WO2015070933A1 - Procédé permettant de revêtir des substrats métalliques d'une couche de conversion et d'une couche sol-gel - Google Patents

Procédé permettant de revêtir des substrats métalliques d'une couche de conversion et d'une couche sol-gel Download PDF

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Publication number
WO2015070933A1
WO2015070933A1 PCT/EP2013/074110 EP2013074110W WO2015070933A1 WO 2015070933 A1 WO2015070933 A1 WO 2015070933A1 EP 2013074110 W EP2013074110 W EP 2013074110W WO 2015070933 A1 WO2015070933 A1 WO 2015070933A1
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compound
groups
radical
group
aqueous
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PCT/EP2013/074110
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German (de)
English (en)
Inventor
Natalja OTT
Sebastian SINNWELL
Katrin Wczasek
Andrea Wiesmann
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Basf Coatings Gmbh
Henkel Ag & Co. Kgaa
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Priority to PCT/EP2013/074110 priority Critical patent/WO2015070933A1/fr
Publication of WO2015070933A1 publication Critical patent/WO2015070933A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/82—After-treatment
    • C23C22/83—Chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
    • C23C18/1208—Oxides, e.g. ceramics
    • C23C18/1212—Zeolites, glasses
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
    • C23C18/1208—Oxides, e.g. ceramics
    • C23C18/1216—Metal oxides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
    • C23C18/122—Inorganic polymers, e.g. silanes, polysilazanes, polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/125—Process of deposition of the inorganic material
    • C23C18/1254—Sol or sol-gel processing
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
    • C23C22/36—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates
    • C23C22/361—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates containing titanium, zirconium or hafnium compounds

Definitions

  • the present invention relates to a method for at least partially coating a metallic substrate comprising at least the steps of (1) applying a zirconium, copper, fluorine-based conversion layer, and (2) subsequently coating the at least partially coated substrate with an aqueous composition the aqueous composition used in step (2) is an aqueous sol-gel composition, an at least partially coated substrate obtainable by this process.
  • the metallic components used for the production usually have to be protected against corrosion, since the demands on the corrosion protection to be achieved are very high, in particular because manufacturers often provide a guarantee against rust through for many years.
  • Such corrosion protection is usually achieved by coating the components or the substrates used for their production with at least one suitable coating.
  • a disadvantage of the known coating methods in particular of the known methods used in the automotive industry, is that these methods usually provide a phosphating step as a pretreatment, in which the substrate to be coated, after an optional cleaning step and before a dip coating step with a metal phosphate such as zinc phosphate in a phosphating step is treated to ensure adequate corrosion protection.
  • This pretreatment usually involves the performance of several process steps in several different and differently heated plunge pools.
  • waste sludge is generated which pollutes the environment and must be disposed of. It is therefore desirable, in particular for economic and ecological reasons, to be able to save such a pretreatment step, but nevertheless to achieve at least the same corrosion protection effect achieved with the known methods.
  • Chromium (VI) should be avoided for reasons of toxicity and carcinogenicity of chromium (VI), as well as chromium (VI) compounds which are well-effective in preventing corrosion. Chromium-containing compositions are known, for example, from US Pat. No. 5,178,690.
  • the prior art proposes various electroless methods which are based on different coating materials and different layer structure.
  • DE 10 2006 053 292 A1 and DE 10 2005 023 728 A1 describe lacquer-layer-forming corrosion protection agents and processes for their current-free application.
  • coating processes are described in which first sheets of galvanized steel are cleaned and then treated with ammonium molybdate and in some cases additionally yttrium nitrate and ammonium nitrate-containing corrosion inhibitors by immersion.
  • a second aqueous coating composition which contains water-dispersible or water-soluble, foreign or self-crosslinking polymers with ligands covalently bound thereto, wherein the ligands are capable of chelating with the metal surfaces to be coated or metal ions released from the surfaces.
  • the second coating compositions described in DE 10 2006 053 292 also contain surface-active substances.
  • US 2006/01334339 A1 describes the application of a phosphomolybdate, colloidal silica and aminosilanes-containing composition, which may additionally contain electrically conductive polyanilines as anticorrosive composition.
  • EP 1 669 475 A1 discloses a pretreatment solution for producing a conversion layer on metallic substrates, wherein the pretreatment solution contains zirconium and at least one hydrolyzable aminosilane compound or its hydrolysates.
  • the pretreatment solution is used in particular for the pretreatment of metallic vehicle bodies.
  • WO 2006/120390 A2 describes a two-layered sol-gel coating, in which the sol-gel layer covering the substrate is preferably a polyamine crosslinker and the second sol-gel layer is an organically modified silicate (a so-called Ormosil ), which is preferably obtained from tetraalkoxysilanes and / or 3-glycidoxypropylmethoxysilane.
  • the first layer may also contain nanoparticles of metal atoms or ions, in particular zirconium, whereby the optical properties, especially the antireflective properties are to be improved.
  • DE 103 32 744 A1 describes silane-based sol-gel pretreatment layers which are produced using fluorine-containing and fluorine-free silanes.
  • US 2006/0099429 A1 relates to a pretreatment composition for metallic surfaces containing hydrolyzable or at least partially hydrolyzed silanes, metal chelates such as zirconium chelates and organic film formers.
  • German laid-open specification DE 103 20 779 A1 discloses anticorrosive coatings for metals with the sequence of layers: metal surface, silicon compound-containing sol layer and a layer based on at least one organosilane.
  • the first sol-layer is preferably obtained from a coating composition comprising an acidic aqueous-alcoholic mixture of a tetraalkoxysilane and an alkyltrialkoxysilane.
  • the organosilane of the second layer is preferably perfluorinated or contains a double bond or a group selected from amino groups or epoxy groups.
  • the US patent application US 2007/0048537 A1 describes a two-layered sol-gel structure for metallic substrates.
  • the first metal-near layer can be obtained using zirconium alkoxides.
  • the second layer serves to fill cracks in the first layer.
  • WO 2006/027007 A1 discloses a method for producing weather-resistant and corrosion-resistant formed sheet metal parts of aluminum or aluminum alloys, which are coated with two sol-gel lacquer layers.
  • the sol-gel lacquer layers can be obtained from coating compositions which preferably contain an aqueous acidic colloidal silicic acid solution and alkoxysilanes such as tetraethoxysilane and methyltrimethoxysilane. It is also possible that the sol-gel coating precedes a pretreatment of the aluminum, in particular a treatment with a chromium-free electrolyte which contains at least one of the elements Ti, Zr, F, Mo or Mn.
  • a disadvantage of the corrosion protection coatings known from the prior art is often that they have very high layer weights and, depending on the substrate material, there are great differences in the layer weights. Often, in particular, steel has insufficient protection against corrosion as a substrate, or there is a lack of filiform corrosion resistance on aluminum as a substrate.
  • the corrosion protection effect should be achieved by means of thin layers with reduction of the layer weight.
  • the corrosion protection effect is to be improved universally on a wide variety of metallic substrates such as steel, galvanized steels, zinc and aluminum.
  • metallic substrates such as steel, galvanized steels, zinc and aluminum.
  • the most homogeneous possible layer structure should be ensured.
  • the coating process should be easy to carry out, in particular, the corrosion protection effect should be obtained without the costly electrocoating.
  • step (2) coating the at least partially, preferably substantially fully coated, substrate immediately following step (1) with an aqueous composition, wherein the aqueous composition used in step (2) is an aqueous sol-gel composition.
  • the coated substrates produced by the process according to the invention in particular coated galvanized steels and aluminum, are distinguished from corresponding comparative examples in particular in that the infiltration as a measure of corrosion protection effect in the case of Process comprising in particular step (2) produced coated substrates significantly less precipitates.
  • the method according to the invention is preferably a method for the at least partial coating of a metallic substrate used in and / or for the automotive industry.
  • the process can be carried out continuously, for example by the coil coating process or batchwise.
  • the method according to the invention is a method for at least partially coating a metallic substrate in which the sol-gel composition applied in the second step forms the outermost layer of the coated substrate after it has dried and / or cured. That is, in this embodiment, the second coating step is not followed by any further coating steps.
  • substrates coated in this way can exhibit antifingerprint properties.
  • the metallic substrates used according to the invention are preferably selected from the group consisting of steel, preferably steel selected from the group consisting of cold-rolled steel, galvanized steel such as dip-galvanized steel, alloy-galvanized steel, and aluminized steel, aluminum and magnesium, in particular galvanized steel, aluminized steel and aluminum.
  • Suitable substrates are in particular parts of bodies or complete bodies of automobiles to be produced.
  • the cleaning and / or degreasing of the substrate is preferably carried out by means of an aqueous alkaline solution of one or more surface-active compounds (detergents) and subsequent rinsing with demineralized water.
  • pH values of 9 to 12, especially 10 to 12 are particularly suitable.
  • Cleaning baths usually have a temperature of from room temperature to 70 ° C, preferably 40 to 60 ° C.
  • the cleaning can be done by simply immersing in a cleaning bath composition, it being advisable to stir the bath composition.
  • the detergent-containing bath cleaning time is usually 30 seconds to 5 minutes, preferably 30 seconds to 2 minutes before rinsing with desalted water, as indicated above, to remove detergent and alkali residues.
  • the metallic substrate used in accordance with the invention may be a substrate which has been partially pretreated with at least one metal phosphate.
  • a pretreatment by means of a phosphating which usually takes place after cleaning the substrate and before the dip-coating of the substrate, is in particular a pretreatment step customary in the automobile industry.
  • a metal phosphate such as zinc phosphate
  • the present invention does not exclude that prior to performing the method according to the invention phosphated, for example metallic substrates are bonded to non-phosphated metallic substrates, and the resulting metallic substrates have both phosphated and non-phosphated areas.
  • Such bonded substrates can also be used in the present process.
  • no phosphating step takes place in the process according to the invention, in particular not before carrying out step (1) of the process according to the invention.
  • the process according to the invention preferably does not comprise a pretreatment step with a metal phosphate to be carried out before step (1) of the process according to the invention.
  • the method comprises a step (1), which is carried out directly before the step (2), namely a
  • (B2) at least one water-soluble compound as a source of fluoride ions, which contains at least one fluorine atom;
  • the Zr atoms preferably have the oxidation state +4 and the copper atoms the oxidation state +2.
  • the aqueous pretreatment composition (B) contains a fluoro complex such as hexafluorozirconate and / or hexafluorozirconic acid due to the components (B1) and (B2) and / or (B3) contained therein.
  • the pretreatment composition (B) has a total concentration of the element Zr not lower than 5 -10 "5 mol / L but not larger than 0.25 mol / L.
  • the concentration is lower than 5-10 " 5 mol / L, insufficient layer thicknesses are achieved in some cases, however, when the concentration exceeds 0.25 mol / L, in some cases, the stability of the pre-treatment composition is lowered.
  • the total Zr concentration is particularly preferably 0.004 to 0.1 mol / L, very particularly preferably 0.01 to 0.05 mol / L.
  • the pretreatment composition (B) has a total concentration of the element Cu not lower than 1 10 ⁇ 5 mol / L but not larger than 1 10 ⁇ 2 mol / L. More preferably, the Cu-total concentration of 1 ⁇ 10 5 to 5 10 "3 mol / l, very particularly preferably 2 10 -5 to 2 10 ⁇ 3 mol / L.
  • the pH of the pretreatment composition (B) is preferably 1 to 6, more preferably 2 to 5.5, and most preferably 3 to 5, such as 3.5. If the substrate is cold-rolled steel or aluminum, it is recommended to set the pH to 3 to 4. For zinc, dip galvanized or electrogalvanised substrates, such as dip galvanized steel and electrogalvanised steel it is recommended to adjust the pH to 4.5 to 5.5. If it falls below a pH of 1, in some cases, the pickling rate is too high and the pretreatment composition (B) is optionally contaminated with metal ions, whereby their stability is reduced and the process stability is at risk.
  • pickling rate is understood to mean the amount of metal ions in grams which dissolves from the metallic substrate per unit area in a specific time interval.
  • the pickling rate is in some cases too low and the film formation insufficient. Also, the bath stability diminishes in some cases.
  • the pretreatment composition (B) contains, in addition to the water-dispersible or water-soluble zirconium and copper compounds, another water-dispersible or water-soluble metal-containing compounds which comprise a metal ion or metalation selected from the group consisting of Ca, Mg, Al, B, Zn, Mn and W and mixtures thereof.
  • a metal ion or metalation selected from the group consisting of Ca, Mg, Al, B, Zn, Mn and W and mixtures thereof.
  • the aluminosilicates preferably have an Al to Si ratio of at least 1: 3.
  • the preparation of such pretreatment solutions is likewise described in WO 2009/1 15504 A1.
  • nanoparticles are understood in particular to be those which have an average particle size (defined here as a median) of 1 to 100 nm (determined by dynamic light scattering in accordance with DIN ISO 13321).
  • the particle size can be determined non-invasively using the Zetasizer Nano Zs from Malvern Instruments GmbH, Hamburg. Unless otherwise stated herein, all standard disclosures refer to the current version of the filing date of the present invention.
  • the conversion layer applied in step (1) represents a conversion layer produced exclusively by zirconium, copper and fluorine compounds.
  • the application of the conversion layer in step (1) of the method according to the invention is preferably carried out by immersing the preferably cleaned and / or degreased substrate in the pretreatment composition (B). That is, the pretreatment composition (B) is preferably used as a dipping bath. Less preferably, the pretreatment solution can also be applied by spraying or other methods conventional for aqueous coating compositions.
  • the deposition of the conversion layer is usually autophoretic, that is, unlike cathodic or anodic dip coatings, without applying a voltage.
  • the metallic substrate is preferably immersed in the dipping bath consisting of the pretreatment composition (B) for 1 to 300 seconds, more preferably 5 to 120 seconds, and most preferably 10 to 80 seconds. If immersion time (immersion time) is less than 1 second, a sufficient film thickness is not obtained in some cases, and at immersion times of more than 300 seconds, the film thicknesses may become too large in some cases and dipping-bath stability may lower.
  • the bath temperature during application of the pretreatment composition (B) by immersion is from room temperature (25 ° C) to 80 ° C, more preferably 25 to 75 ° C and most preferably 30 to 70 ° C such as 35 to 65 ° C or 35 or 65 ° C.
  • Step (1) preferably comprises a final rinsing of the conversion layer with water, in particular desalinated water.
  • Section (2) of the method according to the invention relates to the coating of the at least partially, preferably substantially completely coated, substrate in step (1) with an aqueous composition, wherein the aqueous composition used in step (2) is an aqueous sol-gel composition.
  • Step (2) thus represents a direct (post) coating of the at least partially coated according to step (1) substrate with an aqueous sol-gel composition.
  • the term “coating” or “post-coating” is preferably understood as meaning immersion of the substrate which is at least partially coated according to step (1) into the aqueous sol-gel composition used in step (2). That is, the sol-gel composition is particularly preferably used as an immersion bath. Less preferred is a spraying or spraying of the at least partially coated according to step (1) substrate with the aqueous sol-gel composition used in step (2) or a rolling of the aqueous sol-gel composition used in step (2) in the according to Step (1) at least partially coated substrate.
  • the term “coating” or “subsequent coating” in the context of the present invention means immersing the substrate which is at least partially coated according to step (1) into the aqueous sol-gel composition used in step (2).
  • the aqueous composition used in step (2) of the process according to the invention preferably has a temperature in the range of 8 ° C to 60 ° C, more preferably in the range of 10 ° C to 55 ° C, particularly preferably in the range of 12 ° C to 50 ° C, most preferably in the range of 14 ° C to 45 ° C, in particular in the range of 15 ° C to 40 ° C or in the range of 15 ° C to 37 ° C, more preferably in the range of 17 ° C to 35 ° C, most preferably in the range of 18 ° C to 30 ° C or in the range of 18 ° C to 25 ° C, on.
  • the immersion time is preferably in the range of 1 to 1000 seconds, more preferably 5 to 800 seconds, most preferably in the range of 5 to 100 seconds more preferably in the range of 5 to 60 seconds.
  • the substrate coated with the sol-gel coating is preferably at an exchange rate of 10 to 5000 mm / min, more preferably 100 to 3000 mm / min and most preferably 400 to 1500 mm / min, such as 500 to 1000 mm / min from the dipping bath. If the exchange rate is less than 10 mm / min, the coat thickness of the coating is in some cases too low and exceeds 5000 mm / min, so in some cases the coat thickness of the coat is too high.
  • composition used in step (2) of the method according to the invention is an aqueous composition.
  • aqueous in connection with the aqueous composition or aqueous sol-gel composition used in step (2) of the process according to the invention is preferably understood to mean a liquid composition which acts as a liquid diluent, ie as a liquid solvent and / or dispersant
  • the aqueous composition used according to the invention may additionally contain a proportion of at least one organic solvent, preferably at least one water-miscible organic solvent Group consisting of alcohols such as methanol, ethanol, 1-propanol and 2- Propanol, organic carboxylic acids such as formic acid, acetic acid and propionic acid, ketones such as acetone and glycols such as ethylene glycol or propylene glycol, and mixtures thereof.
  • the proportion of these preferably water-miscible organic solvents is preferably at most 20.0% by weight, more preferably at most 15.0% by weight, very preferably at most 10.0% by weight, in particular at most 5.0% by weight. -%, more preferably at most 2.5 wt .-%, most preferably at most 1, 0 wt .-%, each based on the total amount of the aqueous composition used in step (2) of the inventive composition contained liquid diluents, ie, liquid solvents and / or dispersants, in particular solvents.
  • the aqueous composition used in step (2) of the process according to the invention is in the form of an aqueous solution or aqueous dispersion, in particular in the form of an aqueous solution.
  • the aqueous composition used in step (2) of the process according to the invention preferably has a pH in the range from 1 to 6, preferably in the range from 2.0 to 6.0, very particularly preferably in the range from 3 to 6 or 4 to 5 on.
  • Methods for adjusting pH values in aqueous compositions are known to those skilled in the art.
  • the desired pH of the aqueous composition used in step (2) of the process according to the invention is preferably adjusted by adding at least one acid, more preferably at least one inorganic and / or at least one organic acid.
  • Suitable inorganic acids are, for example, hydrochloric acid, sulfuric acid, phosphoric acid and / or nitric acid.
  • a suitable organic acid is, for example, acetic acid.
  • the desired pH value of the aqueous composition used in step (2) of the process according to the invention is adjusted by addition of phosphoric acid.
  • the aqueous composition used in step (2) of the process of the invention is an aqueous sol-gel composition.
  • the skilled person is familiar with the terms "sol-gel composition", "sol-gel” and the preparation of sol-gel compositions and sol-gels, for example from D. Wang et al., Progress in Organic Coatings 2009, 64, 327-338 or S. Zheng et al., J. Sol-Gel. Be. Technol. 2010, 54, 174-187.
  • an aqueous "sol-gel composition” is preferably understood to mean an aqueous composition for the preparation of which at least one starting compound which contains at least one metal atom and / or semimetal atom such as, for example, M 1 and / or M 2 and at least two hydrolyzable includes groups such as two hydrolyzable groups X 1, which has optionally further comprising at least one non-hydrolysable organic radical such as R 1, is reacted with water and the like.
  • the at least two hydrolyzable groups are in the at least one starting compound contained preferably in each case directly to at least a metal atom and / or at least one semimetal atom in each case bound by means of a single bond.
  • the at least two hydrolyzable groups are split off in a first hydrolysis step and replaced within the at least one starting compound by OH groups, whereby the formation of metal-OH bonds or half-metal OH bonds within the used in the first step at least one starting compound results (hydrolysis step).
  • a condensation of two molecules formed in the first step takes place, for example, by reaction of one of the metal OH bonds of one molecule thus formed with one of the metal OH bonds of the second molecule thus formed (condensation step).
  • the molecule thus formed which comprises, for example, at least one metal-O-metal group (or metal-O-half-metal group or half-metal O-half-metal group) and, in addition, a total of at least two hydrolyzable groups, can then be hydrolyzed again and analogously react with further compounds obtainable after the first hydrolysis step, and then react further in accordance with the resultant compound formed analogously, so that it comes to the formation of chains and in particular of two- or three-dimensional structures.
  • This at least two-step process comprises at least the first hydrolysis Step and at least the second condensation step is referred to as a sol-gel process or as a sol-gel process.
  • a sol or a gel is formed, whereby the aqueous composition is referred to as a sol-gel composition.
  • a pure sol composition is preferably understood to mean a composition in which the reaction products are colloidally dissolved.
  • a sol composition is characterized by a lower viscosity than a gel composition.
  • a pure gel composition is understood to mean a composition which is distinguished by a high viscosity and which has a gel structure. The transition from a sol to a gel composition is preferably characterized by a sudden increase in viscosity.
  • the at least one starting compound required for the preparation of the aqueous sol-gel composition used according to the invention is preferably prepared by stirring in water or adding water to the at least one starting compound. This is preferably done at a temperature in the range of 15 ° C to 40 ° C or in the range of 15 ° C to 37 ° C, more preferably in the range of 17 ° C to 35 ° C, most preferably in the range of 18 ° C to 30 ° C or in the range of 18 ° C to 25 ° C.
  • the preparation may optionally also be carried out at temperatures higher than 40 ° C, for example at a temperature of up to 80 ° C, i.
  • the aqueous sol-gel composition thus obtained is allowed to rest for a period of time in the range of 1-72 hours at a temperature of 18-25 ° C prior to its use in step (2) of the process of the invention.
  • the at least one starting compound which comprises at least one metal atom and / or semimetal atom such as, for example, M 1 and / or M 2 and at least two hydrolyzable groups, for example at least two hydrolyzable groups X 1 , used to prepare the aqueous sol-gel composition may also be at least have a non-hydrolyzable organic radical.
  • This nonhydrolyzable organic radical like
  • a corresponding radical R 1 is preferably bonded directly to the output in a compound contained at least metal atom and / or semi-metal atom such as M 1 and / or M 2 by means of a single bond.
  • the at least two-step process comprising at least the first hydrolysis step and at least the second condensation step results in the formation of chains and in particular of two- or three-dimensional structures which have both inorganic and organic groups.
  • the sol-gel composition thus obtained may be referred to as an inorganic-organic hybrid sol-gel composition.
  • the at least one nonhydrolyzable organic radical such as, for example, the radical R 1 contains at least one reactive functional group, which is preferably selected from the group consisting of primary amino groups, secondary amino groups, epoxide groups, thiol groups, isocyanate groups.
  • phosphorus-containing groups such as phosphonate groups, silane groups, which in turn may optionally have at least one non-hydrolyzable organic radical which optionally has at least one reactive functional group, and groups which have an ethylenically unsaturated double bond such as vinyl groups or (meth ) acrylic groups, most preferably selected from the group consisting of primary amino groups, secondary amino groups, epoxide groups, thiol groups, and groups having an ethylenically unsaturated double bond such as vinyl groups or (meth) Acrylic groups, in particular, is selected from the group consisting of primary amino groups and epoxide groups.
  • a particularly preferred functional group for all embodiments in the context of the present invention is the epoxide group.
  • (meth) acrylic in the context of the present invention in each case the meanings “methacrylic” and / or "acrylic".
  • non-hydrolysable organic radical having at least one reactive functional group is preferably understood in conjunction with a non-hydrolysable organic radical, for example the radical R 1 in the meaning of the present invention is that the non-hydrolyzable organic radical has at least one such functional group which has a reactivity with respect to the optionally present in the binder of the dip paint and / or in the optionally present in the dip paint crosslinking agent reactive functional groups. A reaction of corresponding functional groups may lead to the formation of covalent bonds.
  • the at least one nonhydrolyzable organic radical such as, for example, the radical R 1 need not necessarily have at least one reactive functional group, but may also be a non-hydrolyzable organic radical which has no reactive functional group.
  • non-hydrolyzable organic radical which does not have a reactive functional group in connection with a nonhydrolyzable organic radical such as, for example, the radical R 1 in the context of the present invention preferably means that the nonhydrolyzable organic radical has no such functional group
  • an adjacent coating is a coating, optionally applied in a step (3) following step (2) directly, which has a reactivity towards the binders, including crosslinking agents, of an adjacent coating.
  • a thus-obtained aqueous sol-gel composition in which the at least one starting compound which, in addition to the at least two hydrolyzable groups, such as at least two hydrolyzable groups X 1 comprises at least one nonhydrolyzable organic radical such as R 1, is characterized in particular by the fact that in their production no colloidal hydroxide or colloidal oxide, which is disclosed for example in EP 1 510 558 A1 or WO 03/090938 A1, but an inorganic-organic hybrid sol-gel composition is formed.
  • the aqueous sol-gel composition used in step (2) is obtainable by reaction at least two starting compounds, each of which independently of one another have at least one metal atom and / or semimetal atom such as M 1 and also each independently at least two hydrolyzable groups such as at least two hydrolyzable groups X 1 , wherein the at least two hydrolyzable groups preferably each directly to the in the at least two starting compounds respectively contained metal atom and / or half metal atom are bound by single bonds, with water, preferably at least one of the at least two starting compounds in addition to the at least two hydrolyzable groups also at least one non-hydrolyzable group, more preferably at least one non-hydrolyzable organic radical such for example, the radical R 1 , wherein said non-hydrolyzable group in particular directly to the metal atom contained in the at least one starting compound and / or semimetal atom as M 1 is bonded by means of a single bond and thereby optionally at least one reactive functional group, which is
  • Each of M 1 and M 2 is independently a metal atom or a semimetal atom, preferably at least one of the variables M 1 and M 2 , more preferably both of the variables M 1 and M 2 , being Si,
  • X 1 and X 2 are each independently hydrolyzable
  • Stand for the valence of the metal atom or semimetal metal M 1 preferably stands for +3 or +4, stands for the valence of the metal atom or semimetal M 2 , preferably in each case stands for +3 or +4,
  • R 1 for X 1 a nonhydrolyzable organic radical, for (T) (M 1 ) X (X 1 ) C or for (U) [(M 1 ) X (X 1 ) C ] 2 , preferably represents one nonhydrolyzable organic radical, represents a nonhydrolyzable organic radical
  • R 3 is a nonhydrolyzable organic radical, for (T) (M 1 ) X (X 1 ) C , for (U) [(M 1 ) X (X 1 ) C ] 2
  • (V) (M 2 ) y is (X 2 ) d (R 2 ) or is (W) [(M 2 ) y (X 2 ) d (R 2 )] 2, preferably a nonhydrolyzable organic radical
  • a is x when R 1 is X 1 or
  • a is x-1 when R 1 is a nonhydrolyzable organic radical, (T) (M 1 ) X (X 1 ) C or (U) [(M 1 ) X (X 1 ) C ] 2 each under the condition that a is at least 2, b is y-2,
  • T, U, V and W are each independently a radical having from 1 to 30 carbon atoms and optionally having up to 10 heteroatoms and heteroatom groups selected from the group consisting of O, S and N, c is x-1, preferably with the proviso that c is at least 2 and d is y-2, preferably with the proviso that d is at least 2, with water.
  • hydrolyzable group Any conventional well-known to those skilled hydrolyzable group such as X 1 or X 2 can be used as part of the starting compound at least one for preparing the aqueous sol-gel composition employed, particularly the one component (at least A1) and / or (A2).
  • a "hydrolyzable group” such as the groups X 1 and X 2 of the present invention is preferably a hydrolyzable group selected from the group consisting of halides as defined, preferably fluorides, chlorides, bromides and iodides, in particular fluorides and chlorides, alkoxy groups , Preferably, alkoxy groups OR a , wherein R a is an optionally substituted by a Ci-6-alkoxy group Ci-i6-aliphatic radical, preferably CMO aliphatic radical, particularly preferably Ci-6-aliphatic radical, in particular Ci-6 - Alkyl radical as for methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, or tert-butyl, carboxylate groups, preferably Ci-6-carboxylate groups, in particular carboxylate groups selected from the group consisting of acetate and more preferably diketonate groups selected from the group consisting of ace
  • a "hydrolyzable group” such as those of the groups X 1 and X 2 is an alkoxy group, preferably an alkoxy group OR a , wherein R a is an optionally substituted with a Ci-6-alkoxy group Ci 16-aliphatic radical, preferably Ci-io-aliphatic radical, particularly preferably Ci-6-aliphatic radical, in particular Ci-6-alkyl radical as for methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso Butyl, or tert-butyl, is understood, of which methyl and ethyl are particularly preferred.
  • Ci 16-aliphatic radical preferably Ci-io-aliphatic radical, particularly preferably Ci-6-aliphatic radical, in particular Ci-6-alkyl radical as for methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso Butyl, or tert-butyl
  • valency in connection with metallic atoms or semi-metal atoms, such as M 1 and M 2 is known.
  • the weight for the purposes of the present invention is the oxidation number of each metal atom or metalloid atom such as M 1 and M 2. Significances are preferred for x and y - each independently - from +2, +3 and +4, in particular +3 and +4.
  • Suitable metal atoms such as, for example, M 1 and M 2 are all customary metal atoms, including transition metal atoms, which are part of the at least one starting compound, in particular (A1) and / or (A2), such as Al, Ti, Zr, and Fe, preferably Ti and Zr.
  • Suitable semi-metal atoms, such as, for example, M 1 and M 2 are all customary semimetal atoms which form part of at least one Starting compound, in particular (A1) and / or (A2) may be, such as B and Si, preferably Si.
  • the metal atoms and semimetal ions such as M 1 and M 2 are each independently selected from the group consisting of Al, Ti, Zr, Fe, B and Si, more preferably selected from the group consisting of Ti, Zr and Si, more particularly preferably selected from the group consisting of Zr and Si.
  • the metal atoms and semimetal atoms such as M 1 and M 2 each mean Si.
  • M 1 is selected from the group consisting of Al, Ti, Zr, Fe, B and Si, more preferably selected from the group consisting of Ti, Zr and Si, most preferably selected from the group consisting of Zr and Si, in particular M 1 signifies Si.
  • M 2 is Si.
  • the valences x, y, and z of the metal atoms and semimetal atoms such as M 1 and M 2 are preferably selected so that the metal atoms and half metal atoms such as M 1 and M 2 are each independently selected from the group consisting of Al 3+ , Ti 4+ , Zr 4+ , Fe 3+ , Fe 4+ , B 3+ and Si 4+ , more preferably from the group consisting of Al 3+ , Ti 4+ , Zr 4+ and Si 4+ , more particularly preferably from the group consisting of Ti 4+ , Zr 4+ and Si 4+ , in particular in each case stand for Si 4+ .
  • nonhydrolyzable organic radical Any customary organic radical which is not hydrolyzable can be present as a constituent of the at least one starting compound used for preparing the aqueous sol-gel composition, in particular the at least one component (A1) and / or (A2) serve.
  • non-hydrolysable organic group for example in connection with the radicals R 1, R 2 and R 3 - each independently - preferably a non-hydrolysable organic radical selected from the group consisting of Ci-Cio-aliphatic radicals, Ci- Cio-heteroaliphatic radicals, C3-Cio-cycloaliphatic radicals, 3-10-membered heterocycloaliphatic radicals Radicals, 5-12-membered aryl or heteroaryl radicals, C 3 -C 10 -cycloaliphatic radicals bonded via a C 1-6 aliphatic radical, 3-10-membered heterocycloaliphatic radicals bonded via a C 1-6 aliphatic radical, via a 6-12 aliphatic radical bonded 5-12 membered aryl or heteroaryl radicals, understood, where each of these radicals may optionally contain at least one reactive functional group, provided that the bond of the non-hydrolyzable organic radical to the metal
  • C 1 -C 10 aliphatic radical for the purposes of this invention preferably comprises acyclic saturated or unsaturated, preferably saturated, aliphatic hydrocarbon radicals, ie. Ci-io-aliphatic radicals, each of which may be branched or unbranched and unsubstituted or mono- or polysubstituted, having 1 to 10 carbon atoms, i. Ci-io-Alkanyle, C2-io-alkenyls and C2-io-alkynyls. In this case, alkenyls have at least one C-C double bond and alkynyls at least one C-C triple bond.
  • Ci-io-aliphatic radicals each of which may be branched or unbranched and unsubstituted or mono- or polysubstituted, having 1 to 10 carbon atoms, i. Ci-io-Alkanyle, C2-io-alkenyls and C2-io-alkynyl
  • a C 1 -C 10 aliphatic radical is preferably selected from the group consisting of methyl, ethyl, n-propyl, 2-propyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, iso -Pentyl, neo-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, and n-decyl.
  • d-Cio-heteroaliphatic radical in the context of this invention preferably comprises C 1 -C 10 -aliphatic radicals in which at least one, optionally also 2 or 3, carbon atoms are represented by a heteroatom such as N, O or S or a heteroatom group such as NH, N (Ci-io-aliphatic radical) or N (Ci-io-aliphatic radical) 2 is replaced / are.
  • C 3-10 -cycloaliphatic radical preferably comprises cyclic aliphatic (cycloaliphatic) hydrocarbons having 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms, where the hydrocarbons are saturated or unsaturated (but not aromatic ), unsubstituted or mono- or polysubstituted.
  • the binding of the C3-io-cycloaliphatic radical to the respective general general structure can be achieved via any and possible Ring member of the C3-io-cycloaliphatic radical take place, but preferably takes place via a carbon atom.
  • the C3-io-cycloaliphatic radicals can furthermore be mono- or polysubstituted, for example in the case of adamantyl, bicyclo [2.2.1] heptyl or bicyclo [2.2.2] octyl.
  • a C 3-10 -cycloaliphatic radical is selected from the group comprising cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cycloheptyl.
  • heterocycloaliphatic radical preferably includes aliphatic saturated or unsaturated (but not aromatic) cycloaliphatic radicals having from three to ten, ie, 3, 4, 5, 6, 7, 8, 9, or 10 ring members in which at least a, optionally also 2 or 3 carbon atoms by a heteroatom such as N, O or S or a heteroatom group such as NH, N (Ci-io-aliphatic radical) or N (Ci-io-aliphatic radical) 2 is replaced / are, wherein the The linkage to the general structure above can take place via any and possible ring member of the heterocycloaliphatic radical, but preferably takes place via a carbon atom.
  • aryl in the context of this invention means aromatic hydrocarbons having 6 to 12 ring members, preferably 6 ring members, including phenyls and naphthyls.
  • Each aryl radical may be unsubstituted or monosubstituted or polysubstituted, wherein the aryl substituents may be the same or different and may be in any desired and possible position of the aryl.
  • the attachment of the aryl to the overall general structure can be via any and possible ring member of the aryl radical done.
  • aryl is selected from the group consisting of phenyl, 1-naphthyl and 2-naphthyl.
  • heteroaryl represents a 5- to 12-membered, preferably 5- or 6-membered cyclic aromatic radical containing at least 1, optionally also 2, 3, 4 or 5 heteroatoms, wherein the heteroatoms each independently are selected from the group S, N and O and the heteroaryl radical may be unsubstituted or mono- or polysubstituted; in the case of heteroaryl substitution, the substituents may be the same or different and may be in any and possible position of the heteroaryl.
  • the binding to the general structure above can take place via any and possible ring member of the heteroaryl radical.
  • heteroaryl moiety is selected from the group consisting of benzofuranyl, benzoimidazolyl, benzothienyl, benzothiadiazolyl, benzothiazolyl, benzotriazolyl, benzooxazolyl, benzooxadiazolyl, quinazolinyl, quinoxalinyl, carbazolyl, quinolinyl, dibenzofuranyl, dibenzothienyl, furyl (furanyl), imidazolyl , Imidazothiazolyl, indazolyl, indolizinyl, indolyl, isoquinolinyl, isoxazoyl, isothiazolyl, indolyl, naphthyridinyl, oxazolyl, oxadiazolyl, phenazinyl, phenothiazinyl, phtalazinyl, pyrazolyl, pyridyl (2-pyridy
  • C 3 -C 10 -cycloaliphatic radical attached via a C 1-6 aliphatic radical, 3-10-membered heterocycloaliphatic radical, 5-12-membered aryl or heteroaryl radical preferably means that the radicals mentioned have the meanings defined above and in each case via a Ci-6-aliphatic radical to the respective parent general structure is bound, which may be branched or unbranched, saturated or unsaturated unsubstituted or mono- or polysubstituted.
  • a radical or a group such as, for example, the group X 1 within the compound (A1) or a non-hydrolyzable organic radical such as the radicals R 2 and R 3 within the compound (A2) occurs several times within a molecule, then this radical or these Each group has the same or different meanings: for example, the group for X 1 is OR a , where R a is is a Ci-6-aliphatic radical, and occurs, for example, within the molecule (M 1 ) x (X 1 ) a (R 1 ) a total of three times, then X 1 may, for example, three times each represent O-C2H 5 or may once for O-C2H 5 , once for O-CH 3 and once for O-C3H6. If R 2 and R 3 within (A2) each represent a nonhydrolyzable organic radical, one of these radicals may for example have at least one reactive functional group and the remainder may have no reactive functional group.
  • the radicals T, U, V and W are each independently a radical which has 1 to 30 carbon atoms and may optionally have up to 10 heteroatoms and heteroatom groups selected from the group consisting of O, S and N.
  • the radicals T, U, V and W can be aliphatic, heteroaliphatic, cycloaliphatic, heterocycloaliphatic, aromatic or heteroaromatic, it also being possible to use partially (hetero) aromatic radicals, ie (hetero) aromatic radicals which have at least one aliphatic, heteroaliphatic, cycloaliphatic, and / or heterocycloaliphatic group are substituted.
  • radicals T, U, V and W are bivalent or trivalent and function as bridging organic groups between two or three metal and / or semimetal atoms. If, for example, R 1 is (U) [(M 1 ) X (X 1 ) C ] 2 then U is a trivalent group which has a radical (M 1 ) x (X 1 ) a with two radicals [(M 1 ) X (X 1 ) C ] bridged.
  • all the groups X 1 have the same meaning within the component (A1) used in compound (M 1) x (X 1) a (R 1), particularly preferably all of the groups X 1 within the component (A1) used compound ( M 1 ) x (X 1 ) a (R 1 ) for OR a , where R a is preferably a C 1-6 aliphatic radical, in particular a C 1-6 alkyl radical, most preferably where R a is methyl, Ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, or tert -butyl.
  • all the groups X have the same meaning 2 compound used in the component (A2), more preferably, all groups X 2 in the component (A2) compound used is OR a, wherein R a is a Ci-6 aliphatic group , in particular a Ci-6-alkyl radical, most preferably, wherein R 3 is methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, or tert-butyl.
  • R a is a Ci-6 aliphatic group , in particular a Ci-6-alkyl radical, most preferably, wherein R 3 is methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, or tert-butyl.
  • M 1 and M 2 are each independently selected from the group consisting of Al, Ti, Zr, Fe, B and Si, more preferably selected from the group consisting of Al, Ti, Zr and Si, most preferably selected from the group consisting of Ti, Zr and Si, more preferably selected from the group consisting of Zr and Si, most preferably M 1 and M 2 each denote Si, or M 1 is selected from the group consisting of Al, Ti, Zr, Fe, B and Si, more preferably selected from the group consisting of Al, Ti, Zr and Si, most preferably selected from the group consisting of Ti, Zr and Si, most preferably selected from the group consisting of Zr and Si, most preferably Si, and M 2 is Si,
  • X 1 and X 2 are each independently an alkoxy group O-R a , wherein R a is in each case a Ci-6-aliphatic radical, preferably a Ci-6-alkyl radical, particularly preferably wherein R 3 is Methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, or tert-butyl.
  • aqueous sol-gel composition used in step (2) of the process according to the invention is obtainable by reacting at least one compound (A1) as at least one starting compound in which R 1 is a nonhydrolyzable organic radical which selects at least one reactive functional group from the group consisting of primary amino groups, secondary amino groups, epoxide groups, thiol groups, isocyanate groups, phosphorus-containing groups, and groups having an ethylenically unsaturated double bond, and optionally at least one further compound (A1 ) in which R 1 is X 1 , and optionally at least one further compound (A1) in which R 1 is a nonhydrolyzable organic radical which has no reactive functional group, and optionally at least one compound (A2).
  • R 1 is a nonhydrolyzable organic radical which selects at least one reactive functional group from the group consisting of primary amino groups, secondary amino groups, epoxide groups, thiol groups, isocyanate groups, phosphorus-containing groups, and groups having an
  • the aqueous sol-gel composition used in step (2) is obtainable by reacting at least one compound Si (X 1 ) 3 (R 1 ) as at least one compound (A1 - 1).
  • R 1 therein is a nonhydrolyzable organic radical which has at least one reactive functional group selected from the group consisting of primary amino groups, secondary amino groups, epoxy groups, and groups having an ethylenically unsaturated double bond, and optionally at least one compound Si (X 1 ) 4 as at least one further compound (A1 -2), and optionally at least one compound Si (X 1 ) 3 (R 1 ) as at least one further compound (A1 -3), wherein R 1 herein represents a non-hydrolyzable organic radical having no reactive functional group.
  • the aqueous sol-gel composition used in step (2) is obtainable by reacting at least one compound Si (X 1 ) 3 (R 1 ) as at least one compound (A1 - 1).
  • R 1 therein is a non-hydrolyzable organic radical having at least one reactive functional group selected from the group consisting of primary amino groups, secondary amino groups, epoxide groups, and groups having an ethylenically unsaturated double bond, and at least one compound Si (X 1 ) 4 as at least one further compound (A1 -2), and at least one compound Si (X 1 ) 3 (R 1 ) as at least one further compound (A1 -3), wherein R 1 therein represents a nonhydrolyzable organic radical which has no reactive functional group. and optionally at least one compound Zr (X 1 ) as at least one further compound (A1 -4), with water.
  • sol-gel compositions which, at least using all three compounds (A1 -1), (A1 -2) and (A1-3) in water are particularly effective.
  • the compounds mentioned in the preceding paragraph are very particularly preferred for this purpose (A1 -1), (A1 -2) and (A1 -3) used on Si basis, which corresponds to a simple, but particularly effective embodiment.
  • the aqueous sol-gel composition used in step (2) of the process according to the invention is obtainable by reacting at least one compound Si (X 1 ) 3 (R 1 ) as at least one compound (A1 - 1).
  • R 1 therein is a non-hydrolyzable organic radical having at least one reactive functional group selected from the group consisting of primary amino groups, secondary amino groups, epoxide groups, and groups having an ethylenically unsaturated double bond, in particular at least an epoxide group
  • the nonhydrolyzable organic radical is preferably selected from the group consisting of C 1 -C 10 aliphatic radicals and C 1 -C 10 heteroaliphatic radicals,
  • X 1 is OR a and R a is a Ci -6 alkyl radical, and optionally at least one compound Si (X 1) 4 and at least one further compound (A1 -2) wherein X 1 is OR a, and Ra is a Ci-6-alkyl radical, and optionally at least one compound Si (X 1) 3 (R 1) than at least one other compound (A1 -3), wherein R 1 therein is a nonhydrolyzable organic radical which does not have a reactive functional group, and wherein the nonhydrolyzable organic radical is preferably selected from the group consisting of Ci-Cio-aliphatic radicals, Ci-Cio-heteroaliphatic radicals, 5-12-membered aryl or heteroaryl radicals, and bonded via a Ci-6-aliphatic radical 5-12 membered aryl or heteroaryl radicals, and X 1 is oR a and R a represents a Ci -6 alkyl radical, and optionally at least one compound Zr (X 1) as
  • aqueous sol-gel composition used in step (2) is obtainable by reacting at least one compound Si (X 1 ) 3 (R 1 ) as at least one compound (A1 - 1). wherein R 1 therein is a non-hydrolyzable Ci-Cio-aliphatic organic radical which at least one reactive functional group selected from the group consisting of primary amino groups, secondary amino groups, epoxide groups, and groups containing an ethylenically unsaturated Having double bond,
  • X 1 is OR a and R a is a Ci -6 alkyl radical, and optionally at least one compound Si (X 1) 4 and at least one further compound (A1 -2) wherein X 1 is OR a, and R a is -6 alkyl radical of a C, and optionally at least one compound Si (X 1 ) 3 (R 1 ) as at least one further compound (A1-3), wherein R 1 therein is a non-hydrolysable organic C 1 -C 10 aliphatic radical which has no reactive functional group, and wherein the nonhydrolyzable organic radical R 1 is preferably selected from the group consisting of Ci-Cio-aliphatic radicals, 5-12 membered aryl or heteroaryl radicals, and bound via a Ci-6-aliphatic radical 5-12 membered aryl - or heteroaryl radicals, and X 1 is OR a and R a is a Ci -6 alkyl radical, and optionally at least one compound Zr (X 1 ) as
  • the relative weight ratio of the components (A1-1), (A1-2) and (A1-3) to each other is preferably in a range of 5: 1: 1 to 1: 1: 5 or 5: 1: 1 to 1 : 5: 1 or from 1: 5: 1 to 5: 1: 1 or from 1: 5: 1 to 1: 1: 5 or from 1: 1: 5 to 5: 1: 1 or from 1: 1: 5 to 5: 1: 1 or from 1: 1: 5 to 1: 5: 1 or from 1: 1: 5 to 1: 5: 1 or from 1: 1: 5 to 1: 5: 1.
  • At least four starting compounds are used to prepare the aqueous sol-gel composition used according to the invention, for example four different compounds (A1), for example those described above as (A1-1), (A1-2), (A1-3) and (A1 -4) designated connections, so is the relative weight ratio of the components (A1-1), (A1-2) and (A1-3) and (A1 -4) to each other preferably in a range of 5: 1: 1: 1 to 1: 1: 1: 5 or from 5: 1: 1: 1 to 1: 1: 5: 1 or from 5: 1: 1 to 1: 5: 1 or from 1: 5: 1: 1 to 5: 1: 1 or from 1: 5: 1: 1 to 5: 1: 1 or from 1: 5: 1: 1 to 1: 1: 5: 1 or from 1: 5: 1: 1 to 1: 1: 5: 1 or from 1: 5: 1: 1 to 1: 1: 5: 1 or from 1: 5: 1: 1 to 1: 1: 1: 5 or from 1: 5: 1: 1
  • At least one compound (M 1 ) x (X 1 ) a (R 1 ) is suitable as component (A1), in which R 1 is the meaning X 1 has.
  • examples of such compounds are tetramethoxysilane (TMOS), tetraethoxysilane (TEOS), dimethoxydiethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, tetrabutoxysilane, titanium tetraisopropoxide, titanium tetrabutoxide, zirconium tetraisopropoxide and zirconium tetrabutoxide.
  • TMOS tetramethoxysilane
  • TEOS tetraethoxysilane
  • dimethoxydiethoxysilane dimethoxydiethoxysilane
  • tetrapropoxysilane tetraisopropoxysilane
  • tetrabutoxysilane titanium
  • At least one compound (M 1 ) x (X 1 ) a (R 1 ) is suitable as component (A1) in which R 1 is a is not hydrolyzable organic radical, wherein the non-hydrolyzable organic radical R 1 may optionally have at least one reactive functional group.
  • nonhydrolyzable organic radical R 1 has at least one group which contains a vinyl group as the ethylenically unsaturated double bond
  • vinyltrimethoxysilane VTMS
  • vinyltriethoxysilane vinyltriisopropoxysilane
  • vinyltrichlorosilane vinyltris (2-methoxyethoxy
  • the nonhydrolyzable organic radical R 1 has at least one group which contains a (meth) acryl group as the ethylenically unsaturated double bond
  • Y- (meth) acryloxypropyltrimethoxysilane (MAPTS) Y- (meth) acryloxypropyltriethoxysilane
  • Y are suitable - (meth) acryloxypropyltriisopropoxysilane, ⁇ - (meth) acryloxyethyltrimethoxysilane, ⁇ - (meth) acryloxyethyltriethoxysilane, ⁇ - (Meth) acryloxyethyltriisopropoxysilane, 3- (meth) acryloxypropyltriacetoxysilane (meth) acrylamidopropyltriethoxysilane, (meth) acrylamidopropyltrinnethoxysilane (meth) acrylamidopropyl
  • nonhydrolyzable organic radical R 1 has at least one group which contains an isocyanate group, then, for example, ⁇ -isocyanatopropyltriethoxysilane and / or ⁇ -isocyanatopropyltrimethoxysilane are suitable as component (A1).
  • the nonhydrolyzable organic radical R 1 has at least one group which contains at least one primary and / or secondary amino group, then, for example, 3-aminopropyltrimethoxysilane (APS), 3-aminopropyltriethoxysilane, 3-aminopropyltriisopropoxysilane, 2-aminoethyltri- methoxysilane, 2-aminoethyltriethoxysilane, 2-aminoethyltriisopropoxysilane, aminomethyltrimethoxysilane, aminomethyltriethoxysilane, aminomethyltriisopropoxysilane, 3- (2-aminoethyl) aminopropyltrimethoxysilane (AEAPS), 3- (2-aminoethyl) aminopropyltriethoxysilane, 3- (2-aminoethyl) aminopropyltriisopropoxy silane, 2- (2-aminoethyl) aminoethyltrime
  • the nonhydrolyzable organic radical R 1 has at least one group which contains at least one epoxide group, then, for example, 3 Glycidoxypropyltrimethoxysilane (GPTMS), 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyltriisopropoxyoxysilane, 2-glycidoxyethyltrimethoxysilane, 2-glycidoxyethyltriethoxysilane, 2-glycidoxyethyltriisopropoxyoxysilane, ⁇ - (3,4-epoxycyclohexyl) -ethyltrimethoxysilane, and / or ⁇ - (3,4-epoxycyclohexyl) - ethyltriethoxysilane as component (A1).
  • GTMS Glycidoxypropyltrimethoxysilane
  • 3-glycidoxypropyltriethoxysilane 3-glycidoxypropy
  • nonhydrolyzable organic radical R 1 has at least one group which contains at least one thiol group, then, for example, 3-mercaptopropyltrimethoxysilane (MPTMS), 3-mercaptopropyltriethoxysilane, 3-mercaptopropyltriisopropoxysilane, 2-mercaptoethyltrimethoxysilane, 2
  • MPTMS 3-mercaptopropyltrimethoxysilane
  • 2-mercaptoethyltrimethoxysilane 2-mercaptoethyltrimethoxysilane
  • nonhydrolyzable organic radical R 1 contains at least one group which contains phosphorus, for example dimethylphosphonatoethyltrimethoxysilane, dimethylphosphonatoethyltriethoxysilane (PHS), dimethylphosphonatoethyltriisopropoxysilane, diethylphosphonatoethyltrimethoxysilane, diethylphosphonatoethyltriethoxysilane (PHS and / or diethylphosphonatoethyltriisopropoxysilane) as component (A1) are suitable.
  • At least one compound (M 1 ) x (X 1 ) a (R 1 ) is also suitable as component (A1) in which R 1 is a is not hydrolyzable organic radical, wherein the non-hydrolyzable organic radical R 1 can not have a reactive functional group.
  • nonhydrolyzable organic radical R 1 has no reactive functional group, it is possible, for example, to use methyltrimethoxysilane (MTMS), methyltriethoxysilane (MTES), methyltripropoxysilane, methyltriisopropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltripropoxysilane,
  • MTMS methyltrimethoxysilane
  • MTES methyltriethoxysilane
  • MTES methyltripropoxysilane
  • methyltriisopropoxysilane methyltriisopropoxysilane
  • ethyltrimethoxysilane ethyltriethoxysilane
  • ethyltriethoxysilane ethyltripropoxysilane
  • At least one compound (M 1 ) x (X 1 ) a (R 1 ) is suitable as component (A1) in which R 1 is ( T) (M 1 ) X (X 1 ) C stands.
  • At least one compound (M 1 ) x (X 1 ) a (R 1 ) is suitable as component (A1) in which R 1 is ( U) [(M 1 ) X (X 1 ) C ] 2 .
  • R 1 is ( U) [(M 1 ) X (X 1 ) C ] 2 .
  • tris- [3- (trimethoxysilyl) propyl] isocyanurate is suitable here.
  • At least one compound (M 2 ) y (X 2 ) b (R 2 ) (R 3 ) is suitable as component (A2) in which R 2 and R 3 are each independently a non-hydrolyzable organic radical.
  • 3-glycidoxypropylmethyldiethoxysilane 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, Y- (meth) acryloxypropylmethyldimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropylmethyldiethoxysilane, ⁇ - (meth) acryloxypropylmethyldiethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldiethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-aminopropylmethyldimethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, di-tert-butoxydiacetoxysilane, vinyldimethoxymethyl
  • the solids content of the aqueous sol-gel composition used according to the invention can be determined from the amount of at least one starting compound used to prepare the sol-gel composition by calculation. This method is used in particular when the desired solid body is determined in advance and should be adjusted accordingly. In this case, a complete hydrolysis of the hydrolyzable groups contained in the at least one starting compound such as the hydrolyzable groups X 1 and also a complete condensation of all formed by such a complete hydrolysis of metal OH and / or half-metal OH bonds such as M 1 -OH Bindings accepted.
  • the solids content of the aqueous sol-gel composition used according to the invention is estimated by means of this calculation method.
  • the theoretically calculated solids content can be for each of the at least one starting compound which has been used for the preparation of the aqueous sol-gel composition used according to the invention, according to the general formula
  • Mkond molar mass of the completely condensed starting compound in g / mol
  • M s tart molar mass of the starting compound in g / mol
  • AnteÜ R ezept proportion of the starting compound in the composition in wt .-%.
  • the aqueous sol-gel composition used according to the invention is weighed out in an amount of 2 ⁇ 0.2 g and at a temperature of 130 ° C. in accordance with DIN Dried to EN ISO 3251.
  • At least two starting compounds are used to prepare the aqueous sol-gel composition used according to the invention, for example two different compounds (A1) - hereinafter referred to as (A1a) and (A1b) - the relative weight ratio of these two components is, for example ( A1 a) and (A1 b) to each other in a range from 10: 1 to 1:10, particularly preferably in a range from 7.5: 1 to 1: 7.5, very particularly preferably in a range from 5: 1 to 1: 5, in particular in a range from 2: 1 to 1: 2.
  • At least three starting compounds are used to prepare the aqueous sol-gel composition used according to the invention, for example three different compounds (A1) - hereinafter referred to as (A1a), (A1b) and (A1c) - the relative weight ratio of Components (A1 a) and (A1 c) to each other in a range of 10: 1 to 1: 10, more preferably in a range of 7.5: 1: 1 to 1: 7.5, most preferably in a range of 5: 1 to 1: 5, especially in a range of 2: 1 to 1: 2.
  • compounds (A1) - hereinafter referred to as (A1a), (A1b) and (A1c) - the relative weight ratio of Components (A1 a) and (A1 c) to each other in a range of 10: 1 to 1: 10, more preferably in a range of 7.5: 1: 1 to 1: 7.5, most preferably in a range of 5: 1 to 1: 5, especially in a range of 2
  • the relative weight ratio of the component (A1 a) to the component (A1 b) to the component (A1 c) in a range of 2 ⁇ 0.2: 1 ⁇ 0.2: 1 ⁇ 0.2 to 1 ⁇ 0 , 2: 1 ⁇ 0.2: 1 ⁇ 0.2 or from 1 ⁇ 0.2: 2 ⁇ 0.2: 1 ⁇ 0.2 to 1 ⁇ 0.2: 1 ⁇ 0.2: 1 ⁇ 0, 2 or from 1 ⁇ 0.2: 1 ⁇ 0.2: 2 ⁇ 0.2 to 1 ⁇ 0.2: 1 ⁇ 0.2: 1 ⁇ 0.2.
  • the aqueous sol-gel composition may contain at least one further additive which is preferably selected from the group consisting of hydrolytically and pyrolytically prepared silica, organic and inorganic nanoparticles, each preferably having a particle size in the range of 1 to 150 nm can be determined by means of dynamic light scattering in accordance with DIN ISO 13 321, water-soluble or water-dispersible organic polymers such as polyvinyl alcohol, polyvinyl acetate (with fraction of hydrolyzed acetate groups of 10-99%), polyvinyl butyral, acrylate-based polymer dispersions, epoxy-based polymer dispersions, polyurethane based polymer dispersions or epoxy-acrylic resin miniemulsions, surface-active compounds such as surfactants, emulsifiers, antioxidants, wetting agents, Dispersants, leveling agents, solubilizers, defoaming agents, stabilizers, preferably heat stabilizers, process stabilizers and UV and / or light stabilizers
  • the additive content in the aqueous sol-gel composition used according to the invention can vary very widely depending on the intended use.
  • the content, in each case based on the total weight of the aqueous sol-gel composition used according to the invention, is preferably 0 to 10.0% by weight, preferably 0.1 to 8.0% by weight, more preferably 0.1 to 6.0% by weight, most preferably from 0.1 to 4.0% by weight and in particular from 0.1 to 2.0% by weight, and mixtures thereof.
  • the proportions in% by weight of all components and additives contained in the aqueous sol-gel composition used according to the invention preferably add up to a total of 100% by weight, based on the total weight of the composition.
  • the curing of the coating applied in step (2) is preferably carried out at a temperature of 150 to 190 ° C, more preferably at a temperature of 160 to 180 ° C and most preferably at a temperature of 165 to 180 ° C, such as 175 ° C. If the curing temperature exceeds 190 ° C., there are so-called overburning conditions which can lead to a reduced corrosion protection performance. If the curing temperature falls below 150 ° C., in some cases insufficient drying and / or crosslinking of the coating will occur, as a result of which the corrosion protection performance may also drop.
  • the curing time is preferably 5 to 60 minutes, more preferably 10 to 40 minutes, and particularly preferably 15 to 35 minutes, such as 25 minutes.
  • the sol-gel composition has the meaning "consisting of.”
  • one or more of the other optional components mentioned above may be included in the composition with respect to the aqueous sol-gel composition used according to the invention All components may be included in their preferred embodiments in each case in the composition.
  • the layer thicknesses can be specified, for example, as layer weights in mg / m 2 by means of wavelength-dispersive X-ray fluorescence analysis (RFA) according to DIN 51001 (March 2003).
  • the layer applied in the first step typically and preferably has Zr layer weights of 50 to 250 mg / m 2 , more preferably 80 to 200 mg / m 2 and most preferably 100 to 180 mg / m 2 and Cu layer weights of 5 to 150 mg / m 2 , more preferably 8 to 120 mg / m 2 and most preferably 10 to 90 mg / m 2 .
  • the layer applied in the second step typically and preferably has Si layer weights of 100 to 3000 mg / m 2, more preferably 200 to 2000 mg / m 2, and most preferably 300 to 1800 mg / m 2 .
  • the measuring method is described in more detail in the experimental part.
  • the method according to the invention further comprises at least one step (3) following step (2), namely
  • step (3) one or more further lacquer layers can be applied to the coated substrate obtained after step (2).
  • further lacquer layers to be applied are, for example, filler layers and / or single or multi-layer topcoats.
  • the further or further layers such as a surfacer layer and / or a single-coat or multi-coat topcoat layer, can be applied wet-on-wet ("wet-on-wet" process.)
  • wet-on-wet wet-on-wet
  • Step (3) may also be omitted in a further preferred embodiment.
  • a subsequent lacquer layer can be applied, which is carried out by means of firing after step (3), or in the case of the omission of step (3) after step (2).
  • Step (4) is preferably carried out in an oven. Curing is preferably carried out at an oven temperature in the range of 150 ° C to 190 ° C, more preferably in a range of 160 ° C to 180 ° C.
  • the present invention additionally relates to an at least partially coated metallic substrate obtainable according to the method according to the invention, such as an at least partially coated metal strip or an at least partially coated metallic component.
  • an at least partially coated metallic substrate obtainable according to the method according to the invention, such as an at least partially coated metal strip or an at least partially coated metallic component.
  • Such components may be, for example, bodies and their parts of automobiles such as passenger cars, trucks, motorcycles and buses, and components of household electrical products or even components in the field of equipment panels, cladding, ceiling panels or window profiles.
  • the present invention additionally relates to a component produced from at least one metallic at least partially coated substrate, which is obtainable according to the method according to the invention, preferably a metallic component.
  • the copper-accelerated acetic acid salt spray test serves to determine the corrosion resistance of a coating on a substrate.
  • the copper-accelerated acetic salt spray test is carried out in accordance with DIN EN ISO 9227 CASS (September 2012) for the metallic substrate aluminum (AA6014 (ALU)) coated with the method according to the invention or with a comparative method.
  • the samples to be tested are in a chamber in which at a temperature of 50 ° C continuously for a period of 240 hours, a 5% saline solution is sprayed with controlled pH, wherein the salt solution of copper chloride and acetic acid is added. The mist settles on the samples to be examined and covers them with a corrosive salt water film.
  • the coating of the samples to be examined is scratched with a knife cut to the substrate before the copper-accelerated acetic salt spray test according to DIN EN ISO 9227 CASS, so that the samples can be examined with respect to their Unterwa matterssgrades according to DIN EN ISO 4628-8, since the substrate during the copper-accelerated acetic salt spray test in accordance with DIN EN ISO 9227 CASS corroded along the score line. Due to the progressive corrosion process, the coating is more or less undermined during the test. The degree of submersion in [mm] is a measure of the durability of the coating.
  • This change of climate test serves to determine the corrosion resistance of a coating on a substrate.
  • the climate change test is carried out for the dip galvanized steel (HDG) metallic substrate coated with the method according to the invention or with a comparative method.
  • cycles One cycle (24 hours) consists of 4 hours of a salt spray test in accordance with DIN EN ISO 9227, 4 hours of storage under normal climatic conditions in accordance with DIN 50014-23 / 50-2 including the cooling phase and 16 hours of moist heat storage in a climate according to DIN EN ISO 6270-2 at 40 ⁇ 3 ° C and a humidity of 100%. After 5 cycles, there is a respite break of 48 hours in normal climate according to DIN 50014-23 / 50-2. 10 cycles correspond to a total duration of 14 days, 60 cycles correspond to a duration of 84 days.
  • the coating of the samples to be examined is scratched with a knife cut to the substrate before the climate change test is carried out, so that the samples can be examined for their degree of underdeviation according to DIN EN ISO 4628-8, since the substrate corrodes along the scribe line during the climate change test , Due to the progressive corrosion process, the coating is more or less undermined during the test.
  • the degree of submersion in [mm] is a measure of the durability of the coating.
  • the determination of filiform corrosion serves to determine the corrosion resistance of a coating on a substrate. This determination is carried out in accordance with DIN EN 3665 (August 1997) for the substrate aluminum (ALU) coated with a coating composition according to the invention or with a comparative coating composition over a period of 1008 hours. In this case, the respective coating, starting from a line-shaped violation of the coating, is infiltrated in the form of a line or thread-like undercorrosion. The mean and maximum thread length in [mm] can be measured in accordance with DIN EN 3665 (method 3) and are a measure of the resistance of the coating to corrosion. In addition, the infiltration in [mm] is determined according to PAPP WT 3102 (Daimler). 4. X-ray fluorescence analysis for determining the layer weights of the individual layers
  • the coating weight (in mg per m 2 of surface) of the coating to be examined by wavelength can be determined X-ray fluorescence analysis (XRF) according to DIN 51001 (March 2003).
  • XRF X-ray fluorescence analysis
  • X-ray fluorescence analysis signals are corrected for a separately measured background of an uncoated reference sample.
  • the gross counting rates of the respective sample are used to subtract the gross counting rates of the respective elements of a reference sample (uncoated sheet) (net counting rate). These are converted into coating weights (mg / cm 2 ) by means of an element-specific transfer function (obtained from a calibration measurement). If several layers are applied, the respective coating weight is determined after each application.
  • tetraethoxysilane tetraethylorthosilicate, TEOS, CAS: 78-10-4
  • MTEOS triethoxymethylsilane
  • GLYMO zirconium n-butoxide
  • Binder dispersion (epoxy / acrylate miniemulsion, anionically stabilized, solids 33.4 wt .-%) mixed with stirring. The resulting formulation is stirred for 48 h at room temperature.
  • the product SG04 is a highly opaque, precipitation-free solution with a solids content of 10% by weight
  • Standard test plates dip galvanized steel (HDG) and aluminum AA6014 (ALU) are cleaned under standard conditions (Ridoline 1565-1 (3.0), Ridosol 1400 (0.3%) cleaning time 3 min, temperature 60 ° C) ,
  • zirconium layer weights 150 mg / m 2 (on HDG) and 1 10 mg / m 2 (on ALU) or
  • phosphating or electrocoating with Granodine 958 or Cathoguard 520 should be carried out according to the manufacturer's instructions.
  • a full vehicle body consisting of filler, basecoat and clearcoat is applied (aqueous filler: FU43-7000, 30-35 ⁇ , 10 min at 80 ° C, then 15 min at 150 ° C (object), water-based paint: FW61- 91 1 M, 12-15 ⁇ m, 5 min at room temperature, then 10 min at 80 ° C (object), clearcoat: FF99-0141, 40-45 ⁇ , 5 min at room temperature, then 20 min at 135 ° C.
  • aqueous filler FU43-7000, 30-35 ⁇ , 10 min at 80 ° C, then 15 min at 150 ° C (object)
  • water-based paint FW61- 91 1 M, 12-15 ⁇ m, 5 min at room temperature
  • clearcoat FF99-0141, 40-45 ⁇ , 5 min at room temperature, then 20 min at 135 ° C.
  • the table shows a comparison of the coatings produced according to the invention with a conventional layer of phosphating and cathodic electrodeposition coating.
  • the conventional structure of phosphating and cathodic electrocoating is comparatively complicated and cost-intensive, in particular due to the high energy input for the cathodic electrodeposition coating.
  • the inventive method provides much lower cost and in particular an electroless process management comparably good, in some cases even significantly improved results, in particular with regard to the Filiform corrosion on aluminum.

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Abstract

L'invention concerne un procédé permettant de revêtir au moins en partie un substrat métallique. Ce procédé comprend au moins les étapes consistant à revêtir au moins en partie, de préférence sensiblement intégralement, le substrat d'une composition aqueuse d'agent de revêtement (B) à base de zirconium, de cuivre et de fluor avec formation d'une couche de conversion, et à revêtir le substrat au moins en partie revêtu, de préférence sensiblement intégralement revêtu, et directement après l'étape (1), d'une composition aqueuse, la composition aqueuse utilisée à l'étape (2) étant une composition aqueuse sol-gel. L'invention concerne en outre des substrats et des éléments, lesquels sont revêtus selon le procédé.
PCT/EP2013/074110 2013-11-18 2013-11-18 Procédé permettant de revêtir des substrats métalliques d'une couche de conversion et d'une couche sol-gel WO2015070933A1 (fr)

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