forming. This process should be suitable for economical and environmentally friendly industrial implementation.
  • the object is achieved with a method for coating a metallic strip, the strip or possibly the strip sections produced therefrom in the subsequent process first with at least one corrosion protection layer and then with at least one layer of a lacquer-like polymer-containing layer or / and at least a coating layer is / are coated, the strip being divided into strip sections after coating with at least one corrosion protection layer or after coating with at least one layer of a lacquer-like coating and / or at least one coating layer, the coated strip sections then being reshaped, joined or / and be coated with at least one (further) lacquer-like layer and / or lacquer layer, at least one of the corrosion protection layers being formed by coating the surface with an aqueous dispersion which, in addition to water a), has at least one organic film former which comprises at least contains a water-soluble or water-dispersed polymer, b) a content of cations and / or hexa- or tetrafluoro complexes of cations selected from the group of
  • the aqueous composition used can be largely or completely free of chromium (VI) compounds. It can be used for the pretreatment before a further coating, such as painting, or for the treatment in which the body to be coated may be deformed after the coating, in particular a strip or strip section. Above all, however, it should serve to form a first or / and second pretreatment layer.
  • VI chromium
  • it can optionally contain at least one organic solvent, possibly at least one silane and / or siloxane calculated as silane, possibly at least one corrosion inhibitor and possibly at least one chromium (VI) compound.
  • at least one organic solvent possibly at least one silane and / or siloxane calculated as silane, possibly at least one corrosion inhibitor and possibly at least one chromium (VI) compound.
  • the layer thickness of the dried and possibly also hardened film can be determined approximately via the constituents, the density of the constituents and the coating quantities of titanium or zirconium on the coated surface determined by the X-ray fluorescence analysis.
  • a standard coil coating lacquer F2-647 together with the top coat lacquer F5-618 applied to the dried or hardened film preferably gives an adhesive strength of at most 10% of the detached surface in a T-bend test with a bend T1 according to NCCA.
  • the primer coating is applied in a standardized manner to the coating according to the invention with a layer thickness of approximately exactly 5 ⁇ m, and the top coat lacquer is applied in a standardized manner to this primer coating with a layer thickness of approximately exactly 20 ⁇ m. Then a coated strip section is bent so far that the distance between the two sheet metal halves is exactly one sheet thickness at the bending point. The sheet thickness of the material used was 0.8 mm. At the bending point, the paint adhesion is then checked by means of adhesive tape tear-off and the result of the test is given as the percentage of the area removed.
  • the T-Bend-Test can therefore be seen as a very demanding paint adhesion test for the quality of pretreated and painted metal sheets with regard to the damage to this layer system during subsequent forming.
  • the area portions of the detached area in the T-Bend test are preferably up to 8%, particularly preferably up to 5%, very particularly preferably up to 2%, but the best values are approximately 0%, so that then usually only cracks but no delamination can occur.
  • clean metallic surface here means an unpurified metallic, e.g. freshly galvanized surface that does not require cleaning or a freshly cleaned metallic surface.
  • composition according to the invention for forming a treatment layer or pretreatment layer and / or a paint-like coating :
  • the content of cations and / or hexafluoro complexes of cations selected from the group of titanium, zirconium, hafnium, silicon, aluminum and boron in the aqueous composition (bath solution) is preferably 0.1 to 50 g / L, particularly preferably 0, 2 to 30 g / L, very particularly preferably 0.5 to 10 g / L, in particular 1 to 4 g / L.
  • This information relates to the content of the elemental metal.
  • Cations or hexafluoro complexes of titanium and / or zirconium are particularly preferred.
  • the at least one inorganic compound in particle form is contained in the aqueous composition (bath solution) preferably in a content of 0J to 80 g / L, particularly preferably in a range from 0.2 to 25 g / L, very particularly preferably from 0.5 to 10 g / L, in particular from 1 to 4 g / L.
  • the ratio of the contents of cations and / or hexafluoro complexes of cations selected from the group of titanium, zirconium, hafnium, silicon, aluminum and boron to contents of organic film former in the aqueous composition (bath solution) can vary within wide ranges; in particular it can be ⁇ 1; 1 lie. This ratio is preferably in a range from 0.05: 1 to 3.5: 1, particularly preferably in a range from 0.2: 1 to 2.5: 1.
  • the ratio of the contents of cations and / or hexafluoro complexes of cations selected from the group of titanium, zirconium, hafnium, silicon, aluminum and boron to contents of inorganic compounds in particle form in the aqueous composition (bath solution) can vary within wide ranges; in particular, it can be ⁇ 5.5: 1. This ratio is preferably in a range from 0.05: 1 to 5; 1, particularly preferably in a range of 0.2; 1 to 2.5: 1.
  • the ratio of the contents of organic film former to contents of inorganic compounds in particle form in the aqueous composition (bath solution) can vary within wide ranges; in particular it can be ⁇ 3.8: 1. This ratio is preferably in a range from 0.05: 1 to 3.5: 1, particularly preferably in a range from 0J8: 1 to 2.5: 1.
  • the content of at least one silane and / or siloxane, calculated as silane, in the aqueous composition (bath solution) is preferably 0.1 to 50 g / L, particularly preferably 0.2 to 35 g / L, very particularly preferably 0.5 to 20 g / L, especially 1 to 10 g / L.
  • Such an additive can help to improve the adhesion of an organic coating applied subsequently by reactive functional groups such as amino or epoxy functions.
  • the aqueous composition is preferably also free or largely free of transition metals or heavy metals which are not present in the inorganic compound in particle form in very small particle sizes or / and which are not bound to fluorine, for example as hexa- and / or tetrafluoride, and then not only have to be bound to fluorine.
  • the aqueous composition can also be free or largely free of transition metals or heavy metals which have been deliberately added to the aqueous composition with the exception of the abovementioned additives in particulate form or with the exception of the compounds which are at least partially bound to fluoride.
  • the aqueous composition may have traces or small amounts of impurities in transition metals or heavy metals which, due to a pickling effect, have been removed from the metallic substrate surface and / or the bath containers or pipelines, which were brought in from previous baths or / and which result from impurities in the raw materials come.
  • the aqueous composition is particularly preferably free or largely free of lead, cadmium, iron, cobalt, copper, manganese, nickel, zinc and / or tin. Above all, the use of largely or completely chromium-free aqueous compositions is recommended.
  • the aqueous composition which is largely free of chromium (VI) compounds, only has a chromium content of up to 0.05% by weight on chromium-free metallic surfaces, and a chromium content of on chromium-containing metallic surfaces up to 0.2% by weight.
  • the aqueous composition is preferably also free of phosphorus-containing compounds if these are not bound to polymers or are to be largely bound to these.
  • composition is also preferably free of additions or contents of hydroxocarboxylic acids such as, for example, gluconic acid.
  • the organic film former can be in the form of a solution, dispersion, emulsion, microemulsion or / and suspension.
  • the organic film former can be or contain at least one synthetic resin, in particular a synthetic resin based on acrylate, polyacrylic, ethylene, polyethylene, polyester, polyurethane, silicone polyester, epoxy, phenol, polystyrene, styrene, urea-formaldehyde, their mixtures or / and their copolymers. This can be a cationically, anionically or / and sterically stabilized synthetic resin or polymer or / and their solution.
  • the organic film former is preferably a synthetic resin mixture or / and a copolymer which contains synthetic resin based on acrylate, polyacrylic, ethylene, polyethylene, urea-formaldehyde, polyester, polyurethane, polystyrene and / or styrene, from which during or an organic film is formed after the release of water and other volatile components.
  • the organic film former can be synthetic resin and / or polymer based on polyacrylate, polyethyleneimine, polyurethane, polyvinyl alcohol, polyvinylphenol, polyvinylpyrrolidone, polyaspartic acid or / and their derivatives or copolymers, in particular copolymers with a phosphorus-containing vinyl compound, ethylene-acrylic copolymer, acrylic - Contain modified polyester, acrylic-polyester-polyurethane copolymer or styrene acrylate.
  • the synthetic resin or polymer is preferably water-soluble. It preferably contains free acid groups that are not neutralized in order to allow attack on the metallic surface.
  • the acid number of the synthetic resin can preferably be in the range from 5 to 800, particularly preferably in the range from 50 to 700.
  • the advantage of such synthetic resins in most cases is that it is not necessary to use these synthetic resins or polymers cationically, anionically or sterically to stabilize.
  • the molecular weight of the synthetic resin or the polymer can be in the range from at least 1,000 u, preferably from 5,000 to 250,000 u, particularly preferably in the range from 20,000 to 200,000 u.
  • the phosphorus content of the aqueous composition is largely or wholly bound to organic, in particular polymeric compounds, so that the phosphorus content is virtually non-existent, or not at all, to purely inorganic compounds such as e.g. Orthophosphate is bound.
  • the aqueous composition can be such that it does not contain any corrosion inhibitors, and the coatings formed from it already acquire excellent corrosion protection.
  • it can also contain at least one corrosion inhibitor.
  • the corrosion inhibitor can have at least one organic group and / or at least one amino group.
  • It can be an organic compound or an ammonium compound, in particular an amine or an amino compound, such as, for example, an alkanolamine, a TPA-amine complex, a phosphonate, a polyaspartic acid, a thiourea, a Zr-ammonium carbonate , Benzotriazole, a tannin, an electrically conductive polymer such as a polyaniline and / or their derivatives, which can significantly improve the corrosion protection again. It can be advantageous if the corrosion inhibitor is readily soluble in water and / or readily dispersible in water, in particular with more than 20 g / L.
  • an amine or an amino compound such as, for example, an alkanolamine, a TPA-amine complex, a phosphonate, a polyaspartic acid, a thiourea, a Zr-ammonium carbonate , Benzotriazole, a tannin, an electrically conductive polymer such as a polyaniline and /
  • At least one corrosion inhibitor is particularly important for electrolytically galvanized steel sheets.
  • the addition a corrosion inhibitor can help to achieve the necessary security for corrosion resistance in series production.
  • manganese ions e.g. added as metal in acid solution or in the form of manganese carbonate to the compositions mentioned in the examples improved the alkali resistance.
  • Mn ions with a content in the range of 0.05 to 10 g / L has proven particularly useful here.
  • this addition of manganese resulted in a noticeable improvement not only in alkali resistance, but also in general corrosion resistance and paint adhesion.
  • the aqueous fluorine-containing composition contains a high or very high proportion of complex fluoride, in particular 50 to 100% by weight, based on the fluorine content.
  • the fluorine content in the form of complexes and free ions in the aqueous composition (bath solution) is preferably a total of 0.1 to 14 g / L, preferably 0.15 to 8 g / L, in particular 0.2 to 3 g / L.
  • the aqueous composition contain zirconium as the sole cation or in a higher proportion, ie at least 30% by weight, based on the mixture of cations selected from the group of titanium, zirconium, hafnium, silicon, aluminum and contains boron.
  • the content of such cations in the aqueous composition (bath solution) is preferably a total of 0J to 15 g / L, preferably 0.15 to 8 g / L, in particular 0.2 to 3 g / L.
  • the content of zirconium and / or titanium in the aqueous composition is preferably a total of 0.1 to 10 g / L, particularly preferably 0.15 to 6 g / L, in particular 0.2 to 2 g / L. It was found that none of the cations selected from this group gave better results in terms of corrosion protection and paint adhesion than zirconium, which was present in part or selected from these cations alone. If there is a significant excess of fluoride in relation to the content of such cations, in particular more than 35 mg / L free fluoride, the pickling effect of the aqueous composition is increased. In particular, a content of 35 to 350 mg / L free fluoride can help to better control the thickness of the coating produced.
  • the pickling effect of the aqueous composition will be significantly reduced and a thicker coating will often be formed, which in some cases can even be too thick and is easily subject to filiform corrosion can and also has poorer paint adhesion.
  • the organic film former can also be composed in such a way that it contains (only) water-soluble synthetic resin and / or polymer, in particular one which is stable in solutions with pH values ⁇ 5.
  • the organic film former preferably contains synthetic resin or polymer which has a higher proportion of carboxyl groups.
  • synthetic resins can also be used which only become water-soluble or water-dispersible after reaction with a basic compound such as ammonia, amines and / or alkali metal compounds.
  • the aqueous composition contains at least one partially hydrolyzed or completely hydrolyzed silane.
  • the silane can be an acyloxysilane, an alkylsilane, an alkyltrialkoxysilane, an aminosilane, an aminoalkylsilane, an aminopropyltrialkoxysilane, a bis-silylsilane, an epoxysilane, a fluoroalkylsilane, a glycidoxysilane such as, for example, a glycidoxyalkylane Silane, a mercapto-silane, a (meth) acrylato-silane, a mono-silyl-silane, a multi-silyl-silane, a bis- (trialkoxysilyl-propyl) amine, a bis- (trialkoxysilyl
  • it can be at least one silane in a mixture with a content of at least one alcohol such as ethanol, methanol and / or propanol of up to 8% by weight, based on the silane content, preferably up to 5% by weight, particularly preferably up to 1% by weight, very particularly preferably up to 0.5% by weight, possibly with a content of inorganic particles, in particular in a mixture of at least one amino silane such as, for example, bis-amino silane with at least one Alkoxy silane such as trialkoxy silyl propyl tetrasulfane or a vinyl silane and a bis silyl aminosilane or a bis silyl polysulfur silane and / or a bis silyl aminosilane or an aminosilane and a multi-silyl functional silane.
  • a content of at least one alcohol such as ethanol, methanol and / or propanol of up to 8% by weight, based on the silane content, preferably
  • the aqueous composition can then alternatively or additionally contain at least one siloxane corresponding to the silanes mentioned above.
  • Preferred silanes / siloxanes are those which have a chain length in the range from 2 to 5 carbon atoms and have a functional group which is suitable for reaction with polymers.
  • the addition of at least one silane and / or siloxane can be advantageous in order to form bonding bridges or to promote crosslinking.
  • a finely divided powder, a dispersion or a suspension such as, for example, a carbonate, an oxide, a silicate or a sulfate, in particular colloidal or amorphous particles, is added as the inorganic compound in particle form.
  • particles based on at least one compound of aluminum, barium, cerium, calcium, lanthanum, silicon, titanium, yttrium, zinc and / or zirconium are particularly preferred, in particular particles based on aluminum oxide, barium sulfate, cerium dioxide, rare earth mixed oxide , Silicon dioxide, silicate, titanium oxide, yttrium oxide, zinc oxide and / or zirconium oxide.
  • the at least one inorganic compound is preferably present in particle form in particles with an average particle size in the range from 6 nm to 150 nm, particularly preferably in the range from 7 to 120 nm, very particularly preferably in the range from 8 to 90 nm preferably in the range from 8 to 60 nm, particularly preferably in the range from 10 to 25 nm it is preferred that larger particles have a more platelet-like or elongated grain shape.
  • particles with a higher or high electrical conductivity in particular those of oxides, phosphates, as particles of the compound in particle form.
  • At least one organic solvent can also be added in the process according to the invention.
  • At least one water-miscible and / or water-soluble alcohol, a glycol ether or N-methylpyrrolidone and / or water can be used as the organic solvent for the organic polymers, in the case of using a solvent mixture in particular a mixture of water with at least one long-chain alcohol, such as Propylene glycol, an ester alcohol, a glycol ether and / or butanediol.
  • a solvent mixture in particular a mixture of water with at least one long-chain alcohol, such as Propylene glycol, an ester alcohol, a glycol ether and / or butanediol.
  • the content of organic solvent if any, is preferably from 0J to 10% by weight, in particular from 0.2 to 5% by weight, very particularly from 0.4 to 3% by weight.
  • At least one can be used as the lubricant
  • Wax selected from the group of paraffins, polyethylenes and polypropylene can be added, in particular an oxidized wax or an HD polyethylene. It is particularly advantageous to use the wax as aqueous or as to use anionically or cationically stabilized dispersion because it can then be kept easily homogeneously distributed in the aqueous composition.
  • the melting point of the wax used as a lubricant is preferably in the range from 40 to 160 ° C., in particular in the range from 120 to 150 ° C. It is particularly advantageous, in addition to a lubricant with a melting point in the range from 120 to 165 ° C., to add a lubricant with a melting point in the range from 45 to 95 ° C.
  • a glass transition temperature in the range from ⁇ 20 to + 60 ° C., in particular in amounts of 2 to 30% by weight, preferably 5 to 20% by weight, of the total solids content.
  • the latter lubricant can also be used advantageously alone.
  • a wax content is only advantageous if the coating according to the invention is a treatment layer or if the wax content of a pretreatment layer should not have a disadvantageous effect in the subsequent painting.
  • the acid groups of the synthetic resin and / or the polymer can be reacted with ammonia, with amines such as e.g. Morpholine, dimethylethanolamine, diethylethanolamine or triethanolamine and / or with alkali metal compounds such as e.g. Be neutralized with sodium hydroxide.
  • amines such as e.g. Morpholine, dimethylethanolamine, diethylethanolamine or triethanolamine and / or with alkali metal compounds such as e.g. Be neutralized with sodium hydroxide.
  • the aqueous composition is preferably free of inorganic or organic acids, possibly with the exception of hexafluoro acids.
  • a basic compound can be added to the aqueous composition in order to keep the aqueous composition at a pH in the range from 0.5 to 5.
  • bases selected from ammonia and amine compounds such as e.g. Triethanolamine.
  • the aqueous composition can optionally contain at least one biocide, one defoamer, one adhesion promoter, one catalyst, one corrosion inhibitor, one wetting agent and / or one forming additive. Some additives have multiple functions; for example, many corrosion inhibitors are adhesion promoters and possibly also wetting agents.
  • the water content of the aqueous composition can vary widely. Their water content will preferably be in the range from 95 to 99.7% by weight, in particular in the range from 97.5 to 99.5% by weight, a small part of the water content given here also being replaced by at least one organic solvent can.
  • the water or, if appropriate, water content together with a small amount (up to 3% by weight) of organic solvent is preferably in the range from 97 to 99% by weight, particularly preferably in the range from 97 5 to 98.5% by weight.
  • water is added to the aqueous composition, preferably fully demineralized water or other somewhat purer water quality is added.
  • the pH of the aqueous solution of the organic film former without the addition of further compounds is preferably in the range from 0.5 to 12, in particular less than 7, particularly preferably in the range from 1 to 6 or 6 to 10.5, very particularly preferably in the range from 1, 5 to 4 or 7 to 9, depending on whether the work is in the acidic or rather basic range.
  • the pH of only the organic film former in an aqueous preparation without the addition of further compounds is preferably in the range from 1 to 12.
  • the resulting coating can be a conversion coating or a coating that does not remove and incorporate any of the elements contained in the metallic surface.
  • the coating preferably rests on the very thin oxide / hydroxide layer, which is directly on the metallic surface, or even directly on the metallic surface. Depending on whether you want to apply a thick or thin film, a higher or lower concentration of cations from the above group or fluoride is required.
  • liquid film in the range from 0.8 to 12 ml / m 2 , in particular with a liquid film of approximately 2 ml / m 2 in the no-rinse process (drying process without subsequent rinsing step) applied with a production roll coater or with a liquid film of about 7 ml / m 2 in the no-rinse process applied with a laboratory roll coater.
  • a thicker liquid film is usually applied with a roller application (usually in the range from 2 to 10 ml / m 2 ) than when dipping and squeezing with smooth rubber rollers (usually in the range from 1 to 6 ml / m 2 ).
  • aqueous compositions are preferably used which contain most or almost all components of the bath solution, but not the at least one inorganic see in particle form, which is preferably kept separately and added separately.
  • at least one accelerator as is usually used in phosphating, can also be advantageous here, because this enables accelerated attack on the metallic surface by accelerating the oxidative dissolution of the metal or alloy.
  • at least one peroxide and / or at least one compound based on hydroxylamine, nitroguanidine or nitrate are suitable.
  • the concentrate or the supplementary solution preferably has a concentration which is five to ten times as enriched with respect to the individual components as the bath solution.
  • the aqueous composition can be applied by rolling, flooding, knife coating, spraying, spraying, brushing and / or dipping and, if appropriate, by subsequent squeezing, for example using a roller.
  • the aqueous composition can have a pH in the range from 0.5 to 12, preferably in the range from 1 to 6 or 7 to 9, particularly preferably in the range from 1, 5 to 4 or 6 to 10.5, respectively depending on whether you work in the acidic or more basic area.
  • the aqueous composition can in particular be applied to the metallic surface at a temperature in the range from 5 to 50 ° C., preferably in the range from 10 to 40 ° C., particularly preferably in the range from 18 to 25 ° C.
  • the metallic surface can be kept at temperatures in the range from 5 to 120 ° C., preferably in the range from 10 to 60 ° C., very preferably from 18 to 25 ° C., when the coating is applied.
  • the final drying of such films can take many days, while the essential drying can be accomplished in a few seconds.
  • the filming takes place here, especially when drying in the temperature range from 25 to 95 ° C, possibly also at an even higher temperature.
  • the curing process may take several weeks until the final drying or hardening state is reached. Often, no or only a small proportion of the polymerization will take place by thermal crosslinking, or the proportion of the polymerization will be correspondingly low.
  • the coating according to the invention filmed and cured in this way can be regarded as a corrosion protection layer, in particular as a treatment or pretreatment layer.
  • the hardening state can additionally be accelerated or increased by chemical or / and thermal acceleration of the crosslinking, in particular by heating, or / and by actinic radiation, for example with UV radiation, in which case suitable synthetic resins / polymers and, if appropriate, photoinitiators are then added.
  • suitable synthetic resins / polymers and, if appropriate, photoinitiators are then added.
  • Appropriate additives or process variants can be used to achieve partial, extensive or complete crosslinking of the polymers.
  • Coating according to the invention can be regarded and used as a corrosion protection layer for smaller proportions (in particular 0.05 to 5% by weight of polymers in the aqueous composition) of polymers, and for higher proportions (0.5 to 50% by weight of polymers in of the aqueous composition) of polymers as a primer layer, in particular as a pretreatment primer layer.
  • the coated metallic surface can be dried at a temperature in the range from 20 to 250 ° C., preferably in the range from 40 to 120 ° C., very particularly preferably at 60 to 100 ° C. PMT (peak metal temperature).
  • the necessary dwell time during drying is essentially inversely proportional to the drying temperature: e.g. in the case of band-shaped material, 1 s at 100 ° C or 30 min at 20 ° C, while coated parts depending on the wall thickness must be dried significantly longer. Drying devices based on circulating air, induction, infrared and / or microwaves are particularly suitable for drying.
  • the layer thickness of the coating according to the invention is preferably in the range from 0.01 to 6 ⁇ m, particularly preferably in the range from 0.02 to 2.5 ⁇ m, very particularly preferably in the range from 0.03 to 1.5 ⁇ m, in particular in the range from 0.05 to 0.5 ⁇ m.
  • the coated tapes can be wound into a reel (coil), if necessary after cooling to a temperature in the range from 40 to 70 ° C.
  • the coating according to the invention need not be the only treatment / pretreatment layer which is applied to the metallic surface, but it can also be a treatment / treatment layer under two, three or even four different treatment / treatment layers.
  • it can be applied in a system of at least two such layers as a second layer, for example after an alkaline passivation, for example based on Co-Fe cations.
  • it can also be used in a system of at least three such layers can be applied as a third layer, for example after an activation treatment, for example based on titanium, and after a pretreatment coating, for example with a phosphate such as ZnMnNi phosphate.
  • At least one lacquer and / or at least one lacquer-like coating can then be applied to the coating according to the invention or to the uppermost treatment / pretreatment layer in such a layer system.
  • first apply a primer If necessary, either a lacquer or lacquer-like intermediate layer or the further lacquer sequence, e.g. filler and at least one top coat.
  • a lacquer-like coating is also referred to in the context of this application as a coating of "lacquer".
  • At least one coating of lacquer, polymer, paint, adhesive or / and adhesive carrier can be applied to the partially or completely dried or cured film, for example also a special coating such as e.g. a coating with the property of reflecting IR radiation.
  • the metal parts coated according to the invention with the aqueous composition in particular strips or strip sections, can be reshaped, painted, coated with polymers such as PVC, printed, glued, hot-soldered, welded and / or connected to one another or to other elements by clinching or other joining techniques. Forming, however, usually only takes place after painting. These methods are generally known.
  • the part with a metallic surface coated with the aqueous composition according to the invention can be a wire, a wire winding, a wire mesh, a steel strip, a metal sheet, a cladding, a shield, a body or part of a body, part of a vehicle, trailer , Mobile home or missile, a cover, a housing, a lamp, a lamp, a traffic light element, a piece of furniture or a furniture element, an element of a household appliance, a frame, a profile, a molded part of complicated geometry, a guardrail, radiator or fence element, a bumper, a part made of or with at least one tube and / or a profile, a window, door or bicycle frame or a small part such as a screw, nut, flange, spring or an eyeglass frame.
  • the process according to the invention represents an alternative to the chromate-containing processes mentioned, in particular in the area of surface pretreatment of metal strips before painting, and, compared to them, provides similarly good results in terms of corrosion protection and paint adhesion.
  • the method according to the invention for treating the metal surface cleaned in a conventional manner without a subsequent aftertreatment, such as rinsing with water or a suitable rinsing solution.
  • the method according to the invention is particularly suitable for the application of the treatment solution by means of a so-called roll coater, the treatment liquid being able to be dried in immediately after the application without further downstream process steps such as rinsing steps (dry-in-place technology).
  • the coatings according to the invention are usually far thinner than 0.5 ⁇ m. The thicker the coatings, the more the paint adhesion decreases, although the corrosion protection may be improved somewhat.
  • the coatings according to the invention are very inexpensive, environmentally friendly and can be used on a large industrial scale.
  • corrosion protection layers are applied in the method according to the invention, this can be one to four layers, which may all be applied one after the other directly to one another. At least two or three corrosion protection layers are preferably applied in succession. At least one of these layers has a composition as mentioned in the main claim.
  • Each further of these layers is preferably a corrosion protection layer selected from the group of coatings based on iron-cobalt, Nik- kel cobalt, at least one fluoride, at least one complex fluoride, in particular tetrafluoride or hexafluoride, an organic hydroxy compound, a phosphate, a phosphonate, a polymer, a rare earth compound composed of at least one rare earth element including lanthanum and yttrium, a silane / siloxane, a silicate, cations of aluminum, magnesium and / or at least one transition metal selected from the group of chromium, iron, hafnium, cobalt, manganese, molybdenum, nickel, titanium, tungsten and zirconium or a coating based on nanoparticles, but if necessary at least one further corrosion protection layer can be applied.
  • a corrosion protection layer selected from the group of coatings based on iron-cobalt, Nik- kel cobalt,
  • the at least one further corrosion protection layer can be applied as desired before or / and after the first, second or third corrosion protection layer. It can be important to apply more than one corrosion protection layer (pretreatment layer) because the subsequent lacquer-like or lacquer layers are often kept so thin compared to the lacquer systems according to the prior art that the requirements for corrosion protection must be increased accordingly.
  • the first corrosion protection layer can be applied in a drying process and the second corrosion protection layer in a drying process or rinse process.
  • a drying process is a no-rinse process in which a liquid film is dried on the possibly pre-coated belt.
  • a rinse process is a coating process in which a coating is formed by reaction, in particular when spraying or dipping, in which the coating is subsequently rinsed to remove excess chemicals, and in which the coating is finally dried. Coatings are preferably applied, for example, on the basis of zinc or / and manganese phosphate and mostly with a low nickel content in the no-rinse process. However, many other types of coating can be dried together. In this method, for example, the first corrosion protection layer can be applied in a rinse process and the second corrosion protection layer in a drying process or rinse process.
  • the second corrosion protection layer can be applied in a rinsing step, in particular after the first corrosion protection layer has previously been applied to a galvanizing line.
  • the galvanizing line can preferably be electrolytically galvanized, electrolytically alloy galvanized, hot-dip galvanized, hot-dip galvanized and / or hot-dip alloy galvanized.
  • coatings i.a. Pure zinc, zinc with a purity in the range of 98 to 99.9%, aluminum-zinc alloys, zinc-aluminum alloys and zinc-nickel alloys are applied.
  • the second corrosion protection layer can be applied in a drying process, in particular after the first corrosion protection layer has previously been applied on a galvanizing line.
  • the galvanizing line can preferably be electrolytically galvanized, hot-dip galvanized, hot-dip galvanized and / or hot-dip alloy galvanized.
  • surfaces of aluminum, iron, cobalt, copper, magnesium, nickel, titanium, tin, zinc or aluminum, iron, cobalt, copper, magnesium, nickel, titanium, tin and / or zinc-containing alloys can be coated, in particular electro-galvanized or hot-dip galvanized surfaces.
  • Preferred metallic coatings on the metallic strips are: electrolytically galvanized steel, hot-dip galvanized steel, hot-dip galvanized steel, aluminum alloy coated with pure aluminum.
  • the pretreatment before painting is preferably chromium-free or largely chromium-free, especially to the extent that no chromium is intentionally added.
  • the pretreatment solutions are preferred also poor or free of cobalt, copper, nickel and / or other heavy metals.
  • the polymers, copolymers, crosspolymers, oligomers, phosphonates can be coated with at least one liquid, solution or suspension largely or completely free of chromium compounds before coating with at least one lacquer and / or with at least one lacquer-like polymer-containing layer , Contains silanes and / or siloxanes. Largely free of chromium can mean without deliberate addition of a chromium compound.
  • liquid also includes solvent-free, liquid compounds or mixtures.
  • This method can be characterized in that no lead, cadmium, chromium, cobalt, copper or / and nickel is added to the liquid, solution or suspension for the first or / and second corrosion protection layer.
  • lacquer layers or / and lacquer-like polymer-containing layers can be saved, in particular one pretreatment layer and one lacquer layer ( see tables 2A-J for variants A ff).
  • the liquid, solution or suspension for at least one of the corrosion protection layers and / or paint-like polymer-containing layers can contain, in addition to water, at least one organic film former with at least one water-soluble or water-dispersed polymer, copolymer, block copolymer, crosspolymer, monomer, oligomer, and their derivative (e) k mixture (s) and / or copolymer (s).
  • the share of this organic compounds are preferably in a layer in the range from 60 to 99.8% by weight, based on the solids content
  • the liquid, solution or suspension for at least one of the corrosion protection layers or / and paint-like polymer-containing layers in addition to water can have a total content of cations, tetrafluorocomplexes and / or hexafluorocomplexes of cations selected from the group of titanium, zirconium, hafnium, Silicon, aluminum and boron or / and free or otherwise bound fluorine, in particular 0.1 to 15 g / L complex fluoride based on F 6 , preferably 0.5 to 8 g / L complex fluoride based on F 6 or 0J to 1000 mg / L free fluorine.
  • the proportion of these compounds is preferably in a layer in the range from 5 to 99.9% by weight.
  • the liquid, solution or suspension for at least one of the corrosion protection layers and / or paint-like polymer-containing layers in addition to water, a total content of free or not of Tetra°. Hexafluoro complexes have bound fluorine, in particular 0.1 to 1000 mg / L calculated as free fluorine, preferably 0.5 to 200 mg / L, particularly preferably 1 to 150 mg / L.
  • the liquid, solution or suspension for at least one of the corrosion protection layers, lacquer layers and / or lacquer-like polymer-containing layers in addition to water can contain at least one inorganic compound in particle form with an average particle diameter measured on a scanning electron microscope in the range from 0.003 to 1 Have microns in diameter, preferably in the range of 0.005 to 0.2 microns in diameter, in particular based on Al 2 0 3 , BaS0 4 , rare earth oxide (s), at least one other rare earth compound, Si0 2 , silicate, Ti0 2 , Y 2 0 3 , Zn, ZnO or / and Zr0 2 , preferably in a content in the range from 0J to 80 g / L, particularly preferably in a content in the range from 1 to 50 g / L, very particularly preferably in a content in the range from 2 to 30 g / L.
  • the proportion of these compounds in particle Form is preferably in a layer in the range from 5 to 90% by weight, particularly preferably in the range from 10 to 50% by weight.
  • Electrically conductive particles such as iron oxide, iron phosphide, molybdenum compounds such as molybdenum sulfide, graphite and / or carbon black or / and an addition of conductive polymers can also be used if the sheets are to be joined by welding, if necessary.
  • These corrosion protection layers are preferably free of elemental zinc.
  • the liquid, solution or suspension for at least one of the corrosion protection layers, lacquer layers or lacquer-like polymer-containing layers can have at least one corrosion inhibitor.
  • the corrosion inhibitor can have at least one organic group and / or at least one amino group. It can be an organic compound or an ammonium compound, in particular an amine or an amino compound, such as e.g. an alkanolamine, a TPA amine complex, a phosphonate, a polyaspartic acid, a thiourea, a Zr ammonium carbonate, benzotriazole, a tannin, an electrically conductive polymer such as e.g. contain a polyaniline or / and their derivatives.
  • organic phosphate compounds phosphonate compounds, organic morpholine and thio compounds, aluminates, manganates, titanates and zirconates, preferably of alkylmorpholine complexes, organic Al, Mn, Ti or / and Zr compounds, in particular those olefinically unsaturated carboxylic acids, for example ammonium salt of carboxylic acids such as chelated lactic acid titanate, triethanolamine titanate or zirconate, Zr-4-methyl- ⁇ -oxo-benzene-butanoic acid, aluminum zirconium carboxylate, alkoxypropenolatotitanate or zirconate, titanium or / and zirconium acetate or / and their derivatives, Ti / Zr ammonium carbonate.
  • the proportion of these compounds is preferably in one layer in the range from 5 to 40% by weight.
  • the liquid, solution or suspension for at least one of the corrosion protection layers, lacquer layers or lacquer-like polymer-containing layers can have at least one connection to the particularly slow neutralization of comparatively acidic mixtures and / or to protect unprotected or damaged parts of the metallic surface from corrosion, preferably based on carbonate or hydroxycarbonate or conductive polymers, particularly preferably at least one basic compound with a layer structure such as, for example, Al-containing hydroxy Carbonate hydrate (hydrotalcite).
  • the proportion of these compounds is preferably in a layer in the range from 3 to 30% by weight.
  • the liquid, solution or suspension for at least one of the corrosion protection layers, lacquer layers and / or lacquer-like polymer-containing layers can contain at least one silane and / or siloxane in addition to water, calculated as silane, in particular in a content in the range from 0, 1 to 50 g / L, preferably in a range of 1 to 30 g / L.
  • the liquid, solution or suspension for at least one of the corrosion protection layers, lacquer layers and / or lacquer-like polymer-containing layers in addition to water and / and at least one organic solvent can contain at least one silane and / or siloxane calculated as silane, in particular in a content in Range from 51 to 1300 g / L.
  • the liquid, solution or suspension for at least one of the corrosion protection layers, lacquer layers and / or lacquer-like polymer-containing layers, optionally in addition to water and / and at least one organic solvent can contain at least one silane and / or siloxane calculated as silane, in particular in a range from 0J to 1600 g / L, preferably in a range from 100 to 1500 g / L.
  • the silane may be an acyloxy, an alkyl silane, an alkyltrialkoxysilane, an amino, an aminoalkyl, a aminopropyltrialkoxysilane, a bis-silyl silane, an epoxy silane, a fluoroalkylsilane, a glycidoxy such as a Glycidoxyalkyltrialkoxysilan, an isocyanato silane, a mercapto-silane , a (meth) acrylato-silane, a mono-silyl-silane, a multi-silyl-silane, a bis- (trialkoxysilyl-propyl) amine, a bis- (trialkoxysilyl) ethane, a sulfur- end silane, a bis (trialkoxysilyI) propyltetrasulphan, an ureidosilane such as a (ureidopropyltrial
  • it can be at least one silane in a mixture with a content of at least one alcohol such as ethanol, methanol and / or propanol of up to 8% by weight, based on the silane content, preferably up to 5% by weight, particularly preferably up to 1% by weight, very particularly preferably up to 0.5% by weight, possibly with a content of inorganic particles, in particular in a mixture of at least one aminosilane such as, for example, bis-aminosilane with at least one Alkoxy-silane such as trialkoxy-silyl-propyl-tetrasulfane or a vinylsilane and a bis-silyl-aminosilane or a bis-silyl-polysulfur silane and / or a bis-silyl-aminosilane or an aminosilane and a multi-silyl-functional silane.
  • a content of at least one alcohol such as ethanol, methanol and / or propanol of up to 8%
  • the liquid, solution or suspension for at least one of the corrosion protection layers, lacquer layers or / and lacquer-like polymer-containing layers can contain an organic film former in the form of a solution, dispersion, emulsion, microemulsion or / and suspension.
  • the liquid, solution or suspension for at least one of the corrosion protection layers, lacquer layers and / or lacquer-like polymer-containing layers can contain at least one synthetic resin as organic film former, in particular at least one synthetic resin based on acrylate, ethylene, polyester, polyurethane, silicone polyester, epoxy, Phenol, styrene, styrene butadiene, urea-formaldehyde, their derivatives, copolymers, block copolymers, cross-polymers, monomers, oligomers, polymers, mixtures or / and copolymers.
  • at least one synthetic resin as organic film former, in particular at least one synthetic resin based on acrylate, ethylene, polyester, polyurethane, silicone polyester, epoxy, Phenol, styrene, styrene butadiene, urea-formaldehyde, their derivatives, copolymers, block copolymers, cross-polymers, monomers, oligo
  • polymer is used here - in particular also for the lacquer-like layers - as a generic term for all these variants of synthetic resins and their derivatives, copolymers, block copolymers, cross-polymers, monomers, oligomers, polymers, mixtures and copolymers.
  • the liquid, solution or suspension for at least one of the corrosion protection layers, lacquer layers and / or lacquer-like polymer-containing layers can contain a synthetic resin mixture or / and mixed polymer as organic film-forming agent, which contains a synthetic resin based on acrylate, ethylene, urea-formaldehyde, Contains polyester, polyurethane, styrene or / and styrene butadiene or their derivatives, copolymers, cross polymers, oligomers, polymers, mixtures or / and copolymers from which an organic film is formed during or after the release of water and other volatile constituents.
  • a synthetic resin mixture or / and mixed polymer as organic film-forming agent, which contains a synthetic resin based on acrylate, ethylene, urea-formaldehyde, Contains polyester, polyurethane, styrene or / and styrene butadiene or their derivatives, copolymers, cross polymers,
  • the liquid, solution or suspension for at least one of the corrosion protection layers, lacquer layers and / or lacquer-like polymer-containing layers can be used as organic film-forming resins or / and polymers, copolymers, block copolymers, cross-polymers, monomers, oligomers, polymers, mixtures or / and Contain copolymers or their derivatives based on acrylate, polyethylene imine, polyurethane, polyvinyl alcohol, polyvinyl phenol, polyvinyl pyrrolidone and / or polyaspartic acid, in particular copolymers with a phosphorus-containing vinyl compound.
  • the liquid, solution or suspension for at least one of the corrosion protection layers, lacquer layers and / or lacquer-like polymer-containing layers can contain synthetic resin, the acid number of which is in the range from 5 to 250.
  • the acid number is preferably in the range from 10 to 140, particularly preferably in the range from 15 to 100.
  • the liquid, solution or suspension for at least one of the corrosion protection layers, lacquer layers and / or lacquer-like polymer-containing layers can be synthetic resins and / or polymers, copolymers, block copolymers, crosspolymers, monomers, oligomers, polymers, mixtures or / and copolymers or their Contain derivatives whose molecular weights in the range of at least 1,000 u, preferably of at least at least 5,000 u or up to 500,000 u, particularly preferably in the range from 20,000 to 200,000 u.
  • the liquid, solution or suspension for at least one of the corrosion protection layers, lacquer layers and / or lacquer-like polymer-containing layers synthetic resins and / or polymers, block copolymers, copolymers, crosspolymers, monomers, oligomers, polymers, mixtures or / and copolymers or contain their derivatives, in particular also based on pyrrolidone (s), in particular 0.1 to 500 g / L, preferably 0.5 to 30 or 80 to 250 g / L.
  • the liquid, solution or suspension for at least one of the corrosion protection layers, lacquer layers and / or lacquer-like polymer-containing layers can contain an organic film former, the pH of which in an aqueous preparation without the addition of further compounds is preferably in the range from 1 to 12 in the range from 2 to 10, particularly preferably in the range from 2.5 to 9.
  • the liquid, solution or suspension for at least one of the corrosion protection layers, lacquer layers or / and lacquer-like polymer-containing layers can contain an organic film-forming agent which only contains water-soluble synthetic resins and / or polymers, copolymers, block copolymers, crosspolymers, monomers, oligomers, Contains polymers, mixtures and / or copolymers or their derivatives, in particular those which are stable in solutions with pH values ⁇ 5.
  • the liquid, solution or suspension for at least one of the corrosion protection layers, lacquer layers or / and lacquer-like polymer-containing layers can contain an organic film former whose synthetic resins and / or polymers, copolymers, block copolymers, crosspolymers, monomers, oligomers, polymers, Mixtures or / and copolymers or their derivatives have carboxyl groups.
  • the liquid, solution or suspension for at least one of the corrosion protection layers, lacquer layers or / and lacquer-like polymer-containing layers can contain an organic film former in which the acid groups of the synthetic resins or / and polymers, copolymers, block copolymers, crosspolymers, monomers, Oligomers, polymers, mixtures or / and copolymers or their derivatives with ammonia, with amines such as morpholine, dimethylethanolamine, diethylethanolamine or triethanolamine or / and with alkali metal compounds such as sodium hydroxide are stabilized.
  • an organic film former in which the acid groups of the synthetic resins or / and polymers, copolymers, block copolymers, crosspolymers, monomers, Oligomers, polymers, mixtures or / and copolymers or their derivatives with ammonia, with amines such as morpholine, dimethylethanolamine, diethylethanolamine or triethanolamine or / and with alkali metal compounds such as
  • the liquid, solution or suspension for at least one of the corrosion protection layers, lacquer layers and / or lacquer-like polymer-containing layers contain 0.1 to 200 g / L and preferably 0.3 to 50 g / L of the organic film former, in particular 0.6 to 20 g / L.
  • the liquid, solution or suspension for at least one of the corrosion protection layers, lacquer layers and / or lacquer-like polymer-containing layers can contain 100 to 2000 g / L and preferably 300 to 1800 g / L of the organic film former, in particular 800 to 1400 g / L ,
  • the liquid, solution or suspension for at least one of the corrosion protection layers, lacquer layers and / or lacquer-like polymer-containing layers can contain a proportion of monomers, in particular in the range of at least 5% by weight, preferably of at least 20% by weight. %, particularly preferably of at least 40% by weight.
  • the proportion of water or organic solvent may be reduced and in particular may be less than 10% by weight; under certain circumstances, it can even be largely or completely free of water and / or organic solvents.
  • the liquid, solution or suspension for at least one of the corrosion protection layers, lacquer layers and / or lacquer-like polymer-containing layers can contain at least one organometallic compound, in particular with a content of titanium and / or zirconium. These organometallic compounds are often corrosion inhibitors and often also adhesion promoters.
  • the liquid, solution or suspension for at least one of the corrosion protection layers, lacquer layers and / or lacquer-like polymer-containing layers can contain a content of at least one silane and / or siloxane calculated as silane in the aqueous composition, preferably in a range from 0.2 to 40 g / L, particularly preferably in a range from 0.5 to 10 g / L.
  • the liquid, solution or suspension for at least one of the corrosion protection layers, lacquer layers and / or lacquer-like polymer-containing layers can contain at least one partially hydrolyzed silane, at least one completely hydrolyzed silane and / or at least one siloxane.
  • siloxanes form from the silanes.
  • corresponding siloxanes can also be added.
  • the silanes / siloxanes can either be used alone, in a mixture, e.g. can be used with at least one fluoride complex or together with polymers.
  • the liquid, solution or suspension for at least one of the corrosion protection layers, lacquer layers or / and lacquer-like polymer-containing layers can contain at least one partially hydrolyzed and / or non-hydrolyzed contain drolyzed silane, in particular if the silane content is more than 100 g / L, particularly preferably if the silane content is more than 1000 g / L.
  • the liquid, solution or suspension for at least one of the anti-corrosion layers, lacquer layers and / or lacquer-like polymer-containing layers can each contain at least one acyloxysilane, one alkylsilane, one aminosilane, one bis-silylsilane, one epoxysilane, one fluoroalkylsilane, one glycidoxysilane , an isocyanato-silane, a mercapto-silane, a (meth) acrylato-silane, a mono-silyl-silane, a multi-silyl-silane, a sulfur-containing silane, an ureidosilane, a vinylsilane and / or at least one corresponding siloxane contain.
  • the liquid, solution or suspension for at least one of the corrosion protection layers, lacquer layers and / or lacquer-like polymer-containing layers can be a finely divided powder, a dispersion or a suspension such as e.g. a carbonate, oxide, silicate or sulfate can be added, in particular colloidal or amorphous particles.
  • Particles with an average particle size in the range from 4 nm to 150 nm, in particular in the range from 10, can be added to the liquid, solution or suspension for at least one of the corrosion protection layers, lacquer layers or / and lacquer-like polymer-containing layers as an inorganic compound in particle form up to 120 nm.
  • the average size of the electrically conductive particles of a welding primer can be in the range of 0.02 to 15 ⁇ m.
  • the liquid, solution or suspension for at least one of the corrosion protection layers, lacquer layers and / or lacquer-like polymer-containing layers can be used as an inorganic compound in particle form based on at least one compound of aluminum, barium, cerium, calcium, lanthanum, silicon, titanium , Yttrium, zinc and / or zirconium can be added.
  • the liquid, solution or suspension for at least one of the corrosion protection layers, lacquer layers and / or lacquer-like polymer-containing layers can contain 0.1 to 300 g / L, preferably 0.2 to 60 g / L, of the at least one inorganic compound in particle form contain.
  • the liquid, solution or suspension for at least one of the corrosion protection layers, lacquer layers and / or lacquer-like polymer-containing layers as organic solvent for the organic polymers can contain at least one water-miscible and / or water-soluble alcohol, a glycol ether or a pyrrolidone such as eg N-methylpyrrolidone and / or water are used, in the case of using a solvent mixture, in particular a mixture of at least one long-chain alcohol, such as e.g. Propylene glycol, an ester alcohol, a glycol ether and / or butanediol with water, but preferably only water without an organic solvent.
  • a solvent mixture in particular a mixture of at least one long-chain alcohol, such as e.g. Propylene glycol, an ester alcohol, a glycol ether and / or butanediol with water, but preferably only water without an organic solvent.
  • the liquid, solution or suspension for at least one of the corrosion protection layers, lacquer layers and / or lacquer-like polymer-containing layers can contain an organic solvent content in the range from 0.1 to 10% by weight.
  • the liquid, solution or suspension for at least one of the corrosion protection layers, lacquer layers or / and lacquer-like polymer-containing layers can contain at least one wax selected from the group of paraffins, polyethylenes and polypropylenes, in particular an oxidized wax, as a lubricant ,
  • the wax content in a layer is preferably in the range from 0J to 20% by weight
  • the liquid, solution or suspension for at least one of the corrosion protection layers, lacquer layers and / or lacquer-like polymer-containing layers can contain a wax as a lubricant, the melting point of which is in the range from 40 to 160 ° C., preferably 0.1 to 100 g / L, particularly preferably 20 to 40 g / L or 0.1 to 10 g / L, very particularly preferably 0.4 to 6 g / L, for example a crystalline polyethylene wax.
  • the liquid, solution or suspension for at least one of the corrosion protection layers, lacquer layers and / or lacquer-like polymer-containing layers can contain at least one rare earth element compound, in particular at least one compound selected from the group consisting of chloride, nitrate, sulfate , Sulfamate and complexes, for example with a halogen or with an aminocarboxylic acid, in particular complexes with EDTA, NTA or HEDTA, scandium, yttrium and lanthanum also being regarded as rare earth elements.
  • at least one rare earth element compound in particular at least one compound selected from the group consisting of chloride, nitrate, sulfate , Sulfamate and complexes, for example with a halogen or with an aminocarboxylic acid, in particular complexes with EDTA, NTA or HEDTA, scandium, yttrium and lanthanum also being regarded as rare earth elements.
  • the liquid, solution or suspension for at least one of the corrosion protection layers and / or lacquer-like polymer-containing layers can contain a rare earth element compound of or / and with cerium, in particular in a mixture with other rare earth elements, for example at least partially on the basis of mixed metal ,
  • the content of cerium compounds in a layer is preferably in the range from 0J to 99% by weight, particularly preferably in the range from 25 to 95% by weight.
  • the at least one rare earth element compound in the aqueous solution in a content of 1 to 80 g / L together with a content in the range of at least 10 mg / L chloride, with a peroxide content in the range of 1 to 50 g / L calculated as H 2 0 2 and containing at least one cation selected from the 5th or 6th main group of the Periodic Table of the Elements, in particular bismuths, used in the range from 0.001 to 1 g / L.
  • the content of the at least one rare earth element compound in the aqueous solution is preferably 5 to 25 g / L together with a content in the range of at most 500 mg / L chloride, with a content of peroxide in the range of 5 to 25 g / L calculated as H 2 0 2 and containing at least one cation selected from the 5th or 6th main group of the Periodic Table of the Elements, in particular bismuths, in the range from 0.01 to 0.3 g / L.
  • the liquid, solution or suspension for at least one of the corrosion protection layers, lacquer layers or / and lacquer-like polymer-containing layers can contain at least one oxidizing agent, in particular a peroxide, at least one accelerator and / or at least one catalyst, preferably a compound or ions of Bi, Cu or / and Zn.
  • the liquid, solution or suspension for at least one of the corrosion protection layers, lacquer layers or / and lacquer-like polymer-containing layers can contain at least one compound selected from the group of the mono-, bis- and multi-silanes, in particular:
  • Y 3 Multi-silanes of the general formula Y 3 .
  • silanes can each be hydrolyzed, partially hydrolyzed or / and not hydrolyzed in a solution, emulsion or / and suspension.
  • the total content of silanes or siloxanes per layer can preferably be on the one hand in the range from 0.01 to 20% by weight, on the other hand preferably in the range of 60 to 99.9% by weight.
  • the liquid, solution or suspension for at least one of the corrosion protection layers can contain at least one compound of the type XYZ, X * Y * Z * or / and ⁇ * ⁇ * z * Y * X *,
  • Y is an organic group with 2 to 50 C atoms, where X and Z, identical or different, are OH, SH, NH 2 , NHR ', CN,
  • Y is an organic group R which contains 2 to 50 C atoms, of which at least 60% of these C atoms are present as CH 2 groups,
  • R ' is an alkyl group with 1 to 4 carbon atoms
  • R is an H atom or an alkyl group with 1 to 4 C atoms, preferably a total of 0.01 to 10 g / L, preferably 0.05 to 5 g / L, very particularly preferably 0.08 to 2 g / L.
  • the compound of the type XYZ, ⁇ * ⁇ * Z * or / and ⁇ * ⁇ * z * Y * X * can be suitable for forming self-assembling molecules that can form a layer of these self-assembling molecules, in particular on the metallic surface, preferably a monomolecular layer.
  • the liquid, solution or suspension for at least one of the corrosion protection layers can contain at least one of the following compounds of the type XYZ, X * Y * Z * or / and ⁇ * ⁇ * z * Y * X *:
  • Diethylenetriaminepentamethylenephosphonic acid, 2-phosphonobutane-1, 2,4-tricarboxylic acid Diethylenetriaminepentamethylenephosphonic acid, 2-phosphonobutane-1, 2,4-tricarboxylic acid.
  • the content of compounds of these types in one layer is preferably in the range from 50 to 100% by weight.
  • At least one of the liquids, solutions or suspensions for at least one of the corrosion protection layers and / or lacquer-like polymer-containing layers can contain phosphate and zinc, optionally also manganese, nickel or / and copper.
  • the phosphate content in a layer is preferably in the range from 8 to 100% by weight, particularly preferably in the range from 20 to 95% by weight, very particularly preferably in the range from 60 to 90% by weight.
  • At least one of the liquids, solutions or suspensions for at least one of the corrosion protection layers and / or paint-like polymer-containing layers 0.1 to less than 100 g / L zinc ions, 0.4 to 80 g / L manganese ions, up to 12 g / L nickel ions, up to 100 g / L peroxide calculated as H 2 0 2 and 1 to 500 g / L phosphate ions, calculated as P 2 0 5 and preferably 0.2 to less than 50 g / L zinc ions, 0 , 5 to 45 g / L manganese ions and 2 to 300 g / L phosphate ions, calculated as P 2 0 5 .
  • At least one of the liquids, solutions or suspensions for at least one of the corrosion protection layers and / or lacquer-like polymer-containing layers can contain phosphate, preferably based on Zn or ZnMn, possibly with a nickel content
  • At least one of the liquids, solutions or suspensions for at least one of the corrosion protection layers, lacquer layers and / or lacquer-like polymer-containing layers can contain phosphate, fluoride, tetrafluoride and / or hexafluoride.
  • phosphonate (s) which at least partially align themselves as self-assembling molecules on the metallic surface, and fluoride complexes with separate solutions are preferably formed in largely separate layers.
  • At least one of the liquids, solutions or suspensions for at least one of the corrosion protection layers, lacquer layers and / or lacquer-like polymer-containing layers can contain phosphonate, tetrafluoride and / or hexafluoride.
  • At least one of the liquids, solutions or suspensions for at least one of the corrosion protection layers, lacquer layers or / and lacquer-like polymer-containing layers can contain an organic film former, fluoride, tetrafluoride, hexafluoride or / and at least one inorganic compound in particle form and optionally contain at least one silane,
  • at least one of the liquids, solutions or suspensions for at least one of the corrosion protection layers, lacquer layers and / or lacquer-like polymer-containing layers can contain an additive selected from the group of organic binders, biocides, defoamers, corrosion inhibitors, adhesion promoters, wetting agents, photoinitiators and contain polymerization inhibitors.
  • At least one of the liquids, solutions or suspensions for at least one of the corrosion protection layers, lacquer layers and / or lacquer-like polymer-containing layers can contain at least one filler and / or pigment, in particular at least one electrically conductive pigment, selected from the group of Contain dyes, color pigments, graphite, graphite mica pigments, oxides such as iron oxides, molybdenum compounds, phosphates, phosphides such as iron phosphides, carbon black and zinc.
  • the content of such compounds in a layer is preferably in the range from 0.1 to 60% by weight, particularly preferably in the range from 5 to 35% by weight.
  • an activating treatment preferably an activation based on titanium
  • a corrosion protection layer, lacquer layer or lacquer-like polymer-containing layer can be applied before the application of a corrosion protection layer, lacquer layer or lacquer-like polymer-containing layer.
  • a rinse and / or passivation can be applied, preferably a rinse solution based on rare earth compounds, complex fluorides, silanes, titanium compounds and / or zirconium compounds or one Passivation solution based on rare earth compounds, complex fluorides, silanes, titanium compounds and / or zirconium compounds.
  • At least one of the liquids, solutions or suspensions for at least one of the corrosion protection layers, paint layers or / and paint-like polymer-containing ones Layers contain an organic film former which is cured after application to the metallic substrate by heat and / or actinic radiation - in particular by electron, UV or / and radiation in the range of visible light.
  • At least one of the corrosion protection layers, lacquer layers or / and lacquer-like polymer-containing layers can only be partially cured before gluing, welding and / or forming and can only be fully cured after gluing, welding or / and forming, the first Curing before gluing, welding or / and forming by actinic radiation - in particular by electron, UV or / and radiation in the visible light range - and the second curing after gluing, welding or / and forming preferably thermally - in particular by Radiant heat and / or warm air - takes place.
  • the first hardening is preferably not carried out thermally, in particular by UV radiation, because there are usually no furnaces for heating in the metal strip plant, in particular in the galvanizing belt plant.
  • the second curing is preferably carried out thermally, in particular if the sheet is also to be post-cured.
  • the second curing is preferably carried out by actinic radiation, in particular by UV radiation, because the curing often takes place better than by thermal crosslinking alone.
  • more than one type of hardening can be used in each of the hardening steps.
  • the actinic radiation is referred to in this application as UV radiation and the associated curing as UV curing.
  • the liquid, solution or suspension for at least one of the corrosion protection layers, lacquer layers and / or lacquer-like polymer-containing layers can have a pH in the range from 0.5 to 12, preferably in the range from 1 to 11, particularly preferably in the range from 2 to 10.
  • the liquid, solution or suspension for at least one of the corrosion protection layers, lacquer layers and / or lacquer-like polymer-containing layers can be at a temperature in the range from 5 to 95 ° C., preferably in the range from 5 to 50 ° C. the respective surface are applied, very particularly preferably in the range from 10 to 40 ° C.
  • the substrate and / or the respective surface can be kept at temperatures in the range from 5 to 120 ° C. when the corrosion protection layer (s) are applied. This can be the metallic surface during the first coating.
  • the first or second corrosion protection layer or the base coat can preferably be applied in a temperature range from 10 to 50 ° C.
  • the coated metallic surface can be dried at a temperature in the range from 20 to 400 ° C. PMT (peak metal temperature).
  • the first and second corrosion protection layers can preferably be applied in a temperature range from 15 to 100 ° C., the base coat in particular in a temperature range from 15 to 270 ° C.
  • the coated strips can be cut or wound up into a coil, if necessary after cooling to a temperature in the range from 10 to 70 ° C.
  • the cut strips are coated in the edge region after pressing, cutting or / and punching with a temporarily applied, removable or with a permanently protective coating, e.g. at least one coating based on dry lubricant, phosphate, hexafluoride, paint-like coating or / and paint.
  • a permanently protective coating e.g. at least one coating based on dry lubricant, phosphate, hexafluoride, paint-like coating or / and paint.
  • the liquid, solution or suspension for at least one of the corrosion protection layers, lacquer layers and / or lacquer-like polymer-containing layers can be zen, flooding, knife application, spraying, spraying, brushing or dipping and if necessary by subsequent squeezing with a roller.
  • the coating applied in each case with the liquid, solution or suspension for at least one of the corrosion protection layers, lacquer layers or / and lacquer-like polymer-containing layers can have a layer weight in the range from 0.0005 mg / m 2 to 150 g / m 2 can be set, preferably in the range from 0.0008 mg / m 2 to 30 g / m 2 , particularly preferably in the range from 0.001 mg / m 2 to 10 g / m 2 , in particular in the range from 1 to 6 g / m 2 ,
  • At least one coating of lacquer or of a lacquer-like, polymer-containing coating can be applied to the partially or completely cured film, the first lacquer layer or lacquer-like polymer-containing layer being a coating essentially of a primer , a thin - in the range from 0.1 to 10 ⁇ m, preferably in the range from 0.15 to 6 ⁇ m, particularly preferably in the range from 0.2 to 4 ⁇ m - organically applied polymer-containing material (so-called permanent coating), a reaction primer, a shop primer or a wash primer.
  • a primer such as e.g. a coil coating primer, a primer as a replacement for the cathodic dip coating, a welding primer.
  • At least one coating of lacquer, a mixture of or with can be applied to the at least partially lacquered or lacquer-like coating with a polymer-containing layer or to the at least partially lacquered or lacquer-like coating with a polymer-containing layer
  • Polymers, paint, adhesive and / or adhesive carrier are applied
  • the clean or cleaned and possibly activated metallic surface can be mixed with the liquid, solution or Suspension for one of the corrosion protection layers is brought into contact and at least one film, which may also contain particles, is formed on the metallic surface, which is then dried and optionally additionally cured, the dried and possibly also cured film each having a layer thickness in the May have a range from 0.01 to 100 ⁇ m, in particular a film with a layer thickness in the range from 5 to 50 ⁇ m, particularly preferably in the range from 8 to 30 ⁇ m.
  • Pigments, in particular color pigments or white pigments, metal particles such as zinc particles, fillers of all types such as chalk, oxides such as aluminum oxide, talc or silicates, carbon particles, nanoparticles can be used as particles.
  • At least one lacquer layer as a primer or a lacquer-like polymer-containing layer as a pretreatment primer, primer, primer as a replacement for the cathodic dip lacquer, gliding primer, reaction primer, welding primer and / or wash primer, if appropriate instead of a primer, can be applied.
  • the overall paint build-up may up to 300 ⁇ m, mostly up to 120 ⁇ m, often up to 90 ⁇ m, occasionally up to only 70 ⁇ m, if more than one lacquer or / and lacquer-like layer is used.
  • At least one of the lacquer layers and / or lacquer-like polymer-containing layers can be cured by heat or / and actinic radiation, in particular by UV radiation.
  • the coated tapes or tape sections can be reshaped, painted, with polymers such as e.g. PVC coated, printed, glued, hot soldered, welded and / or connected to one another or to other elements by clinching or other joining techniques.
  • polymers such as e.g. PVC coated, printed, glued, hot soldered, welded and / or connected to one another or to other elements by clinching or other joining techniques.
  • Table 1 Variants of the production process for the coating of steel sheet to be galvanized
  • a strong alkaline cleaner to completely remove organic contaminants such as e.g. Clean grease and oil and other dirt.
  • Acidic pickling spray briefly with sulfuric acid water with pH 1 to 2.
  • Galvanizing hot-dip galvanizing by immersion in a weld pool or electrolytic galvanizing by immersion in a bath with an aqueous solution
  • Zinc solution Coating with technically pure zinc, which may contain certain contaminants, especially aluminum and lead (HDG); Coating with an iron or aluminum-rich zinc alloy such as Galvanne-al ® , Galfan ® or Galvalume ® . 5.
  • electrolytic galvanizing after the deposition of the galvanizing layer, acid pickling to remove any unevenness in the galvanizing layer.
  • phosphate layers are to be applied: coating with an activation solution, in particular based on titanium. 7. If necessary Application of a first corrosion protection layer, e.g. as pre-phosphating.
  • UV radiation for crosslinking the second lacquer-like coating.
  • first lacquer layer as a filler or top coat, possibly modified with a content of nanoparticles.
  • Z number of process steps without all possible intermediate steps that may be necessary, such as pickling, cleaning, activating, rinsing or rinsing or drying.
  • Tables 2A-J Variants of the assignment of process steps and production lines for steel sheet to be galvanized, intermediate steps being omitted
  • the following table clarifies which metallic substrates or metallic coatings on substrates are coated with at least one corrosion protection layer or / and with at least one coating-like coating and which composition the corrosion protection layer preferably has.
  • Table 3 Relationship of the preferred chemical basis of corrosion protection layers or corresponding pre-treatment solutions depending on the metallic substrate or metallic coating on a substrate: goes very well: ⁇ , good: x, possibly: •. 1., 2. and 3. represent different successive coatings. with phosphate contents: if necessary with added nickel
  • the method according to the invention is particularly advantageous because at least some and in the medium term all chemical and paint process steps can be shifted from the automobile plant to the steelworks or aluminum / magnesium rolling mill in the short term.
  • these process sections can run on fast-running production lines, in particular on conveyor systems, and are therefore time-saving, much more uniform, environmental gentle, chemical-saving, water-saving, space-saving, energy-saving, cost-saving and with higher quality.
  • the costs of the pre-treated, painted and ggt formed parts are significantly lower per square meter of the coated surface. There are smaller amounts of sludge than with the previous production method, especially during pre-treatment and painting. Because there are significantly lower volumes of the respective baths.
  • the total time for cleaning and pretreatment can be reduced from 20 to 40 minutes to 15 to 30 seconds.
  • the layer weight of the pretreatment coating can possibly be reduced from 1.5 to 4 g / m 2 to approximately 0.01 to 2 g / m 2 .
  • the chemical consumption during the pretreatment can be reduced from 20 to 40 g / m 2 to 1 to 10 g / m 2 .
  • the painting and baking time can be reduced from 120 to 180 minutes to 0J to 2 minutes - calculated for 2 layers of paint each.
  • the paint consumption drops for 3 layers of paint with 200 to 300 g / m 2 to 80 to 120 g / m 2 for 2 layers of paint.
  • the total costs could drop to about 5 to 20% of today's total costs per m 2 of coated surface.
  • paint or varnish-like layers are applied to the belt and not in the production of parts or body, the costs can be significantly reduced compared to the production of parts or body. Therefore production on a belt, such as on a coil coating line, is preferable to part or body production.
  • concentrations and compositions given relate to the treatment solution itself and not to any higher concentration batch solutions that may be used. All concentration data are to be understood as solids content, i.e. the concentrations relate to the weight proportions of the active components regardless of whether the raw materials used are in diluted form e.g. were presented as aqueous solutions.
  • the surface treatment of the test sheets was always carried out in the same way and comprised the following individual steps:
  • a polyethylene-acrylate copolymer with an acid number of about 30 and a melting range at a temperature in the range from 65 to 90 ° C. was chosen for the experiments.
  • the polyacrylic acid-vinylphosphonate copolymer used had an acid number of about 620 and its 5% aqueous solution had a pH of almost exactly 2.0.
  • the technically pure compounds which hydrolyzed in the aqueous composition and which were converted into siloxanes in particular during drying and curing have been added to the silanes used.
  • the mixing of the individual components could usually be carried out in any order. However, when adding manganese carbonate, zirconium ammonium carbonate or aluminum hydroxide, care must be taken that these substances are first dissolved in the concentrated acidic components before the main amount of water is added. When adding aluminum hydroxide or manganese carbonate, care is taken that these substances are completely dissolved in the aqueous composition.
  • the treatment solution contained water-soluble copolymers based on acrylate and one organic phosphorus-containing acid and an aqueous dispersion of inorganic particles in the form of pyrogenic silica.
  • the solution had the following composition:
  • the silica dispersion contained particles with an average particle diameter measured by scanning electron microscopy in the range from about 20 to 50 nm.
  • the constituents were mixed in the order given and the pH of the solution was then brought to 4.5 with a fluoride-containing ammonia solution set.
  • the aqueous composition contained 3.4 g / L of acids, 4 g / L of solid and, moreover, only water. After application, the solution was dried in a forced air oven at approx. 70 ° C PMT (peak metal temperature). The steel sheets pretreated in this way were coated with a commercially available chrome-free coil coating system.
  • Example 2 Steel sheets were treated as described in Example 1, but with a composition which contained only titanium as the transition metal and the inorganic particles in the form of an aqueous colloidal silica dispersion;
  • silica dispersion contained particles with an average particle diameter measured by scanning electron microscopy in the range from about 8 to 20 nm.
  • the silane compound was first hydrolyzed in an acetic acid solution with stirring for several hours before the remaining constituents were added. A pH of 5 was then set.
  • a 25% stable, aqueous dispersion was obtained by adding a suitable amount of an ammonia solution at about 95 ° C. with stirring and reflux cooling.
  • a treatment solution which was composed as follows was prepared with the dispersion thus obtained:
  • the pH of the treatment solution was adjusted to 8.5. Care was taken to ensure that the pH of the solution was not during production drops below a value of 7.5, otherwise the polymer or the fumed silica could have precipitated. Furthermore, care was taken to ensure that the film was dried at a PMT of at least 80 ° C. Otherwise, the steel strip was treated as described in Example 1.
  • Hot-dip galvanized steel sheets (HDG) with a zinc content of over 95% in the galvanizing layer were cleaned, degreased and subjected to a surface treatment with the composition described below in the same way as the steel sheets in the examples described above:
  • Hot-dip galvanized steel sheets were treated analogously to Example 5, but with a composition which contained the inorganic particles in the form of a colloidal solution:
  • Example 7 According to the Invention:
  • Hot-dip galvanized steel sheets were treated analogously to Example 6, but with a treatment solution, the proportion of inorganic particles of which was five times higher than the composition given in Example 6:
  • Example 3 hot-dip galvanized steel sheets were treated with a composition which, in addition to fluorometalate, polymers and inorganic particles, contained a silane hydrolyzed in aqueous solution.
  • the treatment solution consisted of the following components:
  • the temperature of the sheet surface was at least 80 ° C. while the film was drying.
  • Hot-dip galvanized steel surfaces were treated in accordance with the preceding Example 9 with an alkaline composition of pH 9, which, in addition to the polymer dispersion and the Zr component, contained an aqueous dispersion of TiO 2 particles with an average particle size of 5 nm and which was as follows was composed:
  • hot-dip galvanized steel surfaces were treated with a composition containing TiO 2 , which, in contrast to the previous example, had an acidic pH of 3 and additionally contained aluminum ions in addition to the titanium and zirconium compounds.
  • a composition containing TiO 2 which, in contrast to the previous example, had an acidic pH of 3 and additionally contained aluminum ions in addition to the titanium and zirconium compounds.
  • the Ti0 2 -containing treatment solutions have, in comparison to the Si0 2 - containing compositions usually further improved corrosion protection properties and in particular galvanized surfaces. However, these compositions have a significantly reduced storage stability compared to the Si0 2 -containing solutions.
  • hot-dip galvanized steel sheets were treated with a composition which additionally contained manganese ions:
  • Mn added to the treatment solution on the one hand improves the corrosion protection effect of the coating and in particular increases the resistance of the layer to alkaline media such as e.g. compared to cleaning agents common in coil coating.
  • Example 13 According to the Invention: According to Example 12 according to the invention, hot-dip galvanized steel sheets were treated with a composition which contained a colloidal silica dispersion instead of the Ti0 2 dispersion:
  • Mn to the treatment solution on the one hand improves the corrosion protection effect of the coating and in particular increases the resistance of the layer to alkaline media such as, for example, to cleaning agents customary in coil coating.
  • colloidal Si0 2 was added instead of the Ti0 2 dispersion.
  • Example 14 hot-dip galvanized steel sheets were treated with a composition which contained no hexafluorotitanic acid and a somewhat reduced content of hexafluorozirconic acid or polyacrylic acid:
  • Mn improves the corrosion protection effect of the coating and in particular increases the resistance of the layer to alkaline media such as, for example, to cleaning agents customary in coil coating.
  • the H 2 TiF 6 content was omitted and the H 2 ZrF 6 content was reduced. This improved the paint adhesion.
  • hot-dip galvanized steel sheets were treated with a composition which did not contain any aluminum hydroxide:
  • Mn improves the corrosion protection effect of the coating and in particular increases the resistance of the layer to alkaline media such as e.g. compared to cleaning agents common in coil coating.
  • the pH was adjusted by adding ammonia.
  • the addition of aluminum hydroxide was omitted.
  • Example 9 Based on the composition of Example 9, the polyethylene acrylate content was increased from 5 to 10 g / L. As a result, the coating according to the invention is made thicker.
  • Example 16 According to Example 16 according to the invention, an addition of 0.5 g / L of polyethylene wax with a melting point in the range from 125 to 165 ° C. was added to the composition of Example 16. This significantly improved the lubricity of the coating.
  • Example 18 According to the Invention: The corrosion inhibitor diethylthiourea was added to the aqueous composition of Example 14 according to the invention at 1.0 g / L, which further improved the corrosion resistance and increased the safety for series production.
  • the inorganic compounds in particle form used in the process according to the invention are decisive for the adhesion of a further organic coating applied subsequently and for the corrosion properties of the composite of metal, pretreatment according to the invention and organic coating.
  • steel surfaces were therefore treated with an aqueous composition which largely corresponded to the process according to the invention in terms of its ingredients, but did not contain the important addition of the inorganic particles.
  • the composition contained in detail 2 g / L hexafluorotitanic acid,
  • composition resulted in a significantly reduced corrosion protection compared to the equivalent composition described in Example 2 according to the invention with the addition of a colloidal silica dispersion.
  • Example 6 In comparison to the equivalent composition described in Example 6 according to the invention with the addition of a colloidal silica dispersion, the composition gave both a significantly reduced adhesion of a subsequently applied coil coating coating and a significantly reduced corrosion protection.
  • a suitable organic film former in the form of water-soluble or water-dispersible polymers is also of crucial importance for the corrosion protection effect of the system and the adhesion of a coating applied subsequently. Both the lack of the bath component and the choice of an unsuitable polymer compound have a significant negative impact on corrosion protection and paint adhesion.
  • a polymer system unsuitable for the purposes of the invention stem is an aqueous solution of a polyvinylpyrrolidone from BASF.
  • the composition of the bath solution otherwise corresponded to the method according to the invention.
  • Hot-dip galvanized steel sheets treated with this composition had a significantly reduced paint adhesion as well as poorer corrosion protection compared to the comparable examples according to the invention. What factors at the molecular level make a polymer system suitable for an application in the sense of the invention has not yet been sufficiently clarified.
  • the polymer systems indicated as suitable in the examples according to the invention were determined by screening methods.
  • Table 1 shows the compositions of the test baths listed in the examples for comparison.
  • Table 2 summarizes the results of the corrosion and paint adhesion tests on the coatings obtained with these compositions.
  • Table 1 Overview of the composition of the examples and comparative examples.
  • Polyacrylic stands for polyacrylic acid, Zr (C0 3 ) 2 for a Zr ammonium carbonate.
  • Example 2 Results of the adhesion and corrosion protection results.
  • the adhesion test using the T-Bend test was carried out according to the NCCA standard, i.e. with a bend of T1, the space between the bent sheet metal halves was about 1 mm thick, so that the bend diameter was about 1 mm. After this very strong bend, the paint adhesion was checked by tear tests with adhesive tape and the result was given as a percentage of the area of the paint flaking and delamination.
  • the results show that the treatment solutions according to the invention are used as standard with regard to the adhesion properties of a subsequently applied organic coating and the corrosion properties that can be achieved with the coating structure Chromating processes deliver comparable results.
  • the comparative examples show that the properties of the coating are mainly based on the correct choice of the polymers and the inorganic particles.
  • the treatment method according to the invention can work both in the slightly alkaline and in the acidic pH range if suitable polymer systems are selected for the respective pH range.
  • the coatings of the examples according to the invention only had a layer thickness in the range from 0.01 to 0.2 ⁇ m, mostly in the range from 0.02 or 0.03 to 0J ⁇ m, these coatings were of excellent quality.

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  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Life Sciences & Earth Sciences (AREA)
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Abstract

Procédé d'enduction d'une bande métallique, selon lequel ladite bande, ou éventuellement les segments de bande fabriqués dans la suite du processus à partir de ladite bande, est couverte d'abord avec au moins une couche de protection contre la corrosion, puis avec au moins une couche de type peinture contenant du polymère et / ou au moins une couche de peinture. Après enduction avec au moins une couche de protection contre la corrosion ou après enduction avec au moins une couche de type peinture et / ou au moins une couche de peinture, ladite bande est divisée en segments. Les segments de bande recouverts sont ensuite soumis à un formage, assemblés et / ou enduits à l'aide d'au moins une (autre) couche de type peinture et / ou une couche de peinture. Au moins une des couches de protection contre la corrosion est formée par enduction de la surface avec une dispersion aqueuse qui contient, outre de l'eau, (a) au moins une matière filmogène organique contenant au moins un polymère soluble ou dispersible dans l'eau, (b) une certaine teneur en cations et / ou en hexa- ou tétrafluorocomplexes de cations choisis dans le groupe constitué par titane, zirconium, hafnium, silicium, aluminium et bore, ainsi que (c) au moins un composé inorganique sous forme particulaire dont le diamètre moyen des particules est de l'ordre de 0,005 à 0,02 νm, tel que mesuré à l'aide d'un microscope électronique à balayage. Selon ledit procédé, la surface métallique propre est mise en contact avec la composition aqueuse et un film contenant des particules est formé sur la surface métallique, ledit film étant ensuite séché et éventuellement durci. Ce film séché et éventuellement durci possède une épaisseur de l'ordre de 0,01 à 10 νm.
EP01986707A 2000-10-11 2001-10-10 Procede de pretraitement et d'enduction subsequente de surfaces metalliques avant le formage a l'aide d'une couche de type peinture et utilisation des substrats ainsi recouverts Withdrawn EP1330499A2 (fr)

Applications Claiming Priority (7)

Application Number Priority Date Filing Date Title
DE10050532 2000-10-11
DE10050532 2000-10-11
DE10110830 2001-03-06
DE10110830 2001-03-06
DE10119606 2001-04-21
DE10119606 2001-04-21
PCT/EP2001/011738 WO2002031065A2 (fr) 2000-10-11 2001-10-10 Procede de pretraitement et d'enduction subsequente de surfaces metalliques avant le formage a l'aide d'une couche de type peinture et utilisation des substrats ainsi recouverts

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