EP2296829B1 - Coated substrate and method for its production - Google Patents

Coated substrate and method for its production Download PDF

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Publication number
EP2296829B1
EP2296829B1 EP09749640A EP09749640A EP2296829B1 EP 2296829 B1 EP2296829 B1 EP 2296829B1 EP 09749640 A EP09749640 A EP 09749640A EP 09749640 A EP09749640 A EP 09749640A EP 2296829 B1 EP2296829 B1 EP 2296829B1
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EP
European Patent Office
Prior art keywords
lacquer layer
substrate
process step
decorative
decorative lacquer
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EP09749640A
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German (de)
French (fr)
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EP2296829A1 (en
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Mattthias Koch
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    • 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
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B05D5/06—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain multicolour or other optical effects
    • B05D5/067—Metallic effect
    • 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
    • B05D3/10—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 other chemical means
    • B05D3/107—Post-treatment of applied coatings

Definitions

  • the present invention relates to a process for producing coated substrates and to such coated substrates.
  • Non-metallic as well as in particular metallic substrates are often provided with one or more coatings in order to achieve a particular decorative effect and / or to protect the substrate against certain external influences.
  • coatings are often used to increase corrosion protection.
  • decorative coating systems so-called metallic and effect coatings have proven particularly suitable for metallic substrate surfaces.
  • metal pigments for example aluminum pigments. These are used in particular in the form of platelets, flakes or flakes.
  • an aluminum metal effect paint consisting essentially of either i) white pearlescent pigment and aluminum pigment, ii) white pearlescent pigment, aluminum pigment and white pigment, iii) bismuth oxychloride pigment or iv) bismuth oxychloride pigment and pearlescent pigment, aluminum pigment and / or white pigment ,
  • an aluminum metal effect paint consisting essentially of either i) white pearlescent pigment and aluminum pigment, ii) white pearlescent pigment, aluminum pigment and white pigment, iii) bismuth oxychloride pigment or iv) bismuth oxychloride pigment and pearlescent pigment, aluminum pigment and / or white pigment
  • an aluminum metal effect paint consisting essentially of either i) white pearlescent pigment and aluminum pigment, ii) white pearlescent pigment, aluminum pigment and white pigment, iii) bismuth oxychloride pigment or iv) bismuth oxychloride pigment and pearlescent pigment, aluminum pigment and / or white pigment .
  • effect basecoats with good adhesion to plastic substrates made of polypropylene which, when using paint systems containing binders with physical drying power, chlorinated polyolefins having a chlorine content of 15 to 35 weight percent and having a molecular weight of 7000 to 130000, cellulose acetobutyrate, effect pigment and solvent.
  • chlorinated polyolefins having a chlorine content of 15 to 35 weight percent and having a molecular weight of 7000 to 130000, cellulose acetobutyrate, effect pigment and solvent.
  • a method for painting motor vehicles is described, with which an effect coating can be applied in only one operation on primed in the usual way metal body panels.
  • lacquers containing beta-modification copper phthalocyanine pigments which are at least 50% by weight of platelets at least 10 ⁇ m long and at least 3 ⁇ m wide, and where the ratio of length to width is at least 3, 3: 1 and the pigment has a reflection maximum between 610 and 640 and between 710 and 740 nm.
  • a paint has to contain as binder a mixture of acrylate resins and / or saturated polyesters, each having an OH number of 40 to 200, and a substantially equivalent amount of aliphatic polyisocyanates crosslinking therewith. Finally, such a paint is applied in a single layer with a dry film thickness of 30 to 50 microns and harden.
  • a particularly good order of a metallic effect paint decorative layer succeeds after the DE 197 35 540 C1 if, for the purpose of priming, a filler layer of a pre-crosslinkable powder coating having a layer thickness in the range from 30 ⁇ m to 250 ⁇ m is used first.
  • the present invention was therefore based on the object of making available a coating method and system which can be used to obtain a decoratively perfect metallic effect coating with very good adhesion to the substrate independently of the substrate.
  • the present Another object of the invention was to provide such metallic effect coatings which are provided with outstanding corrosion protection.
  • first metal should also include the alloys mentioned above under d).
  • second metal is intended in the context of the present invention elements of the 4th and 5th group of the Periodic Table of the Elements or compounds of these elements with the above e) connection components, z. For example, oxides.
  • the metallic particles are preferably platelet-shaped metal particles, for example platelet-shaped aluminum particles.
  • the purity of the metals used for the metallic particles is at least 80% by weight, preferably more than 90% by weight, most preferably at least 99% by weight.
  • the metallic particles of the coated substrates obtainable by the process according to the invention, in particular in the metallic particles present on the surface or in the surface region of the binder, there is at least one oxide, double oxide, oxide hydrate, sulfide, halide, nitride, carbide, Carbonitride, boride, silicide, oxyhalide and / or salt of an element of the 4th or 5th group of the Periodic Table of the Elements or mixtures thereof.
  • the abovementioned compounds are present substantially uniformly distributed in the metallic particles, in particular in the metallic particles which are located on the surface or in the surface region of the decorative lacquer layer.
  • the concentration of these compounds incorporated in the metallic particles can change more or less strongly over the thickness of the particles, also continuously, stepwise or in any other way, for example abruptly.
  • these compounds may be present or embedded substantially exclusively in the region of the entire surface of the metallic particles or in the region of only a part of the surface of the metallic particles.
  • the particles treated with the aqueous system may also be in the form of a complete or partially intimately mixed or, if appropriate, only phased, metallic composite particles containing the first metal as described above and embedded therein at least one compound of the second metal, in particular at least one acid, an oxide, double oxide, oxide hydrate, sulfide, halide, nitride, carbide, carbonitride, boride, silicide, oxyhalide and / or salt of the second metal are understood.
  • the embedded or embedded oxides zirconium oxides, titanium oxides or hafnium oxides, the oxifluorides zirconium oxifluorides, titanium oxyfluorides or hafnium oxyfluorides, the acids fluoric acid, fluorotitanic acid or Fluorhafniumklare and the salts fluorozirconate, fluorotitanates or Fluorhafniate represent.
  • oxide-bound zirconium for example oxides of zirconium such as zirconium dioxide, zirconium oxifluorides and / or double oxides of zirconium, for example aluminum / zirconium oxides, are present in the metallic particles.
  • Suitable substrates include, for example, metals, precious metals, metal alloys or glass, ceramics, composite fiber materials, carbon materials, plastics, wood or chipboard.
  • plastics are e.g. PVC, polyurethanes, polyesters, e.g. PBT and PET, polyolefins, especially polypropylene, polyamides, polystyrene, styrene (co) polymers such as ABS, SAN, ASA or MABS, and polyoxyalkylenes, e.g. POM, dar.
  • suitable substrates may be present in addition to metallic components or sections and non-metallic components or sections.
  • shaped bodies of all metals, metal alloys and precious metals are suitable as metallic substrates.
  • suitable substrates are those of aluminum, iron, steel, stainless steel, copper, brass, magnesium, iridium, gold, silver, palladium, platinum, ruthenium, molybdenum, nickel, bronze, titanium, zinc, lead, tungsten or manganese and their Called alloys.
  • Preferred metal substrates or metal substrate surfaces comprise or in particular consist of aluminum or aluminum alloys, magnesium or magnesium alloys or titanium or titanium alloys or of steel or stainless steel. Particular preference is given to the metallic substrates on aluminum and aluminum alloys.
  • diecast substrates e.g. Zinc diecasting, are particularly suitable.
  • the aqueous system contains at least one acid, an oxide, double oxide, oxide hydrate, halide, oxyhalide or salt of an element of the 4th or 5th group, in particular of titanium or zirconium, or mixtures thereof ,
  • the aqueous system is conveniently adjusted to a pH in the range of 1.5 to 6.5.
  • the compounds of the elements of the 4th or 5th group of the Periodic Table of the Elements present in the aqueous system are preferably at least partially introduced or embedded in at least one part of the metallic particles.
  • the decorative lacquer layer is exposed to the aqueous system under pressure, in particular in the form of liquid jets.
  • a particularly effective entry or embedding of the above-mentioned compounds of the 4th and 5th group of the Periodic Table of the Elements in at least a portion of the metallic particles of the decorative coating layer succeeds.
  • the aqueous system may e.g. in the form of a solution, a suspension or an emulsion.
  • the aqueous system is used as a solution, i. the abovementioned compounds, salts and / or acids are present substantially dissolved at least before the application.
  • the conductance of the aqueous system used is preferably in the range from 100 to 2000, particularly preferably in the range from 150 to 1500 and in particular in the range from 200 to 1000 ⁇ S / cm.
  • the temperature of the aqueous system in the process of treating the substrate is in the range of 15 to 50 ° C, preferably in the range of 20 to 40 ° C.
  • a treatment duration of 20 to 120 seconds is sufficient to obtain the substrate according to the invention.
  • the coated surface of the substrate is subjected to a rinsing step with, in particular demineralized, water.
  • the drying step can be carried out, for example, at temperatures in the range from 120 to 180 ° C, for example at about 140 ° C.
  • the water used for rinsing preferably has a conductance of less than 60 mS / cm, preferably less than 50 mS / cm and in particular less than 35 mS / cm.
  • the respective last rinse before the subsequent process step or before a drying process has the above-mentioned guide values.
  • the pH and / or the conductance of the aqueous system are preferably kept substantially constant for the duration of the treatment of the metal layer, in particular within the abovementioned ranges.
  • the substrate provided with the decorative varnish layer may be e.g. by immersion, rinsing or spraying with the aqueous system described above, containing at least one of said compounds of the second metal.
  • the decorative lacquer layer is subjected to this aqueous system under elevated pressure, for example in the form of high-pressure water jets. It has proven to be useful to direct a variety of fine single water jets on the substrate.
  • Suitable pressures for exposure to the aqueous system are e.g. above 0.2 bar, preferably in the range of 0.5 to 50 bar and particularly preferably in the range of 0.2 to 15, in particular from 0.9 to 1.5 bar. These pressures are measured on the surface of the metal layer.
  • the compounds of the second metal which are present in the aqueous system e.g. present as acid or salt, in which metallic particles are converted into an oxide, double oxide, oxide hydrate or oxyhalide.
  • Suitable acids derived from a group 4 element include, for example, hydrofluorozirconic acid (H 2 ZrF 6 ), fluorotitanic acid (H 2 TiF 6 ) and fluoro hafnic acid (H 2 HfF 6 ). Of course, mixtures of different acids can be used. These fluoric acids can be used both in the pure state and also containing impurities, for example fluoric acid. In the aqueous systems, the acids may be present, for example, in amounts of up to 5% by weight, in particular of up to 3.5% by weight, based on the total weight of the aqueous system. Fluoric acid may also be present in the aqueous systems, eg in amounts ranging from 0.1 to 3% by weight.
  • ammonium zirconium carbonate which is available, for example, from Magnesium Electron Inc., under the trade name Bacote 20, used ((NH 4 ) 2 [Zr (OH) 2 (CO 3 ) 2 ] .nH 2 O). It is also possible to use alkali metal and ammonium fluorozirconates, for example Na 2 ZrF 6 , KZrF 6 , (NH 4 ) ZrF 6 , as well as zirconium nitrates, zirconium oxynitrates, zirconium carbonates, zirconium fluorides or zirconium sulfate.
  • the compounds based on the 4th group can be used as such or in any mixture with each other. The same applies to the compounds of the 5th group.
  • aqueous systems in addition to the compounds mentioned or mixtures thereof further ingredients.
  • Nitric acid, fluoric acid, phosphoric acid, salts of said acids, ammonium bifluoride and ammonium sulfate into consideration.
  • a suitable titanium salt provides e.g. Ammonium titanium fluoride.
  • the aqueous system preferably contains fluoride ions in free and / or complexed form.
  • Suitable complexed fluoride ions include fluoroborate salts and acids as well as alkali metal and ammonium bifluorides.
  • complex fluorides of titanium, zirconium, hafnium, silicon and / or boron are particularly suitable. Preference is given to using complex fluorides as zirconium.
  • Suitable aqueous systems may preferably be in addition to the acid, an oxide, double oxide, oxide hydrate, sulfide, halide, nitride, carbide, carbonitride, boride, silicide, oxyhalide and / or salt of the second metal, preferably based on a 4th group element of the Periodic Table of the Elements (IUPAC, formerly designated Group IVb or IV-B), in particular zirconium, titanium and / or hafnium, preferably zirconium, at least one polymeric compound dissolved in the aqueous composition, in emulsion form or in undissolved dispersed form Particles may be present.
  • IUPAC Periodic Table of the Elements
  • polymeric compounds may be mentioned in particular the polyacrylic acid and its salts and esters. These acids, esters and salts may be present in the aqueous solution in dissolved or dispersed form.
  • the amount of polymer component can be varied widely and is preferably in the range of 0.1 to 0.5 g per liter.
  • the process according to the invention comprises after process step a) and before process step d) as process step b) the application of at least one conversion layer to the substrate.
  • conversion layers can be found, for example, in US Pat US 2,825,697 and the US 2,928,763 described.
  • the conversion layer may, for example, also be conventional passivation layers based on nickel, chromium and zinc compounds.
  • the method further comprises after step a) and before step d) as process step c) the application of at least one first and optionally at least one second primer layer on the substrate.
  • at least one first and / or at least one second primer layer is applied at least in regions to the conversion layer.
  • an upstream mechanical smoothing of the metal substrate surface may be provided, for example by means of grinding and / or polishing or burnishing
  • the first and / or the second primer layer can be applied, for example, by means of a wet-paint method and / or a powder-coating method. Suitable examples are powdered polyester resin compounds and epoxy / polyester powder. Suitable epoxy resins as primer layer materials are known commercially, for example, under the trade name "Valophene". As the first and second primer layers, there are also those based on a urethane resin, as in U.S. Pat US 4,431,711 described, into consideration. Alternatively, it is also possible to use polyester or polyacrylate materials such as those described in U.S. Pat WO 2004/014646 A1 be highlighted. Very particular preference is given to the purpose of priming on wet paint process.
  • primer methods in which the curing of the primer layer is not thermal, but by means of UV irradiation. When curing by means of UV radiation regularly no additional heating is required, and in general no heat is generated in this case.
  • Suitable powder coating, wet paint and UV-curing coating systems and their application are well known to those skilled in the art.
  • one or several primer layers can be applied to smooth the surface.
  • the first primer layer as used in particular present on metal substrate surfaces can, is achieved in general an advantageous smoothing of the surface.
  • the primer layer thus regularly constitutes a so-called smoothing layer.
  • a primer layer in general all angular ranges are achieved, so that surface roughnesses can also be compensated in these areas.
  • a further aspect of the method according to the invention further provides that the decorative lacquer layer is applied according to method step d) before the first and / or second primer layer has completely cured.
  • the process according to the invention may further comprise, after process step e) as process step f), the application of at least one, in particular transparent, topcoat.
  • the topcoat can be e.g. a clearcoat or a transparent powder, and is preferably applied by a wet-paint method or a powder-coating method. Furthermore, the invention provides that the cover layer may contain at least one dye or a pigment.
  • the cover layer or the topcoat can generally be one-, two- or multi-component paints. Clearcoats are preferred here. These clearcoats may be e.g. be chemically cross-linking two-component, one-component thermosetting or UV-curable coatings.
  • the topcoat or clearcoat layer can be cured in a separate step subsequent to the production and curing of the decorative lacquer layer or together with the decorative lacquer layer and / or the first or second primer.
  • the substrate may also be used as a topcoat or in addition to the cover layer described above in particular also suitable, known in the art glazes.
  • This can be used, for example, brass, titanium and gold tones as well as individual Shades such as red, blue, yellow, green, etc. and all the anodizing colors are easily set.
  • Another advantage is also that with the inventive method especially wide margins in the color design result, if one tunes the colors or color effects of decorative lacquer layer and topcoat and in particular of primer, decorative lacquer and topcoat each other.
  • a dark colored primer, a high gloss decorative lacquer layer, and a transparent topcoat products with matte chrome finish are obtained without, however, relying on the use of chromium.
  • the decorative lacquer layer is applied in a thickness which is still slightly translucent for the color of the substrate or primer.
  • the decorative lacquer layer applied to the substrate by the method according to the invention can be, for example, a so-called effect lacquer layer or a so-called metallic lacquer layer.
  • this decorative lacquer layer is treated with a first aqueous system according to method step e) such that a first decorative lacquer layer containing metallic particles, containing or consisting essentially of aluminum, on the first decorative lacquer layer treated in this way Gold, silver, lead, vanadium, manganese, iron, cobalt, nickel, copper, palladium, platinum, titanium, zinc, magnesium or alloys of these metals or containing or consisting essentially of brass, bronze or stainless steel, and that second Decorative lacquer layer comprising a second aqueous system containing at least one acid, an oxide, double oxide, oxide hydrate, sulfide, halide, nitride, carbide, carbonitride, boride, silicide, oxyhalide and / or salt of a 4th or 5th group element of the Periodic table of the elements or mixtures thereof, is treated.
  • the method steps d) and e) can not only be run twice in succession, but can also be repeated several times, for example at least three times or at least four times in succession be run through, for example, to achieve a particularly intense and consistent decor effect, especially metallic effect.
  • a different decorative lacquer layer can be applied in the sense of the present invention.
  • the same decorative lacquer layer is applied in each application step.
  • a different aqueous system in the context of the present invention can be used.
  • the same aqueous system is used in each treatment step.
  • the decorative lacquer layer to be applied in process step d) represents a decorative lacquer layer to be cured or dried out and that this decorative lacquer layer is treated with the aqueous system according to process step e) prior to its complete curing and / or drying.
  • the drying step in decorative lacquer layers is also known as the so-called peeling step.
  • water-dilutable coating compositions can be used for the decorative lacquer layer.
  • These coating compositions contain suitable binders, for example polyester, polyacrylate, polyurethane or aminoplast resins, e.g. B. in wasserver Parkernbarer form.
  • the coating composition for the decorative paint layer comprises e.g. an aqueous polymer dispersion comprising an acrylate copolymer and a non-associative thickener.
  • pearlescent pigments such as pearlescent pigments, LCP pigments (liquid crystal polymer) or OV pigments (optical variable), in the coating compositions used for the decorative lacquer layer.
  • Common pearlescent pigments include, for example, metal oxide coated metal pigments, for example, titanium dioxide coated, iron oxide coated, or mixed oxide coated aluminum.
  • Pearlescent pigments also include coated mica.
  • OV pigments are generally pigment platelets with a special one multilayer thin-film interference structure, the layers being composed of a highly reflective metal layer such as aluminum or chromium, a transparent dielectric layer of titanium dioxide or silicon dioxide and a semitransparent metal layer of, for example, nickel or aluminum.
  • proportions of color-providing organic and / or inorganic pigments may also be present in the coating composition for the decorative lacquer layer.
  • the coating compositions used for the decorative lacquer layer in one embodiment contain solvents in an amount of, based on the coating composition, 20 to 80, advantageously 30 to 70, in particular 40 to 65 wt .-% of solvents, for. B. water.
  • the coating compositions for the decorative coating layer may contain conventional coating additives.
  • coating additives By way of example, reference is made to rheology-influencing agents, thickeners, anti-settling agents, leveling agents, light stabilizers, antifoams, wetting agents or mixtures of these components.
  • the decorative lacquer layer can be applied to the substrate by means of known application methods, for example by means of spraying, rolling, knife coating, brushing, roller coating, flooding or dipping.
  • spray or spray application can be used, for example, on known compressed air or Rotationszerstäubungs réellesvon.
  • the decorative coating layer is applied to the substrate by means of spraying, in particular using pressure, for example compressed air.
  • pressure for example compressed air.
  • a concentration gradient of metallic particles within the decorative lacquer layer regularly occurs, with the result that the concentration of metallic particles in the direction of the substrate surface decreases. Accordingly, in this variant, the majority of the metallic particles are often present on or on, and optionally in the near-surface region of the decorative lacquer layer.
  • These metallic particles are particularly suitable for the introduction of the abovementioned compounds of the elements of groups 4 and 5 of the Periodic Table of the Elements by application of the described aqueous system in the sense of the present invention. Without being bound by any theory, it is presently believed that it may be that described above Distribution of metallic particles within the decorative coating layer could be due to electrostatic friction phenomena. Of course, the effect according to the invention is also achieved, for example, when the metallic particles are substantially uniformly distributed in the decorative lacquer layer.
  • Suitable metallic particles for the decorative lacquer layer may, for.
  • wet-chemically or by CVD or PVD processes are prepared, for example by application to naturally or artificially produced micrometer-sized platelets.
  • Particularly suitable metallic particles have form factors, ie ratios of average longitudinal extent to average thickness, in a range from 10 to 7,000, preferably from 50 to 10,000, and particularly preferably from 70 to 200.
  • Preferred average layer thicknesses of the metallic particles present, in particular in platelet form are in a range of 15 to 1000 nm.
  • the average diameter of, in particular of platelet-shaped, metallic particles is in the range from 1 to 500 .mu.m, more preferably in the range from 5 to 100 ⁇ m.
  • the average diameter is here the d 50 value of the cumulative distribution of the size distribution curve, as it is usually measured by laser diffraction method (Frauenhoferbeugung) by means of suitable devices (for example, Cilas 1064) is measured, based.
  • the decorative lacquer layer preferably has a layer thickness not above 150 ⁇ m, advantageously not above 80 ⁇ m, and preferably in the range from 1 to 40 ⁇ m, more preferably in the range from 2 to 35 ⁇ m and particularly preferably in the range from 3 to 30 microns.
  • layer thicknesses above 150 ⁇ m for example in the range from 300 to 450 ⁇ m, for example about 400 ⁇ m.
  • the metallic particles in the decorative lacquer layer can still always come into contact with it during the treatment with the aqueous system, for example because the metallic particles are present on or in the surface and / or because the aqueous system or its Compounds of the second metal in the Decorative paint layer can penetrate, for example, because this is not fully cured or dried out.
  • the cover layer usually has a thickness in the range of 20 to 30 microns.
  • coated substrates obtainable by the process according to the invention can be used, for example, as an accessory for the automotive industry, motorcycle construction, bicycle construction or shipbuilding, for rims, in particular light metal rims, wheels, in particular light metal wheels or as a component thereof, for sanitary appliances, in particular as a fitting, or as a component thereof for internal or external body components or as a component thereof, for handles or handle components, in particular door handles or as a component thereof, for profiles or frames, in particular window frames or as a component thereof, for fitting systems or as a component thereof, in particular signs and door plates, for housing or as a packaging or as a component thereof, for interior or exterior components of ships or as a component thereof, for or as a component of or for jewelery, for or as a component thereof, for interior or external components of aircraft or as a component thereof, for internal or external components of buildings or as a component thereof, for radiators or pipes or as a component thereof, for components of elevators or as a component thereof, for components of electronic components or devices or as
  • substrates can be obtained which are provided with decorative coatings containing metal particles and which are distinguished by a very good adhesion of the decorative layer to the substrate, even at high concentrations of metal particles in the coating composition used.
  • the resulting coated substrates are also characterized by excellent corrosion properties and a very good and consistent glossy effect.

Description

Die vorliegende Erfindung betrifft ein Verfahren zur Herstellung beschichteter Substrate sowie solche beschichteten Substrate.The present invention relates to a process for producing coated substrates and to such coated substrates.

Nicht-metallische wie auch insbesondere metallische Substrate werden häufig mit einer oder mehreren Beschichtungen versehen, um einen besonderen dekorativen Effekt zu erzielen und/oder um das Substrat vor bestimmten äußeren Einflüssen zu schützen. Bei metallischen Substraten dienen Beschichtungen häufig dazu, den Korrosionsschutz zu erhöhen. Als dekorative Beschichtungssysteme haben sich insbesondere für metallische Substratoberflächen so genannte Metallic- und Effektlacke bewährt. Um den Metalliceffekt (Flop) zu erhalten, bedarf es des Einsatzes von Metallpigmenten, beispielsweise Aluminiumpigmenten. Diese werden insbesondere in Form von Plättchen, Flakes oder Flocken eingesetzt. Damit die Aluminiumpigmente, wenn in wässrigen Beschichtungszusammensetzungen vorliegend, nicht unter Wasserstoffbildung reagieren, wird in der WO 88/01637 A1 vorgeschlagen, die eingesetzten A-luminiumpigmente zuvor mit einer Chromsäurelösung zu passivieren, die darüber hinaus einen wasserlöslichen Glykolether und ein wasserlösliches Glykol enthält. Gemäß der DE 44 32 225 A1 lässt sich der optische Eindruck einer Aluminiummetalloberfläche mit einem solchen Aluminiummetalleffektlack erzielen, der im wesentlichen aus entweder i) weißem Perlglanzpigment und Aluminiumpigment, ii) weißem Perlglanzpigment, Aluminiumpigment und Weißpigment, iii) Wismutoxichloridpigment oder iv) Wismutoxichloridpigment sowie Perlglanzpigment, Aluminiumpigment und/oder Weißpigment besteht. Gemäß der DE 195 26 478 A1 lassen sich auch nachträglich zu verformende Polymerfolien mit Effektlacken beschichten, wenn eine Bindemittelkombination auf der Basis eines elastischen Polyurethanharzes und eines harten Melaminharzes verwendet wird. Aus der DE 40 14 212 A1 gehen Effekt-Basislacke mit guter Haftung auf aus Polypropylen bestehenden Kunststoffsubstraten hervor, die bei Verwendung von Lacksystemen, enthaltend Bindemittel mit physikalischem Trocknungsvermögen, chlorierte Polyolefine mit einem Chlorgehalt von 15 bis 35 Gewichtsprozent und mit einem Molekulargewicht von 7000 bis 130000, Celluloseacetobutyrat, Effektpigment und Lösemittel, erhalten werden. In der DE 33 14 777 A1 wird ein Verfahren zum Lackieren von Kraftfahrzeugen beschrieben, mit dem eine Effekt-Lackierung in nur einem Arbeitsgang auf in üblicher Weise grundierte Metall-Karosserieteile aufgebracht werden kann. Hierfür ist es erforderlich, Lacke zu verwenden, die Kupfer-Phthalocyaninpigmente der beta-Modifikation enthalten, die zumindest zu 50 Gewichtsprozent aus Plättchen besteht, die mindestens 10 µm lang und mindestens 3 µm breit sind und wobei das Verhältnis von Länge zu Breite mindestens 3,3 : 1 ist und das Pigment zwischen 610 und 640 und zwischen 710 und 740 nm je ein Reflexionsmaximum aufweist. Ein solcher Lack hat als Bindemittel ein Gemisch aus Acrylatharzen und/oder gesättigten Polyestern, jeweils mit einer OH-Zahl von 40 bis 200, und einer im wesentlichen äquivalenten Menge an damit vernetzenden aliphatischen Polyisocyanaten zu enthalten. Schließlich ist ein solcher Lack in einer einzigen Schicht mit einer Trockenfilmstärke von 30 bis 50 µm aufzutragen und zu härten. Zusätzlich ist dafür Sorge zu tragen, dass mindestens 90 Gewichtsprozent der Pigmentteilchen eine Länge zwischen 10 und 30 µm aufweisen und der Rest der Teilchen eine Länge von höchstens 50 µm aufweist. Ein besonders guter Auftrag einer Metalleffektlackdekorschicht gelingt nach der DE 197 35 540 C1 dann, wenn zunächst zum Zweck der Grundierung eine Füllerschicht aus einem vorvemetzbaren Pulverlack mit einer Schichtdicke im Bereich von 30 µm bis 250 µm eingesetzt wird.Non-metallic as well as in particular metallic substrates are often provided with one or more coatings in order to achieve a particular decorative effect and / or to protect the substrate against certain external influences. For metallic substrates, coatings are often used to increase corrosion protection. As decorative coating systems, so-called metallic and effect coatings have proven particularly suitable for metallic substrate surfaces. In order to obtain the metallic effect (flop), it is necessary to use metal pigments, for example aluminum pigments. These are used in particular in the form of platelets, flakes or flakes. In order for the aluminum pigments, when present in aqueous coating compositions, not to react under hydrogen formation, in the WO 88/01637 A1 proposed to passivate the employed A-lumium pigments beforehand with a chromic acid solution which additionally contains a water-soluble glycol ether and a water-soluble glycol. According to the DE 44 32 225 A1 The visual impression of an aluminum metal surface can be achieved with such an aluminum metal effect paint consisting essentially of either i) white pearlescent pigment and aluminum pigment, ii) white pearlescent pigment, aluminum pigment and white pigment, iii) bismuth oxychloride pigment or iv) bismuth oxychloride pigment and pearlescent pigment, aluminum pigment and / or white pigment , According to the DE 195 26 478 A1 can also be coated subsequently to be deformed polymer films with effect paints when a binder combination based on a flexible polyurethane resin and a hard melamine resin is used. From the DE 40 14 212 A1 For example, effect basecoats with good adhesion to plastic substrates made of polypropylene which, when using paint systems containing binders with physical drying power, chlorinated polyolefins having a chlorine content of 15 to 35 weight percent and having a molecular weight of 7000 to 130000, cellulose acetobutyrate, effect pigment and solvent. In the DE 33 14 777 A1 a method for painting motor vehicles is described, with which an effect coating can be applied in only one operation on primed in the usual way metal body panels. For this purpose, it is necessary to use lacquers containing beta-modification copper phthalocyanine pigments which are at least 50% by weight of platelets at least 10 μm long and at least 3 μm wide, and where the ratio of length to width is at least 3, 3: 1 and the pigment has a reflection maximum between 610 and 640 and between 710 and 740 nm. Such a paint has to contain as binder a mixture of acrylate resins and / or saturated polyesters, each having an OH number of 40 to 200, and a substantially equivalent amount of aliphatic polyisocyanates crosslinking therewith. Finally, such a paint is applied in a single layer with a dry film thickness of 30 to 50 microns and harden. In addition, care must be taken that at least 90% by weight of the pigment particles have a length between 10 and 30 μm and the remainder of the particles have a length of at most 50 μm. A particularly good order of a metallic effect paint decorative layer succeeds after the DE 197 35 540 C1 if, for the purpose of priming, a filler layer of a pre-crosslinkable powder coating having a layer thickness in the range from 30 μm to 250 μm is used first.

Die aus dem Stand der Technik bekannten Effektlacksysteme lassen noch stets Wünsche offen, insbesondere im Hinblick auf deren Haftvermögen und Korrosionsbeständigkeit. Zudem geht bislang eine Optimierung des Haftvermögens häufig zu Lasten des Dekoreffekts. Auch wird regelmäßig festgestellt, dass bei Erhöhung des Anteils der Metallpigmente, beispielsweise zur Erzeugung des Eindrucks einer durchgängigen Metalloberfläche, die Haftung der Dekorschicht auf dem Substrat nicht besonders gut ist.The effect coating systems known from the prior art still leave something to be desired, in particular with regard to their adhesion and corrosion resistance. In addition, an optimization of the adhesion is often at the expense of the decor effect. It is also regularly found that when the proportion of metal pigments is increased, for example to produce the impression of a continuous metal surface, the adhesion of the decorative layer to the substrate is not particularly good.

Es wäre somit wünschenswert, auf Beschichtungssysteme und -verfahren zurückgreifen zu können, die nicht mit den Nachteilen des Stands der Technik behaftet sind. Der vorliegenden Erfindung lag daher die Aufgabe zu Grunde, ein Beschichtungsverfahren und -system zugänglich zu machen, mit dem substratunabhängig eine dekorativ einwandfreie Metalleffektbeschichtung mit sehr gutem Haftvermögen zur Unterlage erhalten werden kann. Der vorliegenden Erfindung lag ferner die Aufgabe zu Grunde, solche Metalleffektbeschichtungen zur Verfügung zu stellen, die mit einem hervorragenden Korrosionsschutz ausgestattet sind.It would thus be desirable to be able to resort to coating systems and methods that do not suffer from the disadvantages of the prior art. The present invention was therefore based on the object of making available a coating method and system which can be used to obtain a decoratively perfect metallic effect coating with very good adhesion to the substrate independently of the substrate. The present Another object of the invention was to provide such metallic effect coatings which are provided with outstanding corrosion protection.

Demgemäß wurde ein Verfahren zur Herstellung eines beschichteten Substrats gefunden, umfassend

  • a) Zurverfügungstellung eines Substrats mit mindestens einer zumindest bereichsweise beschichtbaren Oberfläche,
  • d) zumindest bereichsweises Aufbringen mindestens einer Dekorlackschicht, enthaltend mindestens ein Bindemittel und metallische Partikel, enthaltend oder im wesentlichen bestehend aus - als erstem Metall - Aluminium, Gold, Silber, Blei, Vanadium, Mangan, Eisen, Kobalt, Nickel, Kupfer, Palladium, Platin, Titan, Zink, Magnesium oder Legierungen dieser Metalle oder enthaltend oder im wesentlichen bestehend aus Messing, Bronze oder Edelstahl, und
  • e) Behandeln der Dekorlackschicht mit einem wässrigen System, enthaltend mindestens eine Säure, ein Oxid, Doppeloxid, Oxid-Hydrat, Sulfid, Halogenid, Nitrid, Carbid, Carbonitrid, Borid, Silicid, Oxihalogenid und/oder Salz eines Elements der 4. oder 5. Gruppe des Periodensystems der Elemente - als zweitem Metall - oder Mischungen hiervon.
Accordingly, a process for producing a coated substrate has been found, comprising
  • a) providing a substrate having at least one surface which can be coated at least in regions,
  • d) at least partially applying at least one decorative lacquer layer containing at least one binder and metallic particles, comprising or consisting essentially of - as the first metal - aluminum, gold, silver, lead, vanadium, manganese, iron, cobalt, nickel, copper, palladium, Platinum, titanium, zinc, magnesium or alloys of these metals or containing or consisting essentially of brass, bronze or stainless steel, and
  • e) treating the decorative lacquer layer with an aqueous system comprising at least one acid, an oxide, double oxide, oxide hydrate, sulfide, halide, nitride, carbide, carbonitride, boride, silicide, oxyhalide and / or salt of an element of the 4th or 5th Group of the Periodic Table of the Elements - as second metal - or mixtures thereof.

Der Begriff "erstes Metall" soll im Sinne der vorliegenden Erfindung auch die vorangehend unter d) genannten Legierungen umfassen. Der Begriff "zweites Metall" soll im Sinne der vorliegenden Erfindung Elemente der 4. und 5. Gruppe des Periodensystems der Elemente bzw. Verbindungen dieser Elemente mit den vorangehend unter e) genannten Verbindungskomponenten, z. B. Oxide, umfassen.For the purposes of the present invention, the term "first metal" should also include the alloys mentioned above under d). The term "second metal" is intended in the context of the present invention elements of the 4th and 5th group of the Periodic Table of the Elements or compounds of these elements with the above e) connection components, z. For example, oxides.

Die metallischen Partikel stellen vorzugsweise plättchenförmige Metallpartikel, zum Beispiel plättchenförmige Aluminiumpartikel dar. In einer bevorzugten Ausgestaltung enthalten die metallischen, insbesondere plättchenförmige, Partikel oder bestehen im wesentlichen aus Aluminium, Aluminiumlegierungen, Eisen, Eisenlegierungen, Gold, Goldlegierungen, oder Kupfer oder Kupferlegierungen.The metallic particles are preferably platelet-shaped metal particles, for example platelet-shaped aluminum particles. In a preferred embodiment, the metallic, in particular platelet-shaped, particles or consist essentially of aluminum, aluminum alloys, iron, iron alloys, gold, gold alloys, or copper or copper alloys.

Insbesondere bevorzugt ist, dass die Reinheit der für die metallischen Partikel verwendeten Metalle, vorzugsweise des Aluminiums, mindestens 80 Gew.-%, vorzugsweise mehr als 90 Gew.-%, am besten mindestens 99 Gew.-%, beträgt.It is particularly preferred that the purity of the metals used for the metallic particles, preferably of aluminum, is at least 80% by weight, preferably more than 90% by weight, most preferably at least 99% by weight.

In den metallischen Partikeln der nach dem erfindungsgemäßen Verfahren erhältlichen beschichteten Substrate, insbesondere in den an der Oberfläche bzw. im Oberflächenbereich der Bindemittel enthaltenden Dekorlackschicht befindlichen metallischen Partikel, liegt mindestens ein Oxid, Doppeloxid, Oxid-Hydrat, Sulfid, Halogenid, Nitrid, Carbid, Carbonitrid, Borid, Silicid, Oxihalogenid und/oder Salz eines Elements der 4. oder 5. Gruppe des Periodensystems der Elemente oder Mischungen hiervon vor. In einer Ausführungsform liegen die vorangehend genannten Verbindungen im wesentlichen gleichmäßig verteilt in den metallischen Partikeln, insbesondere in den metallischen Partikeln, die sich an der Oberfläche oder im Oberflächenbereich der Dekorlackschicht befinden, vor. Selbstverständlich kann sich die Konzentration dieser in die metallischen Partikel eingelagerten Verbindungen in einer weiteren Ausführungsform über die Dicke der Partikel auch kontinuierlich, stufenweise oder in sonstiger Weise, zum Beispiel sprunghaft, mehr oder weniger stark ausgeprägt ändern. Auch können in einer Ausführungsform diese Verbindungen im wesentlichen ausschließlich im Bereich der gesamten Oberfläche der metallischen Partikel oder im Bereich nur eines Teils der Oberfläche der metallischen Partikel vorliegen bzw. eingebettet sein. Die mit dem wässrigen System behandelten Partikel können demgemäß auch als eine vollständige oder bereichsweise innige Vermengung bzw. als ein gegebenenfalls auch nur phasenweiser metallischer Kompositpartikel, enthaltend das erste Metall, wie vorangehend beschrieben, und darin vorliegend bzw. eingebettet mindestens eine Verbindung des zweiten Metalls, insbesondere mindestens eine Säure, ein Oxid, Doppeloxid, Oxid-Hydrat, Sulfid, Halogenid, Nitrid, Carbid, Carbonitrid, Borid, Silicid, Oxihalogenid und/oder Salz des zweiten Metalls verstanden werden. Besonders vorteilhafte Eigenschaften insbesondere im Hinblick auf eine gute Anbindung bzw. Haftung der zu Beschichtungsfläche sowie auf guten Korrosionsschutz werden dann erzielt, wenn die eingelagerten bzw. eingebetteten Oxide Zirkoniumoxide, Titanoxide oder Hafniumoxide, die Oxifluoride Zirkoniumoxifluoride, Titanoxifluoride oder Hafniumoxifluoride, die Säuren Fluorzirkonsäure, Fluortitansäure oder Fluorhafniumsäure und die Salze Fluorzirkonate, Fluortitanate oder Fluorhafniate darstellen. Besonders bevorzugt liegen in den metallischen Partikeln oxidisch gebundenes Zirkonium, z.B. Oxide des Zirkoniums wie Zirkoniumdioxid, Zirkoniumoxifluoride und/oder Doppeloxide des Zirkoniums, beispielsweise Aluminium/Zirkoniumoxide, vor.In the metallic particles of the coated substrates obtainable by the process according to the invention, in particular in the metallic particles present on the surface or in the surface region of the binder, there is at least one oxide, double oxide, oxide hydrate, sulfide, halide, nitride, carbide, Carbonitride, boride, silicide, oxyhalide and / or salt of an element of the 4th or 5th group of the Periodic Table of the Elements or mixtures thereof. In one embodiment, the abovementioned compounds are present substantially uniformly distributed in the metallic particles, in particular in the metallic particles which are located on the surface or in the surface region of the decorative lacquer layer. Of course, in a further embodiment, the concentration of these compounds incorporated in the metallic particles can change more or less strongly over the thickness of the particles, also continuously, stepwise or in any other way, for example abruptly. Also, in one embodiment, these compounds may be present or embedded substantially exclusively in the region of the entire surface of the metallic particles or in the region of only a part of the surface of the metallic particles. Accordingly, the particles treated with the aqueous system may also be in the form of a complete or partially intimately mixed or, if appropriate, only phased, metallic composite particles containing the first metal as described above and embedded therein at least one compound of the second metal, in particular at least one acid, an oxide, double oxide, oxide hydrate, sulfide, halide, nitride, carbide, carbonitride, boride, silicide, oxyhalide and / or salt of the second metal are understood. Particularly advantageous properties, in particular with regard to a good bonding or adhesion to the coating surface and to good corrosion protection, are achieved if the embedded or embedded oxides zirconium oxides, titanium oxides or hafnium oxides, the oxifluorides zirconium oxifluorides, titanium oxyfluorides or hafnium oxyfluorides, the acids fluoric acid, fluorotitanic acid or Fluorhafniumsäure and the salts fluorozirconate, fluorotitanates or Fluorhafniate represent. Particularly preferred oxide-bound zirconium, for example oxides of zirconium such as zirconium dioxide, zirconium oxifluorides and / or double oxides of zirconium, for example aluminum / zirconium oxides, are present in the metallic particles.

Als geeignete Substrate kommen zum Beispiel Metalle, Edelmetalle, Metalllegierungen oder Glas, Keramik, Verbundfasermaterialien, Karbonmaterialien, Kunststoffe, Holz oder Spanholz in Betracht.Suitable substrates include, for example, metals, precious metals, metal alloys or glass, ceramics, composite fiber materials, carbon materials, plastics, wood or chipboard.

Besonders geeignete Kunststoffe stellen z.B. PVC, Polyurethane, Polyester, z.B. PBT und PET, Polyolefine, insbesondere Polypropylen, Polyamide, Polystyrol, Styro(co)polymere, wie ABS, SAN, ASA oder MABS, und Polyoxyalkylene, z.B. POM, dar. In geeigneten Substraten können neben metallischen Komponenten oder Abschnitten auch nicht-metallische Komponenten bzw. Abschnitte vorliegen.Particularly suitable plastics are e.g. PVC, polyurethanes, polyesters, e.g. PBT and PET, polyolefins, especially polypropylene, polyamides, polystyrene, styrene (co) polymers such as ABS, SAN, ASA or MABS, and polyoxyalkylenes, e.g. POM, dar. In suitable substrates may be present in addition to metallic components or sections and non-metallic components or sections.

Grundsätzlich eigenen sich als metallische Substrate Formkörper aus allen Metallen, Metalllegierungen und Edelmetallen. Als geeignete Substrate seien exemplarisch solche aus Aluminium, Eisen, Stahl, Edelstahl, Kupfer, Messing, Magnesium, Iridium, Gold, Silber, Palladium, Platin, Ruthenium, Molybdän, Nickel, Bronze, Titan, Zink, Blei, Wolfram oder Mangan sowie deren Legierungen genannt. Bevorzugte Metallsubstrate bzw. Metallsubstratoberflächen umfassen bzw. insbesondere bestehen aus Aluminium oder Aluminiumlegierungen, Magnesium oder Magnesiumlegierungen oder Titan oder Titanlegierungen oder aus Stahl oder Edelstahl. Besonders bevorzugt wird für die metallischen Substrate auf Aluminium und Aluminiumlegierungen zurückgegriffen. Auch Substrate aus Druckguss, z.B. Zinkdruckguss, sind besonders geeignet.In principle, shaped bodies of all metals, metal alloys and precious metals are suitable as metallic substrates. Examples of suitable substrates are those of aluminum, iron, steel, stainless steel, copper, brass, magnesium, iridium, gold, silver, palladium, platinum, ruthenium, molybdenum, nickel, bronze, titanium, zinc, lead, tungsten or manganese and their Called alloys. Preferred metal substrates or metal substrate surfaces comprise or in particular consist of aluminum or aluminum alloys, magnesium or magnesium alloys or titanium or titanium alloys or of steel or stainless steel. Particular preference is given to the metallic substrates on aluminum and aluminum alloys. Also diecast substrates, e.g. Zinc diecasting, are particularly suitable.

Bei einer bevorzugten Verfahrensvariante ist vorgesehen, dass das wässrige System mindestens eine Säure, ein Oxid, Doppeloxid, Oxid-Hydrat, Halogenid, Oxyhalogenid oder Salz eines Elements der 4. oder 5. Gruppe, insbesondere des Titans oder des Zirkoniums, oder Mischungen hiervon enthält. Das wässrige System wird günstiger Weise auf einen pH-Wert im Bereich von 1,5 bis 6,5 eingestellt.In a preferred variant of the method it is provided that the aqueous system contains at least one acid, an oxide, double oxide, oxide hydrate, halide, oxyhalide or salt of an element of the 4th or 5th group, in particular of titanium or zirconium, or mixtures thereof , The aqueous system is conveniently adjusted to a pH in the range of 1.5 to 6.5.

Bei der Behandlung der auf dem Substrat aufgetragenen Dekorlackschicht mit dem genannten wässrigen System werden die in dem wässrigen System vorliegenden Verbindungen der Elemente der 4. oder 5. Gruppe des Periodensystems der Elemente vorzugsweise in zumindest einen Teil der metallischen Partikel wenigstens partiell eingetragen bzw. eingebettet.In the treatment of the decorative lacquer layer applied to the substrate with said aqueous system, the compounds of the elements of the 4th or 5th group of the Periodic Table of the Elements present in the aqueous system are preferably at least partially introduced or embedded in at least one part of the metallic particles.

In einer Weiterentwicklung des erfindungsgemäßen Verfahrens ist vorgesehen, dass die Dekorlackschicht mit dem wässrigen System unter Druck, insbesondere in Form von Flüssigkeitsstrahlen, beaufschlagt wird. Auf diese Weise gelingt in der Regel eine besonders effektive Eintragung bzw. Einbettung der vorangehend genannten Verbindungen der 4. und 5. Gruppe des Periodensystems der Elemente in zumindest einen Teil der metallischen Partikel der Dekorlackschicht.In a further development of the method according to the invention, it is provided that the decorative lacquer layer is exposed to the aqueous system under pressure, in particular in the form of liquid jets. In this way, usually a particularly effective entry or embedding of the above-mentioned compounds of the 4th and 5th group of the Periodic Table of the Elements in at least a portion of the metallic particles of the decorative coating layer succeeds.

Das wässrige System kann z.B. in Form einer Lösung, einer Suspension oder einer Emulsion vorliegen. Bevorzugt wird das wässrige System als Lösung eingesetzt, d.h. die vorangehend genannten Verbindungen, Salze und/oder Säuren liegen darin zumindest vor der Applikation im wesentlichen gelöst vor.The aqueous system may e.g. in the form of a solution, a suspension or an emulsion. Preferably, the aqueous system is used as a solution, i. the abovementioned compounds, salts and / or acids are present substantially dissolved at least before the application.

Der Leitwert des eingesetzten wässrigen Systems liegt vorzugsweise im Bereich von 100 bis 2000, besonders bevorzugt im Bereich von 150 bis 1500 und insbesondere im Bereich von 200 bis 1000 µS/cm. Geeigneter Weise liegt die Temperatur des wässrigen Systems beim Behandlungsvorgang des Substrats im Bereich von 15 bis 50°C, bevorzugt im Bereich von 20 bis 40°C. In der Regel reicht bereits eine Behandlungsdauer von 20 bis 120 Sekunden aus, um das erfindungsgemäße Substrat zu erhalten.The conductance of the aqueous system used is preferably in the range from 100 to 2000, particularly preferably in the range from 150 to 1500 and in particular in the range from 200 to 1000 μS / cm. Suitably, the temperature of the aqueous system in the process of treating the substrate is in the range of 15 to 50 ° C, preferably in the range of 20 to 40 ° C. As a rule, a treatment duration of 20 to 120 seconds is sufficient to obtain the substrate according to the invention.

Als vorteilhaft in Bezug auf Haftvermögen und Korrosionsschutz hat sich unter anderem auch erwiesen, dass nach Verfahrensschritt d) und/oder nach Verfahrensschritt e) die beschichtete Oberfläche des Substrats einem Spülschritt mit, insbesondere vollentsalztem, Wasser unterzogen wird.Among other things, it has also proven to be advantageous with regard to adhesion and corrosion protection that, after process step d) and / or after process step e), the coated surface of the substrate is subjected to a rinsing step with, in particular demineralized, water.

Hieran schließt sich vorzugsweise jeweils mindestens ein Trocknungsschritt zum Trocknen der Oberfläche an. Der Trocknungsschritt kann z.B. bei Temperaturen im Bereich von 120 bis 180°C, beispielsweise bei etwa 140°C, durchgeführt werden. Das zum Spülen eingesetzte Wasser verfügt vorzugsweise über einen Leitwert kleiner 60 mS/cm, vorzugsweise kleiner 50 mS/cm und insbesondere kleiner 35 mS/cm. Insbesondere der jeweils letzte Spülgang vor dem nachfolgenden Verfahrensschritt oder vor einem Trocknungsvorgang verfügt über die voranstehend genannten Leitwerte.This is preferably followed by at least one drying step for drying the surface. The drying step can be carried out, for example, at temperatures in the range from 120 to 180 ° C, for example at about 140 ° C. The water used for rinsing preferably has a conductance of less than 60 mS / cm, preferably less than 50 mS / cm and in particular less than 35 mS / cm. In particular, the respective last rinse before the subsequent process step or before a drying process has the above-mentioned guide values.

Der pH-Wert und/oder der Leitwert des wässrigen Systems werden für die Dauer der Behandlung der Metallschicht vorzugsweise im wesentlichen konstant gehalten, insbesondere innerhalb der vorangehend genannten Bereiche.The pH and / or the conductance of the aqueous system are preferably kept substantially constant for the duration of the treatment of the metal layer, in particular within the abovementioned ranges.

Das mit der Dekorlackschicht versehene Substrat kann z.B. mittels Eintauchens, Spülens oder Besprühens mit dem vorangehend beschriebenen wässrigen System, enthaltend mindestens eine der genannten Verbindungen des zweiten Metalls, behandelt werden. Bevorzugt wird die Dekorlackschicht unter erhöhtem Druck mit diesem wässrigen System beaufschlagt, beispielsweise in Form von Hochdruckwasserstrahlen. Hierbei hat es sich als zweckmäßig erwiesen, eine Vielzahl an feinen Einzelwasserstrahlen auf das Substrat zu richten. Geeignete Drücke für die Beaufschlagung mit dem wässrigen System liegen z.B. oberhalb von 0,2 bar, vorzugsweise im Bereich von 0,5 bis 50 bar und besonders bevorzugt im Bereich von 0,2 bis 15, insbesondere von 0,9 bis 1,5 bar. Diese Drücke werden auf der Oberfläche der Metallschicht gemessen. Insbesondere mit dieser vorangehend beschriebenen Variante kann mindestens eine Säure, ein Oxid, Doppeloxid, Oxid-Hydrat, Sulfid, Halogenid, Nitrid, Carbid, Carbonitrid, Borid, Silicid, Oxyhalogenid und/oder Salz des zweiten Metalls, insbesondere eines Elements der 4. Gruppe des Periodensystems, vorzugsweise Zirkonium, Titan oder Hafnium, in die metallischen Partikel der Dekorlackschicht eingetragen werden.The substrate provided with the decorative varnish layer may be e.g. by immersion, rinsing or spraying with the aqueous system described above, containing at least one of said compounds of the second metal. Preferably, the decorative lacquer layer is subjected to this aqueous system under elevated pressure, for example in the form of high-pressure water jets. It has proven to be useful to direct a variety of fine single water jets on the substrate. Suitable pressures for exposure to the aqueous system are e.g. above 0.2 bar, preferably in the range of 0.5 to 50 bar and particularly preferably in the range of 0.2 to 15, in particular from 0.9 to 1.5 bar. These pressures are measured on the surface of the metal layer. In particular, with this variant described above, at least one acid, an oxide, double oxide, oxide hydrate, sulfide, halide, nitride, carbide, carbonitride, boride, silicide, oxyhalide and / or salt of the second metal, in particular an element of the 4th group of the Periodic Table, preferably zirconium, titanium or hafnium, are introduced into the metallic particles of the decorative lacquer layer.

Ohne an irgendeine Theorie gebunden zu sein, wird gegenwärtig angenommen, dass die Verbindungen des zweiten Metalls, die in dem wässrigen System z.B. als Säure oder Salz vorliegen, in den metallischen Partikeln in ein Oxid, Doppeloxid, Oxid-Hydrat oder Oxyhalogenid überführt vorliegen.Without being bound by any theory, it is presently believed that the compounds of the second metal which are present in the aqueous system e.g. present as acid or salt, in which metallic particles are converted into an oxide, double oxide, oxide hydrate or oxyhalide.

Geeignete Säuren, die auf ein Element der 4. Gruppe zurückgehen, umfassen z.B. Hydrofluorzirkonsäure (H2ZrF6), Fluortitansäure (H2TiF6) und Fluorhafniumsäure (H2HfF6). Selbstverständlich können auch Mischungen unterschiedlicher Säuren eingesetzt werden. Diese Fluorsäuren können sowohl im Reinzustand als auch enthaltend Verunreinigungen, beispielsweise Fluorsäure, eingesetzt werden. In den wässrigen Systemen können die Säuren z.B. in Mengen von bis zu 5 Gew.%, insbesondere von bis zu 3,5 Gew.-%, bezogen auf das Gesamtgewicht des wässrigen Systems, vorliegen. Fluorsäure kann in den wässrigen Systemen, z.B. in Mengen im Bereich von 0,1 bis 3 Gew.-%, ebenfalls zugegen sein. Unter den geeigneten Salzen wird bevorzugt auf Ammoniumzirkoniumcarbonat, das beispielsweise von der Firma Magnesium Electron Inc. unter der Markenbezeichnung Bacote 20 erhältlich ist, eingesetzt ((NH4)2[Zr(OH)2(CO3)2]·n H2O). Ferner können auch Alkalimetall- und Ammoniumfluorzirkonate, beispielsweise Na2ZrF6, KZrF6, (NH4)ZrF6, ebenso wie Zirkoniumnitrate, Zirkoniumoxynitrate, Zirkoniumcarbonate, Zirkoniumfluoride oder Zirkoniumsulfat eingesetzt werden. Die Verbindungen basierend auf der 4. Gruppe können als solche oder in beliebiger Mischung miteinander eingesetzt werden. Das Gleiche trifft auf die Verbindungen der 5. Gruppe zu.Suitable acids derived from a group 4 element include, for example, hydrofluorozirconic acid (H 2 ZrF 6 ), fluorotitanic acid (H 2 TiF 6 ) and fluoro hafnic acid (H 2 HfF 6 ). Of course, mixtures of different acids can be used. These fluoric acids can be used both in the pure state and also containing impurities, for example fluoric acid. In the aqueous systems, the acids may be present, for example, in amounts of up to 5% by weight, in particular of up to 3.5% by weight, based on the total weight of the aqueous system. Fluoric acid may also be present in the aqueous systems, eg in amounts ranging from 0.1 to 3% by weight. Among the suitable salts it is preferred to use ammonium zirconium carbonate, which is available, for example, from Magnesium Electron Inc., under the trade name Bacote 20, used ((NH 4 ) 2 [Zr (OH) 2 (CO 3 ) 2 ] .nH 2 O). It is also possible to use alkali metal and ammonium fluorozirconates, for example Na 2 ZrF 6 , KZrF 6 , (NH 4 ) ZrF 6 , as well as zirconium nitrates, zirconium oxynitrates, zirconium carbonates, zirconium fluorides or zirconium sulfate. The compounds based on the 4th group can be used as such or in any mixture with each other. The same applies to the compounds of the 5th group.

Selbstverständlich ist es ebenfalls möglich, den wässrigen Systemen neben den genannten Verbindungen oder deren Mischungen weitere Bestandteile zuzumischen. Hierfür kommen u.a. Salpetersäure, Fluorsäure, Phosphorsäure, Salze der genannten Säuren, Ammoniumbifluorid und Ammoniumsulfat in Betracht. Ein geeignetes Titansalz stellt z.B. Ammoniumtitanfluorid dar.Of course, it is also possible to admix the aqueous systems in addition to the compounds mentioned or mixtures thereof further ingredients. For this come u.a. Nitric acid, fluoric acid, phosphoric acid, salts of said acids, ammonium bifluoride and ammonium sulfate into consideration. A suitable titanium salt provides e.g. Ammonium titanium fluoride.

Bevorzugt enthält das wässrige System Fluoridionen in freier und/oder komplexierter Form. Als geeignete komplexierte Fluoridionen seien Fluoroboratsalze und -säuren sowie Alkalimetall- und Ammoniumbifluoride genannt. Ganz allgemein sind komplexe Fluoride des Titans, Zirkoniums, Hafniums, Siliziums und/oder Bors besonders geeignet. Bevorzugt wird auf komplexe Fluoride als Zirkoniums zurückgegriffen.The aqueous system preferably contains fluoride ions in free and / or complexed form. Suitable complexed fluoride ions include fluoroborate salts and acids as well as alkali metal and ammonium bifluorides. In general, complex fluorides of titanium, zirconium, hafnium, silicon and / or boron are particularly suitable. Preference is given to using complex fluorides as zirconium.

Geeignete wässrige Systeme können vorzugsweise neben der Säure, einem Oxid, Doppeloxid, Oxid-Hydrat, Sulfid, Halogenid, Nitrid, Carbid, Carbonitrid, Borid, Silicid, Oxyhalogenid und/oder Salz des zweiten Metalls, vorzugsweise basierend auf einem Element der 4. Gruppe des Periodensystems der Elemente (IUPAC; ehemals mit Gruppe IVb oder IV-B bezeichnet), insbesondere Zirkonium, Titan und/oder Hafnium, vorzugsweise Zirkonium, mindestens eine polymere Verbindung enthalten, die in der wässrigen Zusammensetzung gelöst, in Emulsionsform oder in Form ungelöster dispergierter Partikel vorliegen kann.Suitable aqueous systems may preferably be in addition to the acid, an oxide, double oxide, oxide hydrate, sulfide, halide, nitride, carbide, carbonitride, boride, silicide, oxyhalide and / or salt of the second metal, preferably based on a 4th group element of the Periodic Table of the Elements (IUPAC, formerly designated Group IVb or IV-B), in particular zirconium, titanium and / or hafnium, preferably zirconium, at least one polymeric compound dissolved in the aqueous composition, in emulsion form or in undissolved dispersed form Particles may be present.

Unter den polymeren Verbindungen seien insbesondere die Polyacrylsäure sowie deren Salze und Ester genannt. Diese Säuren, Ester und Salze können in der wässrigen Lösung in gelöster oder in dispergierter Form vorliegen. Die Menge an Polymerkomponente kann in weiten Bereichen variiert werden und liegt vorzugsweise im Bereich von 0,1 bis 0,5 g pro Liter.Among the polymeric compounds may be mentioned in particular the polyacrylic acid and its salts and esters. These acids, esters and salts may be present in the aqueous solution in dissolved or dispersed form. The amount of polymer component can be varied widely and is preferably in the range of 0.1 to 0.5 g per liter.

In einer weiteren Ausführungsform umfasst das erfindungsgemäße Verfahren nach Verfahrensschritt a) und vor Verfahrensschritt d) als Verfahrensschritt b) das Aufbringen mindestens einer Konversionsschicht auf dem Substrat. Herkömmliche Konversionsschichten finden sich zum Beispiel in der US 2,825,697 und der US 2,928,763 beschrieben. Bei der Konversionsschicht kann es sich zum Beispiel auch um herkömmliche Passivierungsschichten auf der Basis von Nickel-, Chrom- und Zinkverbindungen handeln.In a further embodiment, the process according to the invention comprises after process step a) and before process step d) as process step b) the application of at least one conversion layer to the substrate. Conventional conversion layers can be found, for example, in US Pat US 2,825,697 and the US 2,928,763 described. The conversion layer may, for example, also be conventional passivation layers based on nickel, chromium and zinc compounds.

In einer weiteren Ausgestaltung umfasst das Verfahren ferner nach dem Verfahrensschritt a) und vor dem Verfahrensschritt d) als Verfahrensschritt c) das Aufbringen mindestens einer ersten und gegebenenfalls mindestens einer zweiten Grundierungsschicht auf dem Substrat. Hierbei ist von besonderem Vorteil, wenn mindestens eine erste und/oder mindestens eine zweite Grundierungsschicht zumindest bereichsweise auf der Konversionsschicht aufgebracht wird. Alternativ zur Aufbringung einer ersten und gegebenenfalls zweiten Grundierungsschicht oder zusätzlich zu der Aufbringung einer Grundierungsschicht kann eine vorgeschaltete mechanische Glättung der Metallsubstratoberfläche, beispielsweise mittels Schleifens und/oder Polierens bzw. Gleitschleifens, vorgesehen seinIn a further embodiment, the method further comprises after step a) and before step d) as process step c) the application of at least one first and optionally at least one second primer layer on the substrate. In this case, it is particularly advantageous if at least one first and / or at least one second primer layer is applied at least in regions to the conversion layer. As an alternative to the application of a first and optionally second primer layer or in addition to the application of a primer layer, an upstream mechanical smoothing of the metal substrate surface may be provided, for example by means of grinding and / or polishing or burnishing

Die erste und/oder die zweite Grundierungsschicht kann bzw. können beispielsweise über ein Nasslackverfahren und/oder ein Pulverbeschichtungsverfahren aufgetragen werden. Geeignet sind zum Beispiel pulverförmige Polyesterharzverbindungen sowie Epoxid/Polyester-Pulver. Geeignete Epoxidharze als Grundierungsschichtmaterialien sind im Handel z.B. unter dem Markennamen "Valophene" bekannt. Als erste und zweite Grundierungsschichten kommen auch solche basierend auf einem Urethanharz, wie in der US 4,431,711 beschrieben, in Betracht. Alternativ kann ebenfalls auf Polyester- oder Polyacrylatmaterialien, wie in der WO 2004/014646 A1 hervorgehoben, zurückgegriffen werden. Ganz besonders bevorzugt wird zum Zweck der Grundierung auf Nasslackverfahren zurückgegriffen. Besonders bevorzugt sind solche Grundierungsverfahren, bei denen die Härtung der Grundierungsschicht nicht thermisch, sondern mittels UV-Bestrahlung erfolgt. Bei der Härtung mittels UV-Strahlung ist regelmäßig keine zusätzliche Erwärmung erforderlich, auch wird im allgemeinen hierbei keine Wärme generiert. Geeignete Pulverlack-, Nasslack- und UV-härtende Beschichtungssysteme sowie deren Aufbringung sind dem Fachmann hinlänglich bekannt. Je nach Oberflächenbeschaffenheit (z.B. porös oder rauh) können eine oder mehrere Grundierungsschichten aufgetragen werden, um die Oberfläche zu glätten. Insbesondere mit der ersten Grundierungsschicht, wie sie vorliegend insbesondere auf Metallsubstratoberflächen zum Einsatz kommen kann, wird im allgemeinen eine vorteilhafte Einglättung der Oberfläche erzielt. Die Grundierungsschicht stellt somit regelmäßig eine sogenannte Glättungsschicht dar. Mit einer Grundierungsschicht werden im allgemeinen sämtliche Winkelbereiche erreicht, so dass auch in diesen Bereichen Oberflächenrauhigkeiten ausgeglichen werden können. Neben der Funktion der Glättung bzw. unabhängig hiervon hat es sich in einigen Ausführungsformen als vorteilhaft erwiesen, die erste bzw. zweite Grundierungsschicht zum Zwecke der Haftvermittlung vorzusehen. Auf diese Weise gelingt häufig eine besonders gute Anbindung der Dekorlackschicht an das beschichtende Substrat.The first and / or the second primer layer can be applied, for example, by means of a wet-paint method and / or a powder-coating method. Suitable examples are powdered polyester resin compounds and epoxy / polyester powder. Suitable epoxy resins as primer layer materials are known commercially, for example, under the trade name "Valophene". As the first and second primer layers, there are also those based on a urethane resin, as in U.S. Pat US 4,431,711 described, into consideration. Alternatively, it is also possible to use polyester or polyacrylate materials such as those described in U.S. Pat WO 2004/014646 A1 be highlighted. Very particular preference is given to the purpose of priming on wet paint process. Particularly preferred are those primer methods in which the curing of the primer layer is not thermal, but by means of UV irradiation. When curing by means of UV radiation regularly no additional heating is required, and in general no heat is generated in this case. Suitable powder coating, wet paint and UV-curing coating systems and their application are well known to those skilled in the art. Depending on the surface condition (eg porous or rough) one or several primer layers can be applied to smooth the surface. In particular, with the first primer layer, as used in particular present on metal substrate surfaces can, is achieved in general an advantageous smoothing of the surface. The primer layer thus regularly constitutes a so-called smoothing layer. With a primer layer, in general all angular ranges are achieved, so that surface roughnesses can also be compensated in these areas. In addition to the function of smoothing or independently thereof, it has proven advantageous in some embodiments to provide the first or second primer layer for the purpose of adhesion promotion. In this way, a particularly good connection of the decorative lacquer layer to the coating substrate often succeeds.

Ein weiterer Aspekt des erfindungsgemäßen Verfahrens sieht ferner vor, dass die Dekorlackschicht gemäß Verfahrensschritt d) aufgetragen wird, bevor die erste und/oder zweite Grundierungsschicht vollständig ausgehärtet ist.A further aspect of the method according to the invention further provides that the decorative lacquer layer is applied according to method step d) before the first and / or second primer layer has completely cured.

Gemäß einer weiteren Ausführungsform kann das erfindungsgemäße Verfahren ferner nach Verfahrensschritt e) als Verfahrensschritt f) das Aufbringen mindestens einer, insbesondere transparenten, Deckschicht umfassen.According to a further embodiment, the process according to the invention may further comprise, after process step e) as process step f), the application of at least one, in particular transparent, topcoat.

Der Deck- bzw. Schutzschichtlack kann z.B. ein Klarlack oder ein transparentes Pulver sein und wird vorzugsweise über ein Nasslackverfahren bzw. ein Pulverbeschichtungsverfahren aufgetragen. Ferner sieht die Erfindung vor, dass die Deckschicht mindestens einen Farbstoff oder ein Pigment enthalten kann.The topcoat can be e.g. a clearcoat or a transparent powder, and is preferably applied by a wet-paint method or a powder-coating method. Furthermore, the invention provides that the cover layer may contain at least one dye or a pigment.

Bei der Deckschicht bzw. dem Decklack kann es sich im allgemeinen um ein-, zwei- oder mehrkomponentige Lacke handeln. Hierbei sind Klarlacke bevorzugt. Bei diesen Klarlacken kann es sich z.B. um chemisch vernetzende zweikomponentige, um einkomponentige wärmehärtende oder um UV-härtende Lacke handeln. Die Deck- bzw. Klarlackschicht kann in einem separaten Schritt im Anschluss an die Herstellung und Aushärtung der Dekorlackschicht oder gemeinsam mit der Dekorlackschicht und/oder der ersten oder zweiten Grundierung ausgehärtet werden.The cover layer or the topcoat can generally be one-, two- or multi-component paints. Clearcoats are preferred here. These clearcoats may be e.g. be chemically cross-linking two-component, one-component thermosetting or UV-curable coatings. The topcoat or clearcoat layer can be cured in a separate step subsequent to the production and curing of the decorative lacquer layer or together with the decorative lacquer layer and / or the first or second primer.

Zur Färbung des Substrats kann ferner als Deckschicht oder zusätzlich zur vorangehend beschriebenen Deckschicht insbesondere auch auf geeignete, dem Fachmann bekannte Lasuren zurückgegriffen werden. Hiermit lassen sich z.B. Messing-, Titan- und Goldtöne sowie individuelle Farbtöne wie rot, blau, gelb, grün, etc. und sämtliche Eloxalfarben ohne weiteres einstellen.For coloring the substrate may also be used as a topcoat or in addition to the cover layer described above in particular also suitable, known in the art glazes. This can be used, for example, brass, titanium and gold tones as well as individual Shades such as red, blue, yellow, green, etc. and all the anodizing colors are easily set.

Von weiterem Vorteil ist zudem, dass sich mit dem erfindungsgemäßen Verfahren insbesondere dann besonders breite Spielräume bei der Farbgestaltung ergeben, wenn man die Farben bzw. Farbeffekte von Dekorlackschicht und Deckschicht sowie insbesondere von Grundierung, Dekorlackschicht und Deckschicht aufeinander abstimmt. Beispielsweise erhält man bei Verwendung einer dunkelfarbigen Grundierung, einer hochglänzenden Dekorlackschicht und einer transparenten Deckschicht Produkte mit mattiertem Chromglanz, ohne jedoch auf die Verwendung von Chrom angewiesen zu sein. Hierbei hat es sich als besonders vorteilhaft herausgestellt, wenn die Dekorlackschicht in einer Dicke aufgetragen wird, die noch stets leicht durchscheinend für die Farbe der Unterlage bzw. Grundierung ist. Hingegen erhält man selbst bei Verwendung einer noch geringfügig durchscheinenden, d. h. lasierenden Dekorlackschicht auf einer hellen Grundierung bzw. Unterlage und Einsatz einer transparenten Deckschicht ein hochglänzendes beschichtetes Substrat, beispielsweise eine Autofelge.Another advantage is also that with the inventive method especially wide margins in the color design result, if one tunes the colors or color effects of decorative lacquer layer and topcoat and in particular of primer, decorative lacquer and topcoat each other. For example, when using a dark colored primer, a high gloss decorative lacquer layer, and a transparent topcoat, products with matte chrome finish are obtained without, however, relying on the use of chromium. It has been found to be particularly advantageous if the decorative lacquer layer is applied in a thickness which is still slightly translucent for the color of the substrate or primer. On the other hand, even when using a slightly translucent, d. H. glaze decorative lacquer layer on a light primer or base and use of a transparent cover layer, a high-gloss coated substrate, such as an auto-rim.

Die nach dem erfindungsgemäßen Verfahren auf das Substrat aufgebrachte Dekorlackschicht kann zum Beispiel eine sogenannte Effektlackschicht oder eine sogenannte Metallic-Lackschicht sein.The decorative lacquer layer applied to the substrate by the method according to the invention can be, for example, a so-called effect lacquer layer or a so-called metallic lacquer layer.

Selbstverständlich ist es ebenfalls möglich, dass nach dem Aufbringen einer ersten Dekorlackschicht diese Dekorlackschicht mit einem ersten wässrigen System gemäß Verfahrensschritt e) behandelt wird, dass auf die derart behandelte erste Dekorlackschicht eine zweite Dekorlackschicht, enthaltend metallische Partikel, enthaltend oder im wesentlichen bestehend aus Aluminium, Gold, Silber, Blei, Vanadium, Mangan, Eisen, Kobalt, Nickel, Kupfer, Palladium, Platin, Titan, Zink, Magnesium oder Legierungen dieser Metalle oder enthaltend oder im wesentlichen bestehend aus Messing, Bronze oder Edelstahl, aufgebracht wird und dass diese zweite Dekorlackschicht mit einem zweiten wässrigen System, enthaltend mindestens eine Säure, ein Oxid, Doppeloxid, Oxid-Hydrat, Sulfid, Halogenid, Nitrid, Carbid, Carbonitrid, Borid, Silicid, Oxihalogenid und/oder Salz eines Elements der 4. oder 5. Gruppe des Periodensystems der Elemente oder Mischungen hiervon, behandelt wird. Hierbei können die Verfahrensschritte d) und e) nicht nur zweimal in Folge durchlaufen werden, sondern können auch mehrmals, beispielsweise mindestens dreimal oder mindestens viermal hintereinander durchlaufen werden, um z.B. einen besonders intensiven und durchgängigen Dekoreffekt, insbesondere Metallic-Effekt, zu erzielen. Bei jedem Beschichtungsschritt kann eine unterschiedliche Dekorlackschicht im Sinne der vorliegenden Erfindung aufgetragen werden. In einer vorteilhaften Ausgestaltung wird in jedem Auftragungsschritt die gleiche Dekorlackschicht aufgetragen. In gleicher Weise kann bei jedem Behandlungsschritt im Sinne der vorliegenden Erfindung ein unterschiedliches wässriges System im Sinne der vorliegenden Erfindung eingesetzt werden. In einer vorteilhaften Ausgestaltung wird in jedem Behandlungsschritt das gleiche wässrige System eingesetzt.Of course, it is likewise possible that, after the application of a first decorative lacquer layer, this decorative lacquer layer is treated with a first aqueous system according to method step e) such that a first decorative lacquer layer containing metallic particles, containing or consisting essentially of aluminum, on the first decorative lacquer layer treated in this way Gold, silver, lead, vanadium, manganese, iron, cobalt, nickel, copper, palladium, platinum, titanium, zinc, magnesium or alloys of these metals or containing or consisting essentially of brass, bronze or stainless steel, and that second Decorative lacquer layer comprising a second aqueous system containing at least one acid, an oxide, double oxide, oxide hydrate, sulfide, halide, nitride, carbide, carbonitride, boride, silicide, oxyhalide and / or salt of a 4th or 5th group element of the Periodic table of the elements or mixtures thereof, is treated. In this case, the method steps d) and e) can not only be run twice in succession, but can also be repeated several times, for example at least three times or at least four times in succession be run through, for example, to achieve a particularly intense and consistent decor effect, especially metallic effect. In each coating step, a different decorative lacquer layer can be applied in the sense of the present invention. In an advantageous embodiment, the same decorative lacquer layer is applied in each application step. Similarly, in each treatment step in the context of the present invention, a different aqueous system in the context of the present invention can be used. In an advantageous embodiment, the same aqueous system is used in each treatment step.

Gemäß einer weiteren Ausgestaltung des erfindungsgemäßen Verfahrens ist vorgesehen, dass die im Verfahrensschritt d) aufzubringende Dekorlackschicht eine auszuhärtende bzw. auszutrocknende Dekorlackschicht darstellt und dass diese Dekorlackschicht vor deren vollständiger Aushärtung und/oder Trocknung mit dem wässrigen System gemäß Verfahrensschritt e) behandelt wird. Der Trocknungsschritt bei Dekorlackschichten ist auch als sogenannter Ablüftschritt bekannt.According to a further embodiment of the method according to the invention it is provided that the decorative lacquer layer to be applied in process step d) represents a decorative lacquer layer to be cured or dried out and that this decorative lacquer layer is treated with the aqueous system according to process step e) prior to its complete curing and / or drying. The drying step in decorative lacquer layers is also known as the so-called peeling step.

Im allgemeinen können für die Dekorlackschicht wasserverdünnbare Beschichtungszusammensetzungen verwendet werden. Diese Beschichtungszusammensetzungen enthalten geeignete Bindemittel, beispielsweise Polyester-, Poylacrylat-, Polyurethan -oder Aminoplastharze, z. B. in wasserverdünnbarer Form.In general, water-dilutable coating compositions can be used for the decorative lacquer layer. These coating compositions contain suitable binders, for example polyester, polyacrylate, polyurethane or aminoplast resins, e.g. B. in wasserverdünnbarer form.

Für die Beschichtungszusammensetzung der Dekorlackschicht kann auf Systeme zurückgegriffen werden, wie sie von gängigen, z. B. wässrigen, Dekorlacken bekannt sind. In einer Ausführungsform stellt die Beschichtungszusammensetzung für die Dekorlackschicht z.B. eine wässrige Polymerdispersion, enthaltend ein Acrylat-Copolymer und einen nicht assoziativ wirkenden Verdicker dar.Systems can be used for the coating composition of the decorative lacquer layer, as they are known from common, eg. As aqueous, decorative paints are known. In one embodiment, the coating composition for the decorative paint layer comprises e.g. an aqueous polymer dispersion comprising an acrylate copolymer and a non-associative thickener.

Zusätzlich zu den metallischen Partikeln können in den für die Dekorlackschicht verwendeten Beschichtungszusammensetzungen auch weitere Effektpigmente wie Perlglanzpigmente, LCP-Pigmente (liquid crystal polymer) oder OV-Pigmente (optical variable) verwendet werden. Übliche Perlglanzpigmente umfassen zum Beispiel metalloxidbeschichtete Metallpigmente, zum Beispiel titandioxidbeschichtetes, eisenoxidbeschichtetes oder mischoxidbeschichtetes Aluminium. Unter Perlglanzpigmente fallen ebenfalls beschichtete Glimmer. Bei OV-Pigmenten handelt es sich im allgemeinen um Pigmentplättchen mit einer speziellen mehrschichtigen Dünnschichtinterferenzstruktur, wobei die Schichten sich aus einer hochreflektierenden Metallschicht wie Aluminium oder Chrom, einer transparenten dielektrischen Schicht aus Titandioxid oder Siliciumdioxid und einer semitransparenten Metallschicht aus beispielsweise Nickel oder Aluminium zusammensetzen.In addition to the metallic particles, it is also possible to use further effect pigments, such as pearlescent pigments, LCP pigments (liquid crystal polymer) or OV pigments (optical variable), in the coating compositions used for the decorative lacquer layer. Common pearlescent pigments include, for example, metal oxide coated metal pigments, for example, titanium dioxide coated, iron oxide coated, or mixed oxide coated aluminum. Pearlescent pigments also include coated mica. OV pigments are generally pigment platelets with a special one multilayer thin-film interference structure, the layers being composed of a highly reflective metal layer such as aluminum or chromium, a transparent dielectric layer of titanium dioxide or silicon dioxide and a semitransparent metal layer of, for example, nickel or aluminum.

Des weiteren können in der Beschichtungszusammensetzung für die Dekorlackschicht auch Anteile an farbgebenden organischen und/oder anorganischen Pigmenten vorhanden sein.Furthermore, proportions of color-providing organic and / or inorganic pigments may also be present in the coating composition for the decorative lacquer layer.

Die für die Dekorlackschicht verwendeten Beschichtungszusammensetzungen enthalten in einer Ausführungsform Lösungsmittel in einer Menge von, bezogen auf die Beschichtungszusammensetzung, 20 bis 80, vorteilhafterweise 30 bis 70, insbesondere 40 bis 65 Gew.-% an Lösemitteln, z. B. Wasser.The coating compositions used for the decorative lacquer layer in one embodiment contain solvents in an amount of, based on the coating composition, 20 to 80, advantageously 30 to 70, in particular 40 to 65 wt .-% of solvents, for. B. water.

Selbstverständlich können die Beschichtungszusammensetzungen für die Dekorlackschicht herkömmliche lacktechnische Additive enthalten. Exemplarisch sei verwiesen auf rheologiebeeinflussende Mittel, Verdicker, Antiabsetzmittel, Verlaufsmittel, Lichtschutzmittel, Antischaummittel, Netzmittel oder Mischungen dieser Komponenten.Of course, the coating compositions for the decorative coating layer may contain conventional coating additives. By way of example, reference is made to rheology-influencing agents, thickeners, anti-settling agents, leveling agents, light stabilizers, antifoams, wetting agents or mixtures of these components.

Die Dekorlackschicht kann mit Hilfe bekannter Auftragsverfahren auf dem Substrat appliziert werden, beispielsweise mittels Sprühens, Walzens, Rakelns, Streichens, Roller Coatings, Flutens oder Tauchens. Für den Spritz- oder Sprühauftrag kann zum Beispiel auf bekannte Druckluft- oder Rotationszerstäubungsauftragsverfahren zurückgegriffen werden. In einer bevorzugten Ausgestaltung wird die Dekorlackschicht mittels Sprühens, insbesondere unter Anwendung von Druck, beispielsweise Druckluft, auf das Substrat aufgebracht. Bei dieser Art von Auftragung kommt es regelmäßig zu einem Konzentrationsgefälle an metallischen Partikeln innerhalb der Dekorlackschicht mit der Folge, dass die Konzentration an metallischen Partikeln in Richtung auf die Substratoberfläche abnimmt. Demgemäß liegt bei dieser Variante häufig der größte Teil der metallischen Partikel auf bzw. an sowie gegebenenfalls im oberflächennahen Bereich der Dekorlackschicht vor. Diese metallischen Partikel, insbesondere solche, die auf bzw. an der Oberfläche der Dekorlackschicht vorliegen, sind besonders geeignet für den Eintrag der vorangehend genannten Verbindungen der Elemente der 4. und 5. Gruppe des Periodensystems der Elemente durch Beaufschlagung mit dem beschriebenen wässrigen System im Sinne der vorliegenden Erfindung. Ohne an irgendeine Theorie gebunden zu sein, wird gegenwärtig angenommen, dass möglicherweise die vorangehend beschriebene Verteilung der metallischen Partikel innerhalb der Dekorlackschicht auf elektrostatische Reibungsphänomene zurückgehen könnte. Selbstverständlich wird der erfindungsgemäße Effekt z.B. auch dann erzielt, wenn die metallischen Partikel im Wesentlichen gleichförmig in der Dekorlackschicht verteilt vorliegen.The decorative lacquer layer can be applied to the substrate by means of known application methods, for example by means of spraying, rolling, knife coating, brushing, roller coating, flooding or dipping. For the spray or spray application can be used, for example, on known compressed air or Rotationszerstäubungsauftragsverfahren. In a preferred embodiment, the decorative coating layer is applied to the substrate by means of spraying, in particular using pressure, for example compressed air. In this type of application, a concentration gradient of metallic particles within the decorative lacquer layer regularly occurs, with the result that the concentration of metallic particles in the direction of the substrate surface decreases. Accordingly, in this variant, the majority of the metallic particles are often present on or on, and optionally in the near-surface region of the decorative lacquer layer. These metallic particles, in particular those which are present on or at the surface of the decorative lacquer layer, are particularly suitable for the introduction of the abovementioned compounds of the elements of groups 4 and 5 of the Periodic Table of the Elements by application of the described aqueous system in the sense of the present invention. Without being bound by any theory, it is presently believed that it may be that described above Distribution of metallic particles within the decorative coating layer could be due to electrostatic friction phenomena. Of course, the effect according to the invention is also achieved, for example, when the metallic particles are substantially uniformly distributed in the decorative lacquer layer.

Geeignete metallische Partikel für die Dekorlackschicht können z. B. nasschemisch oder mittels CVD- oder PVD-Verfahren hergestellt werden, beispielsweise durch Aufbringung auf natürlich oder künstlich hergestellte mikrometergroße Plättchen. Alternativ kann man dünne Metallschichten auf geeigneten Unterlagen aufbringen, die in nachfolgenden Schritten erst abgelöst und dann auf eine geeignete Größe zerkleinert werden. Dieses kann beispielsweise mit Hilfe von Ultraschall geschehen, wie in der US 5,135,812 beschrieben.Suitable metallic particles for the decorative lacquer layer may, for. As wet-chemically or by CVD or PVD processes are prepared, for example by application to naturally or artificially produced micrometer-sized platelets. Alternatively, it is possible to apply thin metal layers on suitable substrates, which are first removed in subsequent steps and then comminuted to a suitable size. This can be done for example by means of ultrasound, as in the US 5,135,812 described.

Besonders geeignete metallische Partikel weisen Formfaktoren, das heißt Verhältnisse von mittlerer Längsausdehnung zur mittleren Dicke, in einem Bereich von 10 bis 7.000, bevorzugt von 50 bis 10.000, und besonders bevorzugt von 70 bis 200 auf.Particularly suitable metallic particles have form factors, ie ratios of average longitudinal extent to average thickness, in a range from 10 to 7,000, preferably from 50 to 10,000, and particularly preferably from 70 to 200.

Bevorzugte mittlere Schichtdicken, der, insbesondere in Plättchenform vorliegenden, metallischen Partikel liegen in einem Bereich von 15 bis 1000 nm. Bevorzugt liegt der mittlere Durchmesser von, insbesondere von in Plättchenform vorliegenden, metallischen Partikeln im Bereich von 1 bis 500 µm, besonders bevorzugt im Bereich von 5 bis 100 µm. Als mittlerer Durchmesser wird hier der d50-Wert der Summendurchgangsverteilung der Größenverteilungskurve, wie sie üblicherweise mittels Laserbeugungsverfahren (Frauenhoferbeugung) mittels geeigneter Geräte (beispielsweise Cilas 1064) gemessen wird, zugrunde gelegt.Preferred average layer thicknesses of the metallic particles present, in particular in platelet form, are in a range of 15 to 1000 nm. The average diameter of, in particular of platelet-shaped, metallic particles is in the range from 1 to 500 .mu.m, more preferably in the range from 5 to 100 μm. As the average diameter is here the d 50 value of the cumulative distribution of the size distribution curve, as it is usually measured by laser diffraction method (Frauenhoferbeugung) by means of suitable devices (for example, Cilas 1064) is measured, based.

Die Dekorlackschicht verfügt in der Regel vorzugsweise über eine Schichtdicke nicht oberhalb von 150 µm, vorteilhafterweise nicht oberhalb 80 µm, sowie vorzugsweise im Bereich von 1 bis 40 µm, weiter bevorzugt im Bereich von 2 bis 35 µm und besonders bevorzugt im Bereich von 3 bis 30 µm. Selbstverständlich können auch Schichtdicken oberhalb von 150 µm zum Einsatz kommen, z.B. im Bereich von 300 bis 450 µm, beispielsweise etwa 400 µm. Es ist hierbei vorzugsweise sicherzustellen, dass die metallischen Partikel in der Dekorlackschicht bei der Behandlung mit dem wässrigen System noch stets mit diesem in Kontakt treten können, beispielsweise weil die metallischen Partikel an oder in der Oberfläche vorliegen und/oder weil das wässrige System bzw. dessen Verbindungen des zweiten Metalls in die Dekorlackschicht eindringen können, z.B. weil diese noch nicht vollständig ausgehärtet oder ausgetrocknet ist.As a rule, the decorative lacquer layer preferably has a layer thickness not above 150 μm, advantageously not above 80 μm, and preferably in the range from 1 to 40 μm, more preferably in the range from 2 to 35 μm and particularly preferably in the range from 3 to 30 microns. Of course, it is also possible to use layer thicknesses above 150 μm, for example in the range from 300 to 450 μm, for example about 400 μm. In this case, it is preferably to be ensured that the metallic particles in the decorative lacquer layer can still always come into contact with it during the treatment with the aqueous system, for example because the metallic particles are present on or in the surface and / or because the aqueous system or its Compounds of the second metal in the Decorative paint layer can penetrate, for example, because this is not fully cured or dried out.

Die Deckschicht verfügt in der Regel über eine Dicke im Bereich von 20 bis 30 µm.The cover layer usually has a thickness in the range of 20 to 30 microns.

Die nach dem erfindungsgemäßen Verfahren erhältlichen beschichteten Substrate können beispielsweise verwendet werden als Zubehörteil für den Automobilbau, Motorradbau, Fahrradbau oder Schiffbau, für Felgen, insbesondere Leichtmetallfelgen, Räder, insbesondere Leichtmetallräder oder als Bestandteil hiervon, für Sanitäreinrichtungsgegenstände, insbesondere als Armatur, oder als Bestandteil hiervon, für Karosserieinnen- oder Außenbauteile oder als Bestandteil hiervon, für Griffe oder Griffkomponenten, insbesondere Türgriffe oder als Bestandteil hiervon, für Profile oder Rahmen, insbesondere Fensterrahmen oder als Bestandteil hiervon, für Beschlagsysteme oder als Bestandteil hiervon, insbesondere Schilder und Türschilder, für Gehäuse oder als Verpackung oder als Bestandteil hiervon, für Innen- oder Außenbauteile von Schiffen oder als Bestandteil hiervon, für Schmuckgegenstände oder als Bestandteil hiervon, für Edelbauteile oder als Bestandteil hiervon, für Innen- oder Außenbauteile von Flugzeugen oder als Bestandteil hiervon, für Innen- oder Außenbauteile von Gebäuden oder als Bestandteil hiervon, für Heizkörper oder Rohre oder als Bestandteil hiervon, für Bauteile von Aufzügen oder als Bestandteil hiervon, für Bauteile von Elektronikkomponenten oder -Geräten oder als Bestandteil hiervon, oder als Bauteil von Kommunikationskomponenten oder -Geräten, insbesondere Handys, oder als Bestandteil hiervon.The coated substrates obtainable by the process according to the invention can be used, for example, as an accessory for the automotive industry, motorcycle construction, bicycle construction or shipbuilding, for rims, in particular light metal rims, wheels, in particular light metal wheels or as a component thereof, for sanitary appliances, in particular as a fitting, or as a component thereof for internal or external body components or as a component thereof, for handles or handle components, in particular door handles or as a component thereof, for profiles or frames, in particular window frames or as a component thereof, for fitting systems or as a component thereof, in particular signs and door plates, for housing or as a packaging or as a component thereof, for interior or exterior components of ships or as a component thereof, for or as a component of or for jewelery, for or as a component thereof, for interior or external components of aircraft or as a component thereof, for internal or external components of buildings or as a component thereof, for radiators or pipes or as a component thereof, for components of elevators or as a component thereof, for components of electronic components or devices or as a component thereof , or as a component of communication components or devices, in particular mobile phones, or as a component thereof.

Mit der vorliegenden Erfindung lassen sich überraschender Weise Substrate erhalten, die mit Metallpartikeln enthaltenden Dekorlackbeschichtungen versehen sind, und die sich durch eine sehr gute Haftung der Dekorschicht auf dem Substrat auszeichnen, und zwar selbst bei hohen Konzentrationen an Metallpartikeln in der verwendeten Beschichtungszusammensetzung. Die erhaltenen beschichteten Substrate zeichnen sich darüber hinaus durch hervorragende Korrosionseigenschaften und einen sehr guten und beständigen Glanzeffekt aus.With the present invention, surprisingly, substrates can be obtained which are provided with decorative coatings containing metal particles and which are distinguished by a very good adhesion of the decorative layer to the substrate, even at high concentrations of metal particles in the coating composition used. The resulting coated substrates are also characterized by excellent corrosion properties and a very good and consistent glossy effect.

Die in der vorstehenden Beschreibung, in den Ansprüchen sowie in den Zeichnungen offenbarten Merkmale der Erfindung können sowohl einzeln aus auch in jeder beliebigen Kombination für die Verwirklichung der Erfindung in ihren verschiedenen Ausführungsformen wesentlich sein.The features of the invention disclosed in the foregoing description, in the claims and in the drawings may be essential both individually and in any combination for the realization of the invention in its various embodiments.

Claims (17)

  1. A method for producing a coated substrate, comprising
    a) providing a substrate having at least one surface coatable at least in areas;
    d) applying at least in areas at least one decorative lacquer layer, particularly an effect lacquer layer or a metallic lacquer layer, including at least one binder and metallic particles including or substantially consisting of aluminum, gold, silver, lead, vanadium, manganese, iron, cobalt, nickel, copper, palladium, platinum, titanium, zinc, magnesium, or alloys of these metals or including or substantially consisting of brass, bronze or stainless steel, wherein the metallic particles are particularly plate-like metal particles;
    e) treating the decorative lacquer layer with an aqueous system including at least one acid, one oxide, double oxide, oxide hydrate, sulfide, halide, nitride, carbide, carbonitride, boride, silicide, oxyhalide and/or salt of an element of the 4th or 5th group of the periodic table of the elements or mixtures thereof.
  2. The method according to claim 1, characterized in that the substrate is formed from metals, noble metals or metal alloys or from glass, ceramics, composite fiber materials, carbon materials, plastic, wood or chipboard or comprises these materials; and that the metallic particles include aluminum, aluminum alloys, iron, iron alloys, gold, gold alloys, copper or copper alloys or consist of aluminum, aluminum alloys, iron, iron alloys, gold, gold alloys, copper or copper alloys; and/or
    that the aqueous system includes at least one acid, one oxide, double oxide, oxide hydrate, halide, oxyhalide or salt of an element of the 4th or 5th group of the periodic table of the elements, particularly titanium or zirconium, or mixtures thereof; and/or that the oxides are zirconium oxides, titanium oxides, or hafnium oxides, the oxyfluorides are zirconium oxyfluorides, titanium oxyfluorides, or hafnium oxyfluorides, the acids are fluorozirconic acids, fluorotitanic acids, or fluorohafnic acids and the salts are fluorozirconates, fluorotitanates, or fluorohafniates.
  3. The method according to any one of the preceding claims, characterized in that the decorative lacquer layer is treated with the aqueous system under pressure, particularly in the form of liquid jets.
  4. The method according to any one of the preceding claims, further comprising after process step a) and before process step d), the process step of
    b) applying at least one conversion coating to the substrate; and/or further comprising after process step a) and before process step d), the process step of
    c) applying at least one first and, where appropriate, at least one second priming coat to the substrate; and, where appropriate, further comprising after process step e), the process step of
    f) applying at least one, particularly transparent, top coat.
  5. The method according to any one of the preceding claims, characterized in that after process step d) and/or after process step e), the coated surface of the substrate is subjected to a rinsing step with, particularly deionized, water.
  6. The method according to any one of the preceding claims, characterized in that after the first application of a first decorative lacquer layer in accordance with process step d), this decorative lacquer layer is treated with a first aqueous system in accordance with process step e); that a second decorative lacquer layer including metal particles including or substantially consisting of aluminum, gold, silver, lead, vanadium, manganese, iron, cobalt, nickel, copper, palladium, platinum, titanium, zinc, magnesium, or alloys of these metals or including or substantially consisting of brass, bronze or stainless steel is applied to the first decorative lacquer layer treated in this way; and that this second decorative lacquer layer is treated with an aqueous system including at least one acid, one oxide, double oxide, oxide hydrate, sulfide, halide, nitride, carbide, carbonitride, boride, silicide, oxyhalide and/or salt of an element of the 4th or 5th group of the periodic table of the elements or mixtures thereof.
  7. The method according to any one of the preceding claims, characterized in that the decorative lacquer layer to be applied in process step d) is a decorative lacquer layer to be hardened and/or dried; and that this decorative lacquer layer is treated with the aqueous system in accordance with process step e) before its complete hardening and/or drying.
  8. The method according to any one of the preceding claims, characterized in that, in process step d), the decorative lacquer layer is applied with an average thickness not exceeding 150 µm, preferably not exceeding 80 µm.
  9. The method according to any one of the preceding claims, characterized in that the decorative lacquer layer is applied by means of spraying, particularly by applying pressure, preferably air pressure.
  10. The method according to any one of the preceding claims, characterized in that the decorative lacquer layer is applied in such a way that at least part of the metallic particles are at the surface of the decorative lacquer layer.
  11. A coated substrate obtainable according to a method in accordance with any one of the preceding claims.
  12. A coated substrate, comprising a substrate having a coatable surface and at least one decorative lacquer layer on the coatable surface, including at least one binder and metallic particles including or substantially consisting of aluminum, gold, silver, lead, vanadium, manganese, cobalt, nickel, copper, palladium, platinum, titanium, zinc, magnesium, or alloys of these metals or including or substantially consisting of brass, bronze or stainless steel, wherein these metallic particles include an oxide, double oxide, oxide hydrate, sulfide, halide, nitride, carbide, carbonitride, boride, silicide, oxyhalide and/or salt of an element of the 4th or 5th group of the periodic table of the elements.
  13. A Substrate according to claim 11 or 12, characterized in that the particles substantially consist of aluminum or include aluminum; and/or that the oxides are zirconium oxides, titanium oxides, or hafnium oxides and the oxyfluorides are zirconium oxyfluorides, titanium oxyfluorides, or hafnium oxyfluorides; and that the substrate is a metal substrate or a plastic substrate; and/or that zirconium, titanium and/or hafnium are present in the metallic particles in oxidically bound form.
  14. The substrate according to any one of claims 11 to 13, further comprising at least one, particularly transparent, top coat which follows the decorative lacquer layer, is particularly present thereon.
  15. The substrate according to any one of claims 11 to 14, characterized in that the decorative lacquer layer has an average thickness not exceeding 150 µm, preferably not exceeding 80 µm.
  16. Use of the substrate according to any one of claims 11 to 15 as an accessory for automobile construction, motorcycle construction, bicycle construction, or shipbuilding; for rims, particularly light metal rims, wheels, particularly light metal wheels, or as part thereof; for sanitary fixtures, particularly as fitting, or as part thereof; for internal or external components of car bodies or as part thereof; for handles or handle components, particularly door handles, or as part thereof; for profiles or frames, particularly window frames, or as part thereof; for hardware systems or as part thereof, particularly plates or door plates; for housings or as packaging or as part thereof; for internal or external components of ships or as part thereof; for decorative objects or as part thereof; for precious components or as part thereof; for internal or external components of aircrafts or as part thereof; for internal or external components of buildings or as part thereof; for heaters or pipes or as part thereof; for components of lifts or as part thereof; for components of electronic appliances or devices or as part thereof, or as component of communication appliances or devices, particularly mobile phones, or as part thereof.
  17. An accessory for automobile construction, motorcycle construction, bicycle construction, or shipbuilding, rims, particularly light metal rims, wheels, particularly light metal wheels, or any part thereof, bumpers, sanitary fixtures, particularly fitting, or any part thereof, for internal or external components of car bodies or any part thereof, for handles or handle components, particularly door handles, or any part thereof, profiles or frames, particularly window frames, or any part thereof, hardware systems or any part thereof, particularly plates or door plates, for housings or as packaging or any part thereof, internal or external components of ships or any part thereof, decorative objects or any part thereof, precious components or any part thereof, internal or external components of aircrafts or any part thereof, internal or external components of buildings or any part thereof, radiators or pipes or any part thereof, components of lifts or any part thereof, components of electronic appliances or devices or any part thereof, or any component of communication appliances or devices, particularly mobile phones, or any part thereof, each comprising at least one substrate in accordance with any one of claims 11 to 15.
EP09749640A 2008-05-23 2009-05-22 Coated substrate and method for its production Not-in-force EP2296829B1 (en)

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PCT/EP2009/003626 WO2009141150A1 (en) 2008-05-23 2009-05-22 Coated substrates and method for the production thereof
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