DE102007046925A1 - Method for producing a metallic and/or non-metallic substrate, which is protected against corrosion in regions and/or is shiny, comprises provisioning a substrate or a carrier layer having a surface, which is coated in regions - Google Patents

Abstract

The method for producing a metallic and/or non-metallic substrate, which is protected against corrosion in regions and/or is shiny, comprises provisioning a substrate or a carrier layer having a surface, which is coated in regions, applying a first priming layer and if necessary a second priming layer on the metallic or plastic substrate and/or cutting and/or polishing the metallic substrate surface, and applying a metallic protective layer or a metal layer comprising a first metal, a first noble metal or a first metal alloy on the coated substrate surface. The method for producing a metallic and/or non-metallic substrate, which is protected against corrosion in regions and/or is shiny, comprises provisioning a substrate or a carrier layer having a surface, which is coated in regions, applying a first priming layer and if necessary a second priming layer on the metallic or plastic substrate and/or cutting and/or polishing the metallic substrate surface, applying a metallic protective layer or a metal layer comprising a first metal, a first noble metal or a first metal alloy on the coated substrate surface by vapor-depositing and/or coating of a coating material and/or a vaporizing material in vacuum, entering the components of acid, oxide, double oxide, oxide-hydrate, sulfide, halide, nitride, carbide, carbonitride, boride, silicide, oxyhalide or salt of the second metal in the metal layer by treating the metal layer with the aqueous system containing the components, and removing and insulating the formed metal layer from the carrier layer. The vapor-depositing and/or coating process is carried out by physical vapor deposition coating, evaporating by an electron beam evaporator and a resistance evaporator, induction evaporation, an arc-evaporation and/or cathodic sputtering coating in a high vacuum. The carrier layer is a plastic carrier foil and has a replacement foil at its coating side, which is coated with the metal layer. The aqueous system has a pH value of 1.5-6.5. The thickness of the metallic protective layer is 30-1 mu m. The coated substrate surface is subjected to a rinsing step with demineralized water after applying the metallic protective layer. The first metal, the first noble metal or the first metal alloy and/or the metallic layer impact under pressure in the form of fluid jets. A transparent coating varnish layer and/or a glaze layer are applied after the metallic protective layer metallic layer applying step or entering step. An independent claim is included for a substrate, which is protected against corrosion in regions and/or is shiny.

Description

The The invention relates to a process for the production of corrosion-protected and in particular high-gloss non-metallic and metallic coated moldings or substrates and Such moldings and their use.

The optical refinement of any substrates in which these substrates a metallic impression is mediated, has long been known. Here are different layers in a variety of order applied to the substrate. Essential requirements for coated Substrates are excellent corrosion resistance as well as an appealing optic which covers the coated substrates, for example as fully metallic or chrome plated substrates. Of particular importance are coated substrates in the automotive industry, for example, in the manufacture of wheels or rims, in particular light-alloy wheels or alloy wheels, of which requires a shiny chrome appearance becomes.

Out The prior art, for example, a method is known, be chromium plating with the alloy wheels. In this The process is only a few thousandths of a millimeter thick chromium layer applied to a light metal rim. Not all To reflect unevenness of the substrate surface must therefore the rims ground before the galvanic coating, highly polished and be prepared thoroughly. Otherwise, all are Pores, scratches and bumps clearly on the coated rim to recognize. Already grinding, mirror polishing and preparing of the substrate are independent of the geometry of the same very difficult and labor intensive. In addition, the galvanic process as such labor-safety technically complex and may be inappropriate Handling endangering the environment. As soon as the galvanic applied chrome surface is injured, it comes to known contact corrosion. Under the influence of z. B. rainwater or snowmelt water, the normally dissolved road salt contains, creates an electrical voltage series between the nobler part (in this case chromium as cover layer) and the less noble metal of the substrate (for example, an aluminum or magnesium alloy). This dissolves the less noble Metal on. Consequently, z. B. a rim in the most unfavorable Case significantly damaged in intercrystalline corrosion which, in turn, critically affect both the visual appearance as well as the strength values of the rim under dynamic load during use. At a disadvantage the galvanic chrome plating is further that the galvanically applied Chrome layer often has a different coefficient of expansion has as the underlying substrate material. This allows Tensions occur that lead to cracks or even flaking.

moreover need in the disposal of the case of the galvanic coating substances used have taken special safety precautions in order to exclude the endangerment of humans and the environment.

Coating processes are also known from the prior art in which chromium is deposited on a rim by sputtering in a high vacuum. The process is operated under high voltage. However, a light metal rim coated in this way by the sputtering process usually does not look like galvanically coated with chromium, ie shiny metallic, but rather like black chrome, and is therefore equipped with a darker surface which is in no way equivalent to a galvanically coated chrome surface. So-called black chrome surfaces are z. B. unacceptable for all shiny sanitary ware. Further, a light metal rim manufactured by a sputter chromium plating method does not meet the test requirements prescribed by the automotive industry as a minimum standard, such as the cross hatch test DIN EN ISO 2409 , the salt spray test (copper chloride / acetic acid) after DIN 50021-CASS (240h) , Condensation constant climate testing after DIN 50017 KK and the chemical resistance test according to VDA 621-412.

From the DE 102 10 269 A1 discloses a method for adhering a substrate to give it a metallic appearance by first applying a primer layer to the substrate and drying it and then treating the primer layer with an inorganic primer. Subsequently, a silver layer is applied. Finally, the applied layers are coated with a protective varnish. In substrates coated by this method, oxidation of the silver layer by the incompletely sealing protective lacquer takes place relatively quickly. This leads to delamination of the silver layer from the substrate and finally to a yellowish discoloration.

In order to achieve a sufficient corrosion protection of metal parts, chromate-containing coatings, also called conversion layers, are often applied. Due to the light yellow iridescent effect of such coatings one speaks also of yellow chroma animals. Unlike anodic protective coatings, chromate conversion coatings often fail to provide protection once the surface is scratched. Chromated surfaces can be obtained by dipping or spraying / spraying. For the application of chromate protective layers on the US 2,825,697 and the US 2,928,763 directed. The application of a conventional chromate conversion layer is also the WO 2004/014646 A1 refer to.

A modified chromate coating comes from the WO 01/51681 A2 according to which a suitable passivating solution has to contain chromium (III) chloride and sodium nitrate.

In the DE 197 02 566 C2 Finally, the process for the gloss coating of vehicle parts by means of a chromate layer is finally modified in such a way that a high-gloss layer of a metal is applied by means of a magnetron in vacuum on a powder coating layer present on the chromate layer. As a result, color effects can be set purposefully without the need for adding external pigments.

Furthermore, from the WO 01/51681 A2 and the DE 602 00 458 T2 It is known that metal coatings can not only be rendered corrosion resistant by treatment with a passivation solution containing chromate, but also that sparingly soluble metal phosphate coatings, for example based on zinc or iron phosphate, can be used for this purpose.

For chromium-free surface treatment can according to the DE 103 32 744 A1 also resort to an aqueous mixture containing an at least partially hydrolyzed fluorine-free silane and an at least partially hydrolyzed fluorine-containing silane.

After DE 602 00 458 T2 it is possible to obtain adequate corrosion resistance by containing a metallic zinc powder and at least one metal salt rust inhibitor, the corrosion inhibitor coating, which is based on magnesium, aluminum, calcium and barium and has an average diameter size of not more than 1 μm. The metal of the metal salt has to be more basic than zinc.

A good corrosion protection arises after the DE 100 49 005 A1 when the process step of treatment with a passivating agent coincides with that of applying a lubricant. The prerequisite for this is that the agent containing the lubricant does not consist essentially of titanium or / and zirconium and also fluorine and a polymer. This new development makes use of long-chain molecular residues, which, as of surface-active substances, for. As surfactants, known, tend to self-assembly. Accordingly, this technology is also known under SAM coating (Self Assembling Molecules).

A chromium-free surface coating of metals that can be applied at high coating speeds is based on the DE 101 49 148 A1 on an aqueous composition containing an organic film former containing at least one water-soluble or water-dispersed polymer having an acid value in the range of 5 to 200, at least one inorganic compound in particle form having a mean particle diameter in the range of 0.005 to 0.3 μm and at least a lubricant, wherein the applied dried film has a layer thickness in the range of 0.01 to 10 microns, a pendulum hardness of 50 to 180 s and such flexibility that when bent over a conical mandrel after DIN ISO 6860 no cracks longer than 2 mm. Suitable organic film formers are synthetic resins based on acrylates, butadienes, ethylene, polyesters, polyurethanes, silicone polyesters, epoxides, phenol, styrene and urea-formaldehyde.

The US 6,896,920 B2 discloses a multilayer gloss coating in which a polymer layer is first to be applied to a metallic substrate surface. Subsequently, this polymer coating is to be provided with a metal layer. On this metal layer, a corrosion-inhibiting inorganic layer is then applied. The final uppermost layer of this multilayer system is a transparent protective lacquer layer. Although identified as being anti-corrosive, in multilayer substrates according to U.S. Pat US 6,896,920 B2 In the CASS salt spray test, a corrosion-induced change in the surface was already detected after 168 hours. However, the automotive industry regularly demands proof of an unchanged surface even after 240 hours.

In the DE 0 870 020 A1 describes a process for the treatment of aluminum surfaces in two successive stages, with which an improved corrosion protection and an improved adhesion for paints, varnishes and the like should be adjusted. In this method, first in a first step, the substrate surface with an aqueous acidic solution containing effective amounts of a) dissolved metals at least one of the elements hafnium, zirconium or titanium, b) phosphate ions, c) fluoride ions, d) a soluble tannin compound and e ) a complex compound which may be, for example, ethylenediaminetetraacetic acid, alkylgluconates or alkylthartrates. In a second, separate process stage, the substrate is with an effective To treat amount of derivatives of specific Polyalkenylphenolpolymeren.

The US 2004/0020565 A1 It is also an object to provide metal substrates with improved corrosion protection and improved adhesion to paints or other coatings, without the need for a chromating step. For this purpose, the formation of a conversion or passivation layer on the metal substrate by treatment with an aqueous system containing in addition to a group IV B fluoric acid (4th group of the Periodic Table of the Elements) also a polyamidoamine / epihalohydrin resin or a cationic polyamine / epihalohydrin Resin, proposed.

Of the EP 1 455 001 A1 For the purpose of corrosion protection of metal substrates, it is appropriate to be able to form a continuous oxide and / or hydroxide layer as rapidly as possible on their surfaces. For this purpose, the metal substrate is immersed in an aqueous solution containing metal ions and fluoride ions, wherein the fluoride ion concentration has to be four times as high as the metal ion concentration.

Finally, the expert takes the US 5,073,403 a method of producing aluminum coated steel cans. According to this method, a chromium layer is first applied to the steel layer, which is then provided with an aluminum layer. This multilayer system can additionally be treated with a solution containing phosphoric acid and chromic acid.

Of the The present invention was based on the object, a method for the production of corrosion-protected and in particular high-gloss substrates as well as by this method Available corrosion protected substrates available to overcome the disadvantages of the prior art. In particular, the invention was the object of a method to be made available with the corrosion-protected Substrates become accessible, even with mechanical Stress or damage over a long period of time Extremely resistant to corrosion and a very appealing Show or retain optics, as is conventional if necessary, obtained by means of galvanic chrome plating. After all The present invention was based on the object, a treatment method for metallic and non-metallic shaped bodies or substrates to make accessible, the apparatus little elaborate and safe even for semi-skilled workers to handle and beyond the user few or no restrictions on the disposal of treatment materials imposed.

• a) Zurverfügungstellung eines Substrats mit mindestens einer zumindest bereichsweise beschichtbaren Oberfläche,
• b) Aufbringen mindestens einer metallischen Schutzschicht auf die beschichtbare Oberfläche des Substrats mittels Aufdampfens bzw. Auftragens eines Beschichtungs- bzw. Aufdampfmaterials, enthaltend i) ein erstes Metall, ein erstes Edelmetall oder eine erste Metalllegierung und ii) mindestens eine Säure, ein Oxid, Doppeloxid, Oxyd-Hydrat, Sulfid, Halogenid, Nitrid, Carbid, Carbonitrid, Borid, Silicid, Oxyhalogenid und/oder Salz eines zweiten Metalls eines Elements der 4. Gruppe und/oder der 5. Gruppe des Periodensystems der Elemente oder Mischungen hiervon.

This object is achieved according to the invention by a method for the production of an at least partially corrosion-protected and / or shiny metallic and / or non-metallic substrate

• a) providing a substrate having at least one surface which can be coated at least in regions,
• b) applying at least one metallic protective layer to the coatable surface of the substrate by vapor deposition or deposition of a coating or vapor deposition material comprising i) a first metal, a first noble metal or a first metal alloy and ii) at least one acid, an oxide, double oxide , Oxide hydrate, sulfide, halide, nitride, carbide, carbonitride, boride, silicide, oxyhalide and / or salt of a second metal of an element of the 4th group and / or the 5th group of the Periodic Table of the Elements or mixtures thereof.

at the vapor-deposition or sputtering material is accessed in the case of the invention Process on substances, in addition to the first metal, the first noble metal or the first metal alloy at least one contain said compounds of the second metal. During vapor deposition Sputtering then gives directly the metallic Protective layer in which said compounds of the second metal registered. Be particularly preferred is the connection of the second metal substantially uniformly distributed in the first metal, precious metal or metal alloy in front. In a further embodiment, at least one of said compounds of the second metal substantially, in particular uniform, over the entire thickness the metallic protective layer distributed. The metallic protective layer Accordingly, it can also be used as an intimate mixture or as a metallic composite layer in which in the first Metal, first precious metal or the first metal alloy the compound embedded in the second metal is understood.

With the method according to the invention, a substrate with a metallic protective layer is obtained, which as such is itself highly protected against corrosion and, moreover, by application to a substrate also protects this substrate, insofar as it is a metallic substrate, from corrosion. While in non-metallic substrates, the property of corrosion protection thus refers to the metallic protective layer, metallic substrates not only a self-corrosion protected metallic protective layer is obtained, but this protective layer provides the metallic substrate with a very effective corrosion protection. At the same time, this metallic protective layer is usually high-gloss, so that high-gloss, very durable substrate surfaces accessible become.

A Further development of the method according to the invention is characterized by the fact that the coating or vapor deposition material gets by getting the first metal, the first precious metal or the first metal alloy with an 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 group element and / or the 5th group of the Periodic Table of the Elements or mixtures thereof treated.

Especially preference is given here to the elements of the fourth group of the periodic table, in particular zirconium, titanium and hafnium, more preferably Zirconium, used. Of course can also be any mixtures of compounds of a second metal, for example one or more oxides, double oxides, Oxide hydrates and / or oxyhalides, in particular oxyfluorides, side by side in the metal layer to form the metallic protective layer available. Furthermore, any mixtures of Connec tions of several second metals, z. Zirconia and titania, present side by side in the metallic protective layer. Accordingly come in a preferred embodiment of the invention Process as acid, oxide, double oxide, oxide hydrate, sulfide, Halide, nitride, carbide, carbonitride, boride, silicide, oxyhalide or salt of a second metal an acid, an oxide, double oxide, oxide hydrate, Sulfide, halide, nitride, carbide, carbonitride, boride, silicide, Oxyhalide, especially oxyfluoride, or a salt of titanium, Zirconium and / or hafnium are used. Particularly advantageous Results regarding corrosion protection and possibly also Shininess occurs when the oxides are zirconium oxides, titanium oxides or hafnium oxides, the oxyfluorides zirconium oxyfluorides, titanium oxyfluorides or hafnium oxyfluorides, the acids fluoric acid, Fluorotitanic acid or fluorophosphonic acid and the Salts fluorozirconate, fluorotitanates or Fluorhafniate represent.

• i) Zurverfügungstellung einer Trägerschicht,
• ii) Aufbringen mindestens einer Metallschicht aus dem ersten Metall, dem ersten Edelmetall oder der ersten Metalllegierung mittels Aufdampfens bzw. Auftragens dieses ersten Metalls, dieses ersten Edelmetalls oder dieser ersten Metalllegierung, insbesondere im Vakuum, auf einer beschichtbaren Oberfläche der Trägerschicht, und
• iii) Eintragen mindestens einer Säure, eines Oxids, Doppeloxids, Oxid-Hydrats, Sulfids, Halogenids, Nitrids, Carbids, Carbonitrids, Borids, Silicids, Oxyhalogenids und/oder Salzes des zweiten Metalls in die Metallschicht gemäß Schritt ii) durch Behandeln der Metallschicht mit einem wässrigen System, enthaltend mindestens eine Säure, ein Oxid, Doppeloxid, Oxid-Hydrat, Sulfid, Halogenid, Nitrid, Carbid, Carbonitrid, Borid, Silicid, Oxyhalogenid und/oder Salz des zweiten Metalls, wobei das zweite Metall ein Element der 4. Gruppe und/oder der 5. Gruppe des Periodensystems der Elemente oder Mischungen hiervon darstellt, und
• iv) Ablösen und Isolieren der gebildeten Metallschicht von der Trägerschicht.

In a further embodiment of the process according to the invention, it is provided that a coating or vapor deposition material is used which is obtained via the following process steps:

• i) provision of a carrier layer,
• ii) applying at least one metal layer of the first metal, the first noble metal or the first metal alloy by means of vapor deposition or deposition of this first metal, this first noble metal or this first metal alloy, especially in vacuo, on a coatable surface of the carrier layer, and
• iii) introducing 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 into the metal layer according to step ii) by treating the metal layer with an 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 the second metal, the second metal being an element of the 4. Group and / or the 5th group of the Periodic Table of the Elements or mixtures thereof, and
• iv) peeling and insulating the formed metal layer from the carrier layer.

The can be obtained in this way very thin metal films for example rolled up or slightly crumpled up Form be used for the vapor deposition. Also is it readily possible the detached thin ones Transfer metal films or metal film residues into an evaporation boat. Of course, those of the carrier layer detached, treated metal films also in compressed or more compressed form for the vapor deposition, for example in a helix or a boat in the invention Procedures are used.

The Evaporation or application in step b) or step ii) is done with the skilled person known vapor deposition techniques, for. B. by means of physical Vapor deposition (PVD) coating, vapor deposition by means of an electron beam evaporator, Vapor deposition by means of a resistance evaporator, induction evaporation, ARC evaporation and / or cathode sputtering (sputter coating), each preferably in a high vacuum.

• c) Eintragen mindestens einer Säure, eines Oxids, Doppeloxids, Oxyd-Hydrats, Sulfids, Halogenids, Nitrids, Carbids, Carbonitrids, Borids, Silicids, Oxyhalogenids und/oder eines Salz des zweiten Metalls in die Metallschicht gemäß Schritt b) durch Behandeln der Metallschicht mit einem wässrigen System, enthaltend mindestens eine Säure, ein Oxid, Doppeloxid, Oxyd-Hydrat, Sulfid, Halogenid, Nitrid, Carbid, Carbonitrid, Borid, Silicid, Oxyhalogenid und/oder Salz eines Elements der 4. Gruppe und/oder der 5. Gruppe des Periodensystems der Elemente oder Mischungen hiervon.

According to a particularly preferred embodiment, the process according to the invention further comprises after process step b) as a further step:

• c) introducing at least one acid, an oxide, double oxide, oxide hydrate, sulfide, halide, nitride, carbide, carbonitride, boride, silicide, oxyhalide and / or a salt of the second metal into the metal layer according to step b) by treating the metal layer with an 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 group 4 element and / or 5. Group of the Periodic Table of the Elements or mixtures thereof.

Obviously, the method according to the invention is technically far removed from a conventional galvanic chrome plating, however, with regard to the gloss effect, gloss retention and cor resistance to at least equal results.

suitable Substrates can be both metallic and non-metallic Be nature. As suitable non-metallic substrates z. B. containing or from wood, chipboard, glass, carbon materials, Ceramic or plastic into consideration. Particularly suitable plastics make PVC, polyolefins, especially polypropylene, polyamides and Polyoxyal kylenes, z. B. POM, in suitable substrates In addition to metallic components or sections also non-metallic Components or sections are available.

in principle are suitable as metallic substrates molding of all Metals, metal alloys and precious metals. As suitable substrates are exemplary of such aluminum, iron, steel, steel, stainless steel, Copper, brass, magnesium, iridium, gold, silver, palladium, platinum, Ruthenium, molybdenum, nickel, bronze, titanium, zinc, lead, Tungsten or manganese and their alloys called. preferred Include metal substrates or metal substrate surfaces or in particular consist of aluminum or aluminum alloys, Magnesium or magnesium alloys or titanium or titanium alloys. In one embodiment, this is high-purity aluminum, Magnesium or titanium, in particular with an aluminum, magnesium or titanium content of at least 90 wt .-%, in particular at least 99% by weight, based on the total weight of the metallic protective layer, used. Of course, in one Another embodiment also less pure metallic Substrate materials, for example, less pure aluminum, magnesium or titanium. Particularly preferred is for the metallic substrates on aluminum and aluminum alloys resorted.

According to one Further development includes the invention Method in a preferred embodiment, in particular for metallic substrates, between steps a) and b) the step a '): applying at least a first and, where appropriate, one second primer layer on the, in particular metallic or Plastic, substrate and / or grinding and / or polishing of, in particular metallic, substrate surface.

in this connection It is often beneficial that the first and / or second Primer layer after application in at least one subsequent Heat treatment step cured and / or baked become.

alternative for applying a first and optionally second primer layer or in addition to the application of a primer layer may be an upstream mechanical smoothing of the metal substrate surface, for example by means of grinding and / or polishing or finishing, be provided. Polished or polished metal surface often already have such a surface finish, that by applying a metallic protective or composite layer according to step b) of the method according to the invention a very corrosion-protected substrate is obtained.

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 commercially available for. B. known under the brand 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. Accordingly, the base layer may also be a topcoat or clearcoat. Depending on the finish (eg porous or rough) one or more primer layers may be applied to smooth the surface. In particular, with the first primer layer, as it can be used in particular in the present case on metal substrate surfaces, an advantageous flattening of the surface is achieved in general. 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.

According to the invention may also be provided, a conventional conversion layer, for. B. as in the US 2,825,697 or the US 2,928,763 described to apply to the substrate. Alternatively or additionally, according to another embodiment, the coatable surface of the substrate with an aqueous system containing at least one acid, an oxide, a double oxide, a Oxide hydrate, a sulfite, a halide, nitride, carbide, carbonitride, boride, silicide, an oxyhalide and / or a salt of a second metal as described above.

If the substrate is a metal substrate, it has proven advantageous on a regular basis, in particular if this metal substrate is taken directly from the respective production process, to clean the surface of the substrate in a suitable manner. For example, in a first preparatory step, the metal substrate surface can be degreased with alkaline or acidic reagents. Such degreasing agents are offered, among other things, by Henkel KGaA under the trade name Riduline ^®. So that no degreasing reagents remain on the surface, which could possibly impair the subsequent processing steps, a rinsing step with water follows regularly. Commercial degreasing steps are also known under the terms Abkoch- or Beizentfetten. Alternatively, a metal surface may be anodically degreased in an electrolytic degreasing bath.

moreover it has in some cases as appropriate proved the surface of the metal substrate, in particular the degreased metal substrate surface, at least one To undergo Dekapierschritt. For the decoration of the Metal substrate surface is set z. As an acid rinse one. A suitable Dekapierlösung accordingly z. B. diluted hydrochloric acid (1:10 vol / vol) is. As a result As a rule, one obtains a substantially oxide-free one Metal surface.

As well Like the degreasing step, the picking step also becomes general completed by a rinse step. Here it is proved to be very effective, at least towards the end of the wash cycle, preferably throughout the rinse, demineralised water to use.

In a preferred embodiment, the metallic Protective or composite layer according to step b) of the inventive method degreased on a and / or decanted metal substrate surface. According to another embodiment may also be the first and optionally the second primer layer on a degreasing and / or decanted metal substrate surface be applied.

Becomes the metal substrate surface is polished and / or ground or sliding ground, often the degreasing and / or Dekapierschritt omitted. Usually, this is Type of surface treatment sufficient material of this surface removed, which then also on the surface overlying or adherent contaminants or other components to be removed. If the surface is polished or ground, can also frequently also on the application of a first and if necessary second primer are dispensed with. With the polishing or Grinding is usually already such a flat or smooth surface get that sapping by applying a Primer is no longer required. At best, if that Metal substrate has numerous angles and corners that are not It is easy to polish or grind sufficiently be commendable, a first and possibly also to follow a second priming step.

Glass- and ceramic substrates are usually already so smooth per se that it is a polishing step or the application of additional Primer layers not needed. This also applies in general on plastic substrates too. Should plastic substrates with a particularly smooth surface, especially with high reliability, are obtained, it is usually carried on at least one primer layer. Suitable primer layers for plastic substrates put z. As clearcoats or UV coatings. Wood substrates, partly also ground and / or polished wood substrates, require however, often at least one primer layer before the metallic protective layer or the metal layer is applied can be.

According to one further optional embodiment of the invention is provided, that before step b) at least one adhesion promoter for the metallic protective layer on the surface of the substrate, the first primer layer and / or the second primer layer applied or generated on this surface. One suitable adhesion promoter may, for. B. by at least one plasma pretreatment, preferably by means of at least one oxygen plasma and / or at least one polymer plasma, in particular comprising hexa methyldisiloxane, be generated or applied. It can also be provided that as adhesion promoter, at least one inorganic or organometallic adhesion promoter is applied. In this case, preference is given to a tin (II) salt in acidic solution or at least one arm-containing silane in alkaline Resorted to.

Plastic moldings that can be treated by the method according to the invention, z. B. be made of ABS, SAN, ASA, PPE, ABS / PPE, ASA / PPE, SAN / PPE, PS, PVC, PC, ABS / PC, PP, PE, EPDM, polyacrylates, polyamides, POM or Teflon. If the application of a primer layer is required, these primer materials are preferably applied by wet coating. For highly heat-resistant plastics, the powder coating process also occurs in operation.

In front the application of the metallic protective or composite layer according to step b) the substrate surface is preferably dried, to be free of water residues.

advantageously, be after the process step b) the resulting surfaces rinsed with water. Preference is at least towards the end this rinsing step, preferably during the entire rinsing step, demineralised water (also as deionised water known) used.

The Thickness of the process step b) of the invention Method to be applied to the substrate metallic protective or composite layer or is preferably in the range of 20 nm to about 10 microns, more preferably in the range of 30 nm to 5 microns and in particular in the range of 50 nm to 1 micron. Very satisfactory results, for example, with layer thicknesses achieved in the range of 50 nm to 120 nm. The invention Results are already regularly with average Layer thicknesses less than 100 nm.

According to the invention the first metal for the metallic protective or composite layer according to step b), in particular aluminum, gold, Brass, bronze, silver, lead, vanadium, manganese, iron, cobalt, Nickel, copper, palladium, platinum, chromium, magnesium, titanium, zinc, Stainless steel or alloys of these metals. A particularly suitable protective / composite layer includes aluminum or an aluminum alloy.

Especially it is preferred that the purity of the first metal, preferably of aluminum, at least 80% by weight, preferably more than 90% by weight, most preferably at least 99% by weight.

For the application of the metallic protective layer according to step b) can be used on known Aufdamf- and sputtering process become. These are z. B. the method of physical Vapor Deposition (PVD) coating, the vapor deposition by means of a Electron beam evaporator, the vapor deposition by means of a resistance evaporator, Induction evaporation, ARC evaporation and sputtering, each preferably in a high vacuum. The metallic protective or Kompsitschicht can for example on the substrate or on its coatable surface, the first primer layer, applied to the second primer layer and / or the adhesion promoter become. Preference is given to the physical vapor deposition coating method (PVD) and sputtering used. This comes resistance-heated Metallwendel or Metallschiffchenverdampfer used, wherein Tungsten coils of various shapes are preferred. In the PVD process In general, an evaporator is equipped with coils, which are clamped on insulated evaporator rails can.

One Another preferred method for depositing the metal protective layer on the substrate is sputtering (sputtering). there a cathode is placed in an evacuated container, which is connected to the negative pole of a power supply. The Coating material that is atomized becomes immediate mounted in front of the cathode and become the substrates to be coated opposite the coating material to be atomized arranged. Furthermore, argon can be used as process gas through the container which finally has an anode, which is connected to the positive pole of a power supply. After this the container has been pre-evacuated become cathode and Anode connected to the power supply. Through the targeted and controlled intake of argon becomes the mean free path the charge carrier significantly lowered. In the electric field Argon atoms are ionized between the cathode and the anode. The positive charged particles become negatively charged with high energy Accelerated cathode. On impact and by particle collisions in the coating material, this is converted into the vapor phase, accelerated and condensed with high energy into free space then on the substrates to be coated.

Further usable in the method according to the invention Vapor deposition method using an electrode beam evaporation, Resistance evaporation, induction evaporation and / or evaporation using a thermal, non-stationary arc (ARC evaporation).

Also can be provided in the inventive method be that after step b) at least one heat treatment step is carried out.

The Coating or vapor deposition material is obtained, for example through bearings of the first metal, the first precious metal or the first metal alloy, for example in the form of films, plates, Tapes, wires or rods, in particular films, in the 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 an element the 4th or 5th group of the Periodic Table of the Elements. According to one Design uses deionized water for this aqueous System.

In each heating coil preferably becomes an exact predetermined amount Vapor deposition material, for example in the form of films, for example wound film pieces, tapes, wires, Rods or platelets, given. After closing and evacuating the vapor deposition, z. B. a PVD system can the evaporation by switching on the power supply, causing the Spirals are made to start to glow. By further energy supply, the vapor deposition material is converted into the gas phase, so that it can deposit on the substrate to be coated. The known from the expert evaporation of metal boats runs in a similar way. In the metal boats lie the previously described coating or vapor deposition materials in front. The boats are mostly made of refractory metal sheets, For example, made of tungsten, tantalum or Moleden.

Especially preferably lies in the metallic protective or composite layer at least one oxide, double oxide, oxide hydrate and / or oxyhalide in particular based on an element of the fourth group of the Periodic Table, in particular zirconium fluoride, zirconium oxyfluoride and / or zirconia. Zirconia is particularly preferred. As double oxides come z. As aluminum / zirconium oxides into consideration. Furthermore, according to another embodiment preferred that in the composite layer, a second metal, in particular on the base of zirconium, titanium and / or hafnium, oxide bound is present.

Suitable acids, which are due to a member of the 4th group include, for. Hydrofluorocarboxylic 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 containing impurities, such as fluoric acid, in the aqueous systems. In the aqueous systems, the acids z. B. in amounts of up to 5 wt .-%, in particular of up to 3.5 wt .-%, based on the total weight of the aqueous system, are present.

hydrofluoric acid can in the aqueous systems, eg. B. in amounts in the range from 0.1 to 3 wt .-%, also be present.

Among the suitable salts it is preferred to use ammonium zirconium carbonate, which is obtainable, for example, from the company Magnesium Electron Inc. under the trade name Bacote 20 ((NH ₄ ) ₂ [Zr (OH) ₂ (CO ₃ ) ₂ ] .n H 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.

Of course it is also possible to use the aqueous systems in addition to the compounds mentioned or mixtures thereof further constituents admix. For this u come. a. Nitric acid, Fluoric acid, phosphoric acid, salts thereof Acids, ammonium bifluoride and ammonium sulfate into consideration. A suitable titanium salt provides z. B. ammonium titanium fluoride.

Prefers The aqueous system contains fluoride ions in free and / or complexed form. As suitable complexed fluoride ions fluoroborate salts and acids and alkali metal and ammonium bifluorides. In general, complex fluorides of titanium, zirconium, hafnium, silicon and / or boron in particular suitable. Preferably, complexes of fluorides are used 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 a second metal, preferably based on an element the fourth group of the Periodic Table of the Elements (IUPAC; Group IVb or IV-B), in particular zirconium, titanium and / or Hafnium, at least one polymeric compound contained in the aqueous composition dissolved, in emulsion form or in the form of undissolved dispersed particles can.

Under the polymeric compounds are in particular the polyacrylic acid and their salts and esters mentioned. These acids, esters and salts may be in the aqueous solution in dissolved or dispersed form. The amount on polymer component can be varied within a wide range and is preferably in the range of 0.1 to 0.5 g per liter.

When polymeric materials also include polymethylvinylmaleic acid and polymethylvinylmaleic anhydride in question. suitable Polyacrylic acids ideally have over a molecular weight of up to 500,000. Preference is also often recourse to mixtures of suitable polymer compounds. Examples are mixtures comprising polyacrylic acid, their salts or esters with polyvinyl alcohol called. Suitable polymers further comprise hydroxyethyl ethers of cellulose, ethylene maleic anhydride, Polyvinyl pyrolidine and polyvinyl methyl ether.

Particularly preferred polymeric components For the purposes of the present invention, a crosslinked polyester comprising a multiplicity of carboxylic acid functionalities and a multiplicity of hydroxyl groups which may have reacted partially or completely with one another. In this cross-linked polyester polymer may be, for. Example, to the reaction product of a first polymer containing carboxylic acid functionalities, with a second polymer containing hydroxyl groups act. For example, polyacrylic acid and polymethylvinyl-maleic anhydride may be considered as such first polymers, while polyvinyl alcohol is a suitable second polymer. Interestingly, both the reaction product of the above-mentioned first and second polymers as well as their mixture is suitable as a constituent of the aqueous system for the treatment by the process according to the invention. In addition, such an aqueous solution may additionally preferably contain fluoric acid. Suitable salts of said polyacrylic acid come z. As ammonium salts in question.

Also suitable as a suitable polymer is 3- (N-C _1-4 -alkyl-N-2-hydroxethylaminomethyl) -4-hydroxystyrene, in particular when hexafluororic acid is used as compound of the 4th group. In addition, if desired, the homopolymer of 4-hydroxystyrene may also be present, with an average molecular weight in the range of 3,000 to 6,000 US 5,089,064 be removed.

In a further preferred embodiment are in the metallic Protective layer next to an acid, an oxide, double oxide, Oxide hydrate, sulfide, halide, nitride, carbide, carbonitride, boride, Silicite, oxyhalide and / or salt of the second metal also also at least one acid, an oxide, double oxide, oxide hydrate, Sulfide, halide, nitride, carbide, carbonitride, boride, silicide, oxyhalide and / or a salt of the first metal, the first precious metal and / or the first metal alloy. Particularly preferred are in the metallic protective layer in addition to an oxide, double oxide, oxide hydrate and / or oxyhalide the second metal at least one oxide, double oxide, oxide hydrate and / or an oxyhalide of the first metal, the first precious metal and / or the first metal alloy.

The aqueous systems may further contain fatty acids, fatty alcohols and / or in particular fatty amines or any mixtures thereof. The fatty amines may also be in the form of their ammonium salts. Fat amines according to the present invention thus also include the corresponding ammonium salts. In this case, recourse is preferably made to compounds with saturated fatty alkyl chains. The length of the linear fatty alkyl chains is preferably in the range of C ₈ to C ₂₄ . Preferred fatty amines or the corresponding ammonium compounds are based on a C ₁₂ , C ₁₄ , C ₁₆ or C ₁₈ alkyl radical. Suitable fatty acids include, for. B. Capric acid.

About that In addition, suitable aqueous systems with polyoxyalkylene glycol ether, in particular polyoxyethylene glycol ethers, polypropylene glycol ethers and their mixtures, be offset. This can be used on all common recourse to commercially available glycol ethers become.

suitable pH values for the aqueous systems are or are preferably in the range of 1.5 to 6.5, preferably in the range from 1.5 to 5.0, and especially from 2.0 to 4.5. Should the pH of the aqueous systems are raised, are suitable especially ammonia or ammonium hydroxide, z. B. in the form of a 3% ammonia solution. In addition, can recourse to conventional, known in the art bases become.

Of the Conductance of the aqueous system used is preferably in the range of 100 to 2000, more preferably in the range of 150 to 1500 and in particular in the range of 200 to 1000 μS / cm.

The previously described optional components of the aqueous Systems are in a preferred embodiment, individually or in any combination, also in the metal layer before and are then also part of the metallic protective or composite layer.

According to one advantageous embodiment of the present invention is provided that after the application of the metallic protective layer according to step b) and optionally after the optional step c) the thus coated Substrate a rinsing step with, in particular demineralized, Water is subjected. This is preferably followed in each case at least one drying step for drying the surface at. The drying step may, for. B. at temperatures in the range from 120 to 180 ° C, for example at about 140 ° C, be performed. The used for rinsing Water preferably has a conductance less than 60 mS / cm, preferably less than 50 mS / cm and in particular less than 35 mS / cm.

Especially the last rinse before the subsequent process step or before a drying process has over the aforementioned conductances.

The pH and / or conductance of the aqueous system are determined for the duration of the loading treatment of the vapor-deposition and sputtering materials is preferably kept substantially constant, in particular within the aforementioned ranges.

The Aufdampf- or sputtering material can, for. B. by dipping, spooling or spraying with the aqueous described above System containing at least one of said compounds of the second metal, to be treated. For example, the first one becomes Metal, the first precious metal or the first metal alloy Step b) and optionally the metal layer in the optional Step iii) under increased pressure with this aqueous System applied, for example in the form of high-pressure water jets. It has proved to be useful, a To direct a variety of fine single water jets on the substrate. suitable Pressures for the aqueous System are z. B. above 0.2 bar, preferably in the range from 0.5 to 50 bar and more preferably in the range of 0.2 to 15, in particular from 0.9 to 1.5 bar. These pressures will be measured on the surface of the metal layer. Also with of the 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 a second Metal, in particular an element of the 4th group of the periodic table, preferably zirconium, titanium or hafnium, introduced into the metal layer become.

The aqueous systems, to which for the admission the first metal, the first precious metal or the first metal alloy before process step b), for the treatment of the metal layer in the optional process step c) and for the production the vapor-deposition material in the optional production step iii) can be resorted to in their general and preferred compositions as previously described in detail, essentially coincide.

suitably the temperature of the aqueous system is during the treatment process of the substrate in the range of 15 to 50 ° C, preferably in the range from 20 to 40 ° C. As a rule, one treatment period is enough from 20 to 120 seconds to the inventive To obtain substrate.

In In a preferred embodiment, the proportion of iron ions in the aqueous system not above 10 ppm.

With The invention also proposes that after step b) a protective or topcoat or glaze are applied can. The protective or topcoat can z. As a clearcoat or a transparent powder and is preferably over Applied wet-paint process or a powder coating process. Furthermore, the invention provides that the protective lacquer at least one dye or may contain a pigment.

to Coloring of the substrate can also be particularly useful resorted to suitable, known to those skilled glazes become. This can be z. B. brass, titanium and gold tones as well as individual colors like red, blue, yellow, green, etc. and all Eloxalfarben easily set.

The The present invention further relates to coated substrates which obtainable by the process according to the invention are. The object underlying the invention is therefore also solved according to another aspect by an at least partially corrosion-protected and in particular a glossy substrate comprising a metallic one and / or non-metallic substrate and at least one metallic A composite layer comprising the first metal, the first noble metal or the first metal alloy in the form of a metal layer and therein in particular distributed substantially uniformly, present or embedded or embedded at least one compound, a Acid and / or a salt of the second metal, in particular at least one acid, an oxide, double oxide, oxide hydrate, Sulfide, halide, nitride, carbide, carbonitride, boride, silicide, Oxyhalide, in particular oxyfluoride, and / or salt of the second Metal.

The Substrates according to the invention can, for example as a mirror, mirrored material or as an accessory used for the automotive industry. Prefers is the use as a light metal rim or alloy wheel for the automotive industry. Of course you can Also body parts, whether plastic or metal, with he inventive method with a metallic Protective or composite layer are provided. The invention Substrates are of course not on the uses mentioned limited.

The present invention accordingly comprises coated metallic and non-metallic substrates comprising, in order, a substrate, for example of plastic, aluminum or an aluminum alloy, and a metallic composite layer as described above, in particular based on aluminum , Optionally, in this embodiment, the substrate surface to be provided with the metallic protective or composite layer is in polished and / or polished form. In a further preferred embodiment, the coated structure according to the invention comprises, in this order, a substrate, preferably with a ge ground and / or polished substrate surface, a, optionally chromium-free, conversion layer and a metallic protective or composite layer, as described above. According to a further advantageous embodiment, a coated substrate according to the invention, in this order, has a substrate, optionally with a polished and / or ground surface, a first and optionally a second primer layer and a metallic protective or composite layer, as described above. Furthermore, an alternative substrate coated according to the invention comprises, in order, a substrate, optionally with a polished and / or ground substrate surface, a, preferably chromium-free, conversion layer, a first primer layer and optionally a second primer layer, and a metallic protective or composite layer, as described above. All of the above-mentioned embodiments may additionally be covered with a preferably transparent topcoat layer and / or glaze layer.

Of the Invention is based on the surprising finding that by the inventive method Substrate provided with a metallic protective coating That will provide excellent corrosion resistance as well has a very attractive chrome look. Under a chrome look In the present case, it should be understood to mean one which is customary only adjusted during galvanic chrome plating of substrates. Such Optics are known from the prior art not available. With the method of the present invention can an adherently coated, corrosion-protected, high-gloss Substrate even with complex geometry, such as a light metal rim or a plastic paint emblem such as the Mercedes star, received optically identical to electroplated substrates is and at the same time all test requirements met the automotive industry.

The Substrates of the invention show outstanding Corrosion resistance, even if the Surface mechanical damage experienced have, for example, by stone chipping or by scribing. Especially was also not expected to be metal substrates, in particular Aluminum substrates that represent glossy parts, such as They usually only with particularly high-quality chrome components can be found. The beneficial effects in terms of corrosion resistance and shine, of course, even when on the application of a primer layer on the substrate or the Application of a final topcoat layer omitted becomes.

Across from Conventional methods, the invention is characterized Procedure by using ecologically harmless Components and process steps and can for the Production of a variety of glossy components are used. exemplary may be called wheel rims, such as automobile, motorcycle and bicycle rims, ornaments of any kind, e.g. B. Moldings, body exterior and interior components, such as rearview mirror covers, Front panels, bonnet covers and brackets, sanitary appliances, like faucets, and reflector surfaces, for example at Headlamps, especially automobile headlamps. Furthermore, can any kind of handles, such as door handles, as well any kind of frame, for example window frames, and also Packaging articles and housings, for example from the cosmetics industry, such as lipstick cases, manufactured according to the inventive method be. In addition, for example, the most varied Components of motorcycles and bicycles or other means of transport, Component components, as used in the furniture industry find, pipes, towel rails, radiators, components of Elevators, interior and exterior components of aircraft, any reflectors, ornaments, mobile phone shells or Components, such as those used in house construction, according to the invention Be coated method. Particularly suitable are the inventive coated substrates also for use in shipbuilding and can be used both indoors and in particular used for exterior components. This shows the quality of the coated according to the invention Products mindful of long-lasting corrosion resistance and consequently a high-quality chromium-like Shine also by sea water, for example spray, not impaired becomes.

From Special advantage is also that problems due to different coefficients of expansion, as with galvanic chromium-plated substrates are observed regularly, no longer occur. The according to the invention Process coated substrates are no longer prone to cracking or to flake off. Thus, for example, high-gloss Plastic substrates accessible, the most diverse Applications, for example in the automotive industry or the white Goods, can be used.

The in the above description and in the claims disclosed features of the invention can be used individually, as well as in any combination for realization the invention in its various embodiments be essential.

QUOTES INCLUDE IN THE DESCRIPTION

This list The documents listed by the applicant have been automated generated and is solely for better information recorded by the reader. The list is not part of the German Patent or utility model application. The DPMA takes over no liability for any errors or omissions.

Cited patent literature

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Cited non-patent literature

• - DIN EN ISO 2409 [0005]
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Claims (32)

Process for producing an at least partially corrosion-protected and / or shiny metallic and / or non-metallic substrate a) Provision a substrate having at least one at least partially coatable surface, b) Applying at least one metallic protective layer to the coatable Surface of the substrate by means of vapor deposition or application a coating or vapor deposition material, in particular in a vacuum, containing i) a first metal, a first noble metal or a first metal alloy and ii) at least one acid, a Oxide, double oxide, oxide hydrate, sulfide, halide, nitride, carbide, Carbonitride, boride, silicide, oxyhalide and / or salt of a second Metal of an element of the 4th group and / or the 5th group of the Periodic table of the elements or mixtures thereof. Method according to claim 1, characterized in that that the coating or vapor deposition material is obtained, by the first metal, the first precious metal or the first Metal alloy with an 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 group element and / or the 5th group of the Periodic Table of the Elements or mixtures thereof, treated. Method according to claim 1 or 2, characterized that the coating or vapor deposition over the following process steps are obtained: i) Provision a carrier layer, ii) applying at least one Metal layer of the first metal, the first precious metal or the first metal alloy by means of vapor deposition or applying this first metal, this first precious metal or this first metal alloy, especially in a vacuum, on a coatable surface of the Carrier layer, and iii) register at least one Acid, an oxide, double oxide, oxide hydrate, sulfide, Halides, nitrides, carbides, carbonitrides, borides, silicides, oxyhalides and / or salt of the second metal in the metal layer according to step ii) by treating the metal layer with an 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 the second metal, wherein the second Metal is an element of Group 4 and / or Group 5 of the Periodic Table represents the elements or mixtures thereof, and iv) detachment and isolating the formed metal layer from the carrier layer. Method according to one of the preceding claims, characterized in that the vapor deposition or application in step b) or step ii) by means of physical vapor deposition (PVD) coating, Vapor deposition by means of an electron beam evaporator, vapor deposition by means of a resistance evaporator, induction evaporation, ARC evaporation and / or cathode sputtering (sputter coating), respectively preferably in a high vacuum, happens. Method according to claim 3 or 4, characterized the carrier layer is a carrier film, in particular a plastic carrier film. Method according to one of claims 3 to 5, characterized in that the carrier layer on those Coating side, which is coated with the metal layer, a release coat. Method according to one of the preceding claims, further comprising after process step b) as a further step: c) Introducing at least one acid, an oxide, double oxide, Oxide hydrate, sulfides, halides, nitrides, carbides, carbonitrides, Borides, silicides, oxyhalides and / or a salt of the second Metal in the metal layer according to step b) by treating the metal layer with an 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 group element and / or the 5th group of the Periodic Table of the Elements or mixtures thereof. Method according to one of claims 2 to 7, characterized in that the aqueous system a pH in the range of 1.5 to 6.5. Method according to one of the preceding claims, characterized in that the first metal is aluminum, gold, silver, Lead, vanadium, manganese, magnesium, iron, cobalt, nickel, copper, Palladium, platinum, titanium, zinc, stainless steel or alloys of these Metals, especially brass or bronze, contains. Method according to one of the preceding claims, characterized in that the metallic substrate is aluminum, Brass, bronze, magnesium, iron, copper, steel, stainless steel, titanium or alloys of such compounds and that the non-metallic Substrate glass, ceramics, carbon materials, plastic, wood or Chipboard covers. Method according to one of the preceding claims, further comprising between steps a) and b) the step: a ') Applying at least a first and possibly a second Primer layer on the, in particular metallic or plastic, Substrate and / or grinding and / or polishing of, in particular metallic, substrate surface. Method according to one of the preceding claims, characterized in that the first metal is brass, bronze, magnesium, Titanium or aluminum or a magnesium, titanium or aluminum alloy includes. Method according to one of the preceding claims, characterized in that the thickness of the according to method step b) protective layer in the range of 5 nm to 10 microns, preferably in the range of 20 nm to 5 μm and especially preferably in the range of 30 nm to 1 micron, is. Method according to one of the preceding claims, characterized in that after step b) or after step c) at least one, in particular transparent, cover layer, in particular Topcoat layer, and / or applied at least one glaze layer becomes. Method according to one of the preceding claims, characterized in that after the application of the metallic Protective layer after step b) and / or c) the coated substrate surface a rinsing step with, in particular demineralized, water is subjected. Method according to one of the preceding claims, characterized in that as acid, oxide, double oxide, Oxide hydrate, sulfide, halide, nitride, carbide, carbonitride, boride, Silicide, oxyhalide or salt of a second metal an acid, an oxide, double oxide, oxide hydrate, sulfide, halide, nitride, carbide, Carbonitride, boride, silicide, oxyhalide, in particular oxyfluorides, or a salt of titanium, zirconium and / or hafnium become. Method according to claim 15, characterized in that that the oxides zirconium oxides, titanium oxides or hafnium oxides, the Oxyfluorides zirconium oxyfluorides, titanium oxyfluorides or hafnium oxyfluorides, the acids fluoric acid, fluorotitanic acid or Fluorhafniumsäure and the salts fluorozirconate, fluorotitanates or Fluorhafniate represent. Method according to one of the preceding claims, characterized in that the aqueous system and / or the metallic protective layer further comprises at least one polymeric compound; at least a fatty acid, a fatty alcohol and / or a fatty amine; at least one polyoxyalkylene ether, in particular polyglycol ether, and / or fluoride ions in free and / or complexed form. Method according to one of claims 2 to 18, characterized in that the first metal, the first precious metal or the first metal alloy prior to step b) and / or the metallic layer according to step b) with the aqueous system Pressure, in particular in the form of liquid jets, acted upon. Method according to one of the preceding claims, characterized in that after step b) or c) at least one, in particular transparent, cover layer, in particular topcoat layer, and / or at least one glaze layer is applied. At least partially protected against corrosion and in particular a glossy substrate comprising a substrate and at least one metallic protective layer available according to a method according to the preceding claims. At least partially protected against corrosion and in particular a glossy substrate according to claim 21, comprising a substrate and at least one metallic protective layer, comprising as first metal, first noble metal or first metal alloy Aluminum, Gold, Brass, Bronze, Silver, Lead, Vanadium, Manganese, Magnesium, iron, cobalt, nickel, copper, palladium, platinum, titanium, Zinc, stainless steel or alloys of these metals and at least one Acid, an oxide, double oxide, oxide hydrate, sulfide, halide, Nitride, carbide, carbonitride, boride, silicide, oxyhalide, in particular Oxyfluoride, and / or salt of a second metal of an element of 4. group and / or 5th group of the periodic table of elements or Mixtures thereof. Substrate according to Claim 21 or 22, characterized that the acid, the oxide, double oxide, oxide hydrate, sulfide, Halide, nitride, carbide, carbonitride, boride, silicide, oxyhalide and / or salt of the second metal over substantially all or almost the entire thickness of the metallic protective layer in the first metal, the first noble metal or the first metal alloy, in particular, is substantially uniform, distributed. Substrate according to one of Claims 21 to 23, characterized in that the thickness of the metallic protective layer in the range of 5 nm to 10 μm, preferably in the range from 20 nm to 5 μm, and more preferably in the range of 30 nm to 1 μm. Substrate according to one of claims 21 to 24, characterized in that the metallic substrate of metals, precious metals or metal alloys, in particular aluminum or an aluminum alloy, and that the non-metallic substrate of glass, ceramic, carbon materials, plastic, wood or chipboard is formed. Substrate according to one of claims 21 to 25, further comprising between the substrate and the metallic protective layer at least one primer layer. Substrate according to one of claims 21 to 26, characterized in that the metallic protective layer bearing Surface of the substrate at least partially polished, honed, degreased and / or decapitated surface represents. Substrate according to one of claims 21 to 27, characterized in that the first metal is magnesium, titanium or Aluminum or that the first metal alloy bronze, brass, one Aluminum, magnesium or titanium alloy. Substrate according to one of claims 21 to 28, characterized in that the acid, the oxide, double oxide, Oxide hydrate, sulfide, halide, nitride, carbide, carbonitride, boride, Silicide, oxyhalide or the salt of the second metal on zirconium, Titanium or hafnium based. Substrate according to one of claims 21 to 29, characterized in that the proportion of the acid, the Oxides, double oxides, oxide hydrate, sulfides, halides, nitrides, Carbides, carbonitrides, borides, silicides, oxyhalides, in particular Oxyfluorids, and / or the salt of the second metal in the metallic Protective layer, based on its total weight, in the range of From 0.2 to 10% by weight and in particular from 1 to 7% by weight, lies. Substrate according to one of Claims 21 to 30, characterized in that the substrate is an aluminum substrate and that the metallic protective layer according to step b) and optionally c) comprises an aluminum layer in which oxidic bound titanium, zirconium and / or hafnium, in particular zirconium dioxide, preferably substantially uniformly distributed, is present. Use of a substrate according to one of the claims 21 to 31 as a mirror, mirrored material or reflector, in particular for headlamps or luminaires or lamps, or as a component thereof; Accessory for the automotive industry, motorcycle construction or bicycle building sector or as part of it; Rim, in particular Alloy wheel, or wheel, in particular light metal, or as a component of this for the automotive sector or for the motorcycle or bicycle building sector; Sanitary fittings, in particular as a fitting, or as a component thereof; Karosserieinnen- or external component or as a component thereof; Handle or handle component, in particular door handle, or as a component thereof; profile or frames, in particular window frames, or as a component thereof; Housing or as packaging or as a component thereof; Inside- or external component of ships or as a component thereof; Ornament or as a component thereof; furniture component or as part of it; Internal or external component of aircraft or as a component thereof; Internal or external component of buildings or as a component thereof; radiator or pipe or as a component thereof; Component of elevators or as part of it; Component of electronic components or equipment or as a component thereof; or as a component of communications components or devices, in particular cell phones, or as part of it.