HK40010262B - Coated substrates and method for the production of coated substrates and their use - Google Patents

Description

The present invention relates to a process for the manufacture of coated substrates and coated substrates and the use of these coated substrates.

Metallic and non-metallic components are often coated to produce a smooth and/or glossy surface. These are usually multilayer coating systems. In addition to the desire to maintain a surface with a high-quality appearance, such coating systems are also regularly used to achieve a pronounced corrosion protection. A permanent corrosion protection is often destroyed by mechanical damage. In many cases, even with minor mechanical damage, surface corrosion protection coating begins. This can also have a sub-layer application phase in addition to discoloration.

According to DE 38 33 119 C2, a corrosion-resistant chromated metal surface with a very good adhesion to a substrate is obtained by applying an electroplating coating directly to the chromate layer without intermediate drying.

The problem of corrosion protection or the production of smooth coated surfaces is often solved by increasing the material load, i.e. the thickness of the coating system, for individual layers or for several layers at once.

Corrosion resistant coatings, especially for metal substrates, still show considerable potential for improvement in terms of adhesion and corrosion protection, especially for mass-produced products, especially those with demanding geometries.

It is also often not trivial to produce high-quality substrates that can be easily and cost-effectively reproduced in mass production. Such surfaces usually require the use of galvanic technology. To obtain so-called black chrome coatings, which often provide a particularly noble appearance, the effort must be increased once again.

The present invention was therefore intended to provide coated substrates which are no longer affected by the disadvantages of the state of the art and which, in particular, also in mass production, provide coated products with improved corrosion resistance and/or very good adhesion and/or high surface properties. The aim is also to provide coated products which do not immediately show undergoing phenomena of undergoing mechanical surface damage, especially when not associated with the defoliation of layers. Furthermore, the invention was intended to provide coated substrates which, even with more complex structures, including a coating layer, have a similarly high coating performance across the entire geometry, including a coating layer.

Accordingly, a process for the production of a coated metallic substrate or a coated non-metallic substrate, in particular a plastic substrate, was developed which included: (b) the provision of an application system for the application of a metal layer, in particular a vacuum vaporizer or a sputter system, and the provision of at least one plasma generator and/or at least one corona system, in particular in the application system for the application of a metal layer, such as a vacuum vaporizer or a sputter system, or as part of it;in particular plastic substrate, with a vacuum (d1) and plasma treatment with the plasma generator of the metallic substrate or non-metallic substrate, in particular plastic substrate, or the coating surface of the non-metallic substrate, in particular plastic substrate, or metallic substrate, in vacuum (d2);in particular, plastic substrate, or the coating surface of the metallic substrate or non-metallic substrate, in particular, plastic substrate, as specified in step (e) or (f); (h) coating the metallic substrate or non-metallic substrate with the ground layer, in particular, plastic substrate, with a vacuum (h1) and plasma treatment with the plasma generator of the ground layer as specified in step (g) in the step (h2); (i) if applicable, treatment of the grey coating obtained after step (g) or (h), in particular, h1) and h2), with at least one organic compound of silicon, in particular by plasma polymerisation, in particular, polyoxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxyloxylo(k) the application of at least one layer of metal, containing or consisting of a metal selected from the group consisting of aluminium, silver, gold, lead, vanadium, manganese, magnesium, iron, cobalt, nickel, copper, chromium, palladium, molybdenum, tungsten, platinum, titanium, zirconium and zinc, in particular aluminium, or containing or consisting of an alloy of metal selected from the group consisting of brass, bronze, steel, in particular stainless steel, aluminium, magnesium and titanium alloys, obtained by application directly to the treated layer by steam and/or sputtering techniques by means of a plasma plasma layer (i) or (j) or, where appropriate, by plasma plasma treatment (Bandrolol) or, in particular, by chemical treatment (Crystal), in accordance with the following formula:(n) Plasma treatment with the plasma generator of the layer, in particular the polysiloxane layer, as described in step (m) in vacuum, undo) Application of at least one coating, in particular transparent and/or coloured, to the treated layer, in particular the polysiloxane layer, as described in step (n).

In a feasible design, the method of the invention shall include, in addition to steps (a) and (b), where appropriate, (c) the sequence of steps (d1), (d2), (g), (h1), (h2), (k), (m), (n) and (o), preferably in immediate succession.

The method of the invention also includes such suitable embodiments in which steps (g), (h), in particular (h1) and (h2), (k), (m), (n) and (o), or steps (g), (h1) and (h2), (j), (k), (l), (m), (n) and (o), or steps (d1) and (d2), (g), (h1) and (h2), (k), (m), (n) and (o), or steps (d1) and (d2), (e), (f), (g), (h1) and (h2), (k), (m), (n) and (o), in particular, excluding steps (i) and (j), are each directly followed by one another.

(k) The application of a polysiloxane layer, in particular plasma generated, may be provided in an appropriate embodiment before the metal layer application step.

Err1:Expecting ',' delimiter: line 1 column 98 (char 97)

In a particularly suitable design, in particular as specified above, the layer to which the metal layer is applied in step (k) shall be subjected to a plasma treatment with the plasma generator in vacuum prior to step (k).

(b) to provide an application equipment for the application of a metal layer, namely a vacuum vaporizer or a sputter system, and to provide at least one plasma generator, in particular in the vaporizer or sputter system, or as part of it, (c) to clean at least one surface surface that can be coated in at least one area, where appropriate;(d2) (e) Treatment of the metallic substrate or non-metallic substrate, in particular the plastic substrate, or the coated surface of the metallic substrate or non-metallic substrate, in particular the plastic substrate, with at least one silicon-organic compound by plasmapolymerization, in particular by formation of a polysiloxane layer, in vacuum (d2); (f) Plasma treatment with the plasma generator of the layer, in particular the polysiloxane layer, where appropriate, in accordance with at least one step; (g) Application of a basic surface treatment to the metallic or non-metallic substrate, in particular the plastic substrate or the plastic substrate, in particular the metallic or non-metallic substrate, in accordance with at least one step;(h) applying the metallic substrate with the base layer or the non-metallic substrate with the base layer, in particular plastic substrate, with a vacuum (h1) and plasma treatment with the plasma generator of the base layer according to step (g) in vacuum (h2); (i) if applicable, treatment of the base layer with at least one silicon organic compound, in particular by means of plasma polymerization, obtained after step (g) or (h) and (h2), in particular by means of plasma polymerisation, in particular in vacuum, in particular by forming a polysilox layer; (j) if applicable, treatment with the plasma generator of the base layer, in particular polysiloxane, according to step (i), in particular by means of a plasma treatment, in vacuum, or (i) in the case of metallic aluminium, at least one aluminium layer, orMagnesium or titanium alloying with the application equipment by steam and/or sputtering directly on the treated layer of foundation as described in step h2), or (i) or (j), (l) where applicable, plasma treatment with the plasma generator of the metal layer as described in step k), (m) treatment of the metal layer obtained by step k) or (l) with at least one silicon-organic compound by plasma polymerisation, in particular by forming a polysiloxane layer in vacuum, (n) plasma treatment with the plasma generator of the layer, in particular the polysiloxane layer, as described in step m) in vacuum, undock (n) application of at least one particularly transparent and/or painted coating layer, in particular the polysiloxane layer, as described in step n).

In this variant, step (f) is optional and may in individual cases contribute to further improvement of the liability and further protection against corrosion.

For some applications of the method of the invention, it has been shown to be advantageous to have a polysiloxane layer, in particular plasma generated, on each side of the metal layer, preferably each having undergone a plasma treatment.

The method of the invention involves, in step (g), the application of a coating layer, which can, for example, compensate for unevenness of substrates of lower quality to be coated.

It has been shown to be advantageous to essentially follow the above steps directly after each other. This means in particular that after the plasma treatment steps, prolonged storage should be avoided. Rather, it is advantageous to follow the next step directly. It has also been shown that it is not necessary to interpolate further steps in addition to the previous steps.

Suitable non-metallic substrates include glass, ceramics, stone materials, composite materials, carbon materials, plastic or wood. The method of the invention described herein is particularly suitable for coating plastic substrates to obtain products with a high gloss permanence. Suitable plastic substrates include or consist of, for example, PVC, polyurethane, polyacrylates, polyesters, e.g. PBT and PET, polyolefins, in particular polyethylene, polycarbonates, polyamide, polypropylene, polystyrene, styrene or polyethylene polymers, such as ABS-ABS, SAN, ASAPC or polyoxybenzene, e.g. PAM, PAM, PAM, PAM, PAM, PAM, PAM, PAM, PAM, PAM, PAM, PAM, PAM, PAM, PAM, PAM, PAM, PAM, PAM, PAM, PAM, PAM, PAM, PAM, PAM, PAM, PAM, PAM, PAM, PAM, PAM, PAM, PAM, PAM, PAM, PAM, PAM, PAM, PAM, PAM, PAM, PAM, PAM, PAM, PAM, PAM, PAM, PAM, PAM, PAM, PAM, PAM, PAM, PAM, PAM, PAM, PAM, PAM, PAM, PAM, PAM, PAM, PAM, PAM, PAM, PAM, PAM, PAM, PAM, PAM, PAM, PAM, PAM, PAM, PAM, PAM, PAM, PAM, PAM, PAM, PAM, PAM, PAM, PAM, PAM, PAM, PAM, PAM, PAM, PAM, PAM, PAM, PAM, PAM, PAM, PAM, PAM, PAM, PAM, PAM, PAM, PAM, PAM, PAM, PAM, PAM, PAM, PAM, PAM, PAM, PAM, PAM, PAM, PAM, PAM, PAM, PAM, P

For metal substrates, metals and metal alloys may be used, with the most suitable metal substrates being selected from the group consisting of aluminium, aluminium alloys, iron, iron alloys, in particular steel or stainless steel, copper, copper alloys, titanium, titanium alloys, zinc, zinc alloys, nickel, nickel alloys, molybdenum, molybdenum alloys, magnesium, magnesium alloys, lead, lead alloys, tungsten, tungsten alloys, manganese, manganese alloys, brass, bronze, nickel-press casting, zinc-press casting and aluminium casting or any mixture thereof.

For many applications, it has been shown that cleaning and/or degreasing the metal substrates by treatment with dry ice is sufficient. In many cases, degreasing is already sufficient. Without any theory, it is currently assumed that the following steps of the invention will lead to a sufficiently efficient and effective process of conversion of the metal surfaces into a dry form and removal of all the metal particles, for example, the 906 EP and the 852 EP, and to the purification of the metal in a dry form and removal of all the metal particles in the process.

The surface of metal substrates can be degreased, for example, with alkaline or acidic reagents. Commercial degreasing steps are also known as decoction or pickling oils. Alternatively, a metal surface can be anodized in an electrolytic degreasing bath.

For some embodiments it is advantageous to subject the metal substrate surface, especially the degreased one, to at least one decarburization step. For decarburization of the metal substrate surface, for example, an acidic rinse bath is used. A suitable decarburizing solution is therefore, for example, diluted hydrochloric acid (1:10 vol/vol). The result is usually a metal surface essentially free of oxides.

The metallic substrate surface can then be phosphate and/or passivated, in place of or at the degreasing step, which is particularly suitable for substrates made of or containing aluminium.

The method of applying a coating according to the method of the invention is known to the skilled person, for example by the wet coating process, the powder coating process or the UV curing coating system. Accordingly, the coating can be applied in a preferred design, in particular on UV curing powdered polyester resin compounds or epoxy/polyester powder. This result is surprising in that UV curing coatings, such as ground coatings, are regularly exposed to very hard layers of a gloss coating and are difficult to manipulate further by means of an electrical or thermal layer and/or can lead to cracks.

The appropriate silicon organic compounds are known to the professional; for this purpose, at least one amino-containing silane, in particular aminopropyltriethoxysilan, hexamethyldisiloxane, tetramethyldisiloxane or any mixture thereof, is used in an appropriate design; hexamethyldisiloxane and tetramethyldisiloxane are particularly preferable, hexamethyldisiloxane being regularly particularly suitable.

Suitable silicon organic compounds also include, as monomer or comonomer building blocks, compounds of the following formula (I): Other Other The test chemical is a chemical that is used to produce a specific chemical. Other Other where the substitutes and indices have the following meanings: m0, 1, 2 or 3, in particular 2 or 3,R1C1- to C10 hydrocarbon residues, in particular a C1 to C10 hydrocarbon chain which may be interrupted by oxygen or nitrogen, in particular methyl, ethyl or i- or n-propyl, preferably i- or n-propyl,R2like or various hydrolysable groups, in particular alkoxy groups such as methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy or t-butoxy, in particular methoxy or ethoxy,R3like or various C1 to C5 groups, in particular methyl, ethyl or i- or n-propyl, preferably i- or n-propyl, in particular a polymeric functional group of 4 to 10 ω-methacrylic alcohols, in particular an organic carbon atom with an unstable functional group of 1 to 6 ω-methacrylic alcohols, in the form of an organic carbon atom with an unstable functional group of 4 to 10 ω-methacrylic alcohols, in the form of an organic carbon atom with an unstable functional functional group of 1 to 6 ω-methacrylic alcohols.

Particularly suitable residues X include, for example, vinyl, alkylvinyl, especially methyl, ethyl or propyl vinyl, (Meth) acryloxyalkyl, especially (Meth) acryloxymethyl, (Meth) acryloxyethylene or (Meth) acryloxypropyl, especially (Meth) acryloxypropyl.

An appropriate embodiment of the process of the invention provides that the organic compound is supplied by a supply line from a container outside the application plant for the application of a metal layer, in particular outside the vacuum chamber of the vacuum vaporizer, to a container of that application plant, in particular a vacuum chamber. It is also possible that a dye, in particular a dye, is added to the organic compound. Accordingly, the processes of the invention are also characterized by an appropriate design by combining at least one organic compound, in particular for plasma polymerization, with at least one dye, in particular a dye, in the application plant for the application of a chemical, in the form of a metallic compound, in a suitable form.

For the implementation of the process according to the invention, an application system for the application of a metal layer may therefore be used, comprising at least one container, in particular, outside the application system for the application of a metal layer, in particular, outside the vacuum chamber of the vacuum evaporator, for the reception of a silicon-organic compound with a supply line to the application system, in particular to the vacuum chamber.

Good adhesion without any restriction on corrosion resistance can be obtained in particular by the treatment step with at least one organic compound of silicon such as hexamethyldisiloxane, in particular by plasma polymerisation, in the presence of at least one reactive gas such as oxygen, nitrogen, carbon dioxide, hydrogen, carbon monoxide, hydrogen peroxide, water vapour, ozone and/or air, in particular in the presence of oxygen or air, in the form of a polysiloxane layer in the presence of at least one reactive gas such as oxygen, nitrogen, carbon dioxide, hydrogen, carbon monoxide, hydrogen peroxide, water vapour, ozone and/or air. The addition of reactive gases, in particular air or oxygen, in the polymerisation process, in particular plasma generated, results in harder polysiloxane layers than the production of such conventional polysiloxane layers without the use of more hardened polysiloxane layers.The above described embodiment of the co-use of reactive gases in the production of the polysiloxane layer, in particular plasma generated, is preferably used in at least one step of the treatment with at least one silicon organic compound, in particular by plasma polymerisation, in the formation of a polysiloxane layer or in each step of the production of a polysiloxane layer.In step m, the plasma treatment is preferably made from an inert gas, in particular oxygen, by means of a plasma gas, and in step d, the plasma treatment is preferably made with an argon containing plasma gas.

Alternatively, for the generation of a suitable plasma, mixtures of at least one inert gas, in particular argon, and a reactive gas such as oxygen, nitrogen, carbon dioxide, hydrogen, carbon monoxide, hydrogen peroxide, water vapour, ozone and/or air can be used to generate a suitable plasma. Preferably oxygen and surface matter, especially nitrogen, are used. Finally, it is also possible to use a plasma containing only reactive gases, such as nitrogen, hydrogen, carbon monoxide, hydrogen oxide, to activate a plasma in order to generate a plasma such as oxygen. This is done in a regular way, for example, by using a plasma gas/oxygen that is activated by the plasma and which produces oxygen.

Accordingly, a particularly suitable design of the process may provide that the plasma treatment step with the plasma generator is to be carried out using at least one inert gas, in particular argon, or using at least one inert gas, in particular argon, and oxygen, nitrogen, carbon dioxide, hydrogen, carbon monoxide, hydrogen peroxide, water vapour, ozone and/or air, in particular oxygen, or using oxygen, nitrogen, hydrogen, carbon monoxide, carbon monoxide, carbon peroxide, hydrogen peroxide, water vapour, ozone and/or air, in particular oxygen, in particular, or with the exclusion of input gases.

The present invention is particularly well solved by such processes as are described in the invention, where the plasma treatment described in step (d2) and/or (f), in particular, d2), using argon, in an appropriate configuration excluding air or oxygen, and/or the plasma treatment described in step (h2) and/or (j), in particular, j), using oxygen, in an appropriate configuration excluding inert gases such as argon, is performed.

The method of the invention has the major advantage that almost all the steps of the process in the application plant for the application of a metal layer can be carried out. This concerns, in addition to the application of the broad metal layer, the activation of surfaces by means of plasma treatment with the plasma generator, as well as the application of the layer formed by silicon-organic compounds, in particular the polysiloxane layer, in particular by means of plasma polymerization. Only the cleaning steps, the application of the grinding layer and the application of the coating layer are regularly carried out outside the said application plant. Accordingly, it may be appropriate to provide that the activation of surfaces, in particular the plasma coating with a polysiloxane fan/sputnik, is carried out before any application of the layer, in particular the application of any vacuum or vacuum-forming material, in particular any material or material, in particular the composition of the silicon-organic compound or sputnik, and in particular the deposition of any material or material, in particular the deposition of any material or material, in any vacuum-forming material or material, in any installation, in particular the installation, in any installation, in any installation, in any installation, in any installation, in any structure, in any installation, in any installation, in any structure, in any structure, in any structure, in any structure, in any structure, in any structure, in any structure, in any place, and any material, in any material, in any material, in any material, in any material, in any material, in any material, in any material, in any material, in any material, in any material, in any material, in any form, in any form, in any form, in any form, in any form, in any form, in any form, in any form, or in any form, in any form, in any form, in any form, in any form, in any form, in any form, in any form, in any form, in any form, or in any form, in any form, in any form, in any form, in any form, or in any form, or any form, including any, including any, including any, including any, including any, including any, including any, including any, including, including, including, including, including

The coating layer may be formed from polyacrylate resins, polyester resins, aminoplast resins or polyurethane compounds. The methods of the present invention prefer to apply coatings which are based on a UV-curable coating material. Accordingly, a preferred coating layer is a UV-curable coating layer. The coating layer may be obtained, for example, by a clear coating or a transparent powder coating. The coating layer is preferably based on a wet coating process or a powder coating process. The coating layer may be based on one, two or more UV-curable coating materials, for example, while the coating layer may be based on a chemical coating process, which may be used for the purpose of converting the coating layer into a base coating or a powder coating process.

It was also found that the method of the invention can be used to apply the coating step by means of electrostatic painting, which leads to a further reduction in the amount of coating material required for the coating layer. This also ensures a very uniform coating application. This also makes the so-called circular coating much more effective, i.e. it also covers areas that are not or only partially accessible by direct spraying. The method of electrostatic coating is known to the expert. The method of the invention allows the electrostatic coating to be applied to the applied coating, e.g. aluminum coating, in a suitable way. This method can also be applied to the applied electrostatic coating in a positive direction.

The coating layer is generally 10 to 50 μm thick, preferably 20 to 30 μm thick. The essential feature of the invention for the methods described is that the coating material is applied to a polysiloxane layer previously activated by plasma treatment and/or corona treatment, which in turn is obtained preferably by plasma polymerization, preferably without substantial time delay.

For example, the techniques of physical vapor deposition (PVD), chemical vapor deposition (CVD), evaporation by an electron beam evaporator, evaporation by a resistance evaporator, induction evaporation, ARC evaporation or cathode or anode dust (sputter coating) can be used to order the metal layers.

Suitable vacuum evaporators include, for example, cathode-ray burners and anode-ray burners. As the expert knows, a metal layer is predominantly made of metal. This does not entirely exclude additives, such as those used in carbon-based stainless steel. Preferably, the metal content of the present layer is much greater than 90%, particularly 95% and ≥ 98% by weight.

The PVD process generally uses resistance-heated metal coil or metal ship evaporators, with the preference for tungsten coils of various shapes. In the PVD process, a evaporator is generally equipped with coils that can be clamped to insulated evaporator sheets. Each coil preferably contains a specific amount of metal to be evaporated. After the PVD system is closed and evacuated, the evaporation can be carried out by turning on the power supply, which allows the coils to evaporate the coil, which is usually done in a specific way.

Another preferred method for removing the metal layer on the substrate is the sputter process, which involves placing a cathode in an evacuated container connected to the negative pole of a power supply. The coating material to be sputtered is mounted directly in front of the cathode and the substrates to be coated are placed opposite the coating material to be dusted. Further argon gas can be passed through the container, which eventually has an additional energy which is positively connected to the positive pole of a power supply. After the sputter has been pre-evacuated, the cathode and anode are connected to the supply vessel.

The metallic layers obtained by the above methods and equipment preferably have an average, in particular absolute, thickness in the range of 1 nm to 150 nm, in particular in the range of 5 nm to 120 nm. In a very suitable design of the substrate coated in accordance with the invention, the metallic layer is set, for example, with a thickness in the range of 60 nm to 120 nm, preferably with a thickness in the range of 75 nm to 110 nm. At these thicknesses, the metallic layer, in particular the aluminium layer, is overlapping, i.e. essentially non-transparent or translucent on the surface. This allows high gloss layers to be obtained.

In accordance with a method which is also particularly suitable, the layer of metal, in particular the aluminium layer, applied with the application device in step k, is applied in a thickness, in particular evaporated or sprayed, such that the metal layer is transparent or translucent to visible light, in particular also after step l), m), n) and/or o) or after step m), n) and/or o), except for step l. Alternatively, the layer of metal, in particular the aluminium layer, applied with the application device in step k, may be provided in a thickness, in particular evaporated or sprayed, such that the metal layer is transparent and non-translucent to visible light.

The methods of the present invention may also be used to colour the coating on the non-metallic and metallic substrates by applying to the coating layer at least one dye, e.g. at least one pigment and/or at least one dye, from a coating material. Also, lasers known to the skilled can be used to colour the coating layer, e.g. to obtain brass, titanium and gold tones or individual colours such as red, blue, yellow, green, etc. or colours of aloxal. For example, pigments such as pigment, LCP-P (liquid crystal polymer) or variable-P (optical) pigments can also be processed in the coating layer.

The invention is further solved by a coated metallic or nonmetallic substrate obtained or available by the method described above, in this order, preferably in immediate succession, (e) at least one layer, in particular one layer, formed from at least one silicon-organic compound by means of plasma polymerisation, in particular a polysiloxane layer; Other (i) at least one layer, in particular one layer, formed from at least one silicon-organic compound, in particular by plasma polymerisation, and in particular a polysiloxane layer;K) at least one layer, in particular one metal layer, applied by a vaporization and/or sputtering technique;M) at least one layer, in particular one layer, formed from at least one silicon-organic compound, in particular a polysiloxane layer, by plasma polymerisation;O) at least one layer, in particular one, in particular a transparent and/or coloured covering layer.

In the design specified above, such metallic substrates coated in accordance with the invention and such non-metallic substrates coated in accordance with the invention will solve the invention particularly well, where the metallic or non-metallic substrate to be coated is a substrate treated in vacuum with a plasma, in particular argon plasma, as described in A. and/or a layer composed of at least one silicon-organic compound, in particular a polysiloxane layer, as described in E.

A non-inventive method for the manufacture of a coated substrate, in particular a coated ceramic, glass or stone substrate, is also disclosed, including: (b) where appropriate, the provision of an application system for the application of a metal layer, in particular a vacuum vaporizer or a sputter system, and the provision of at least one plasma generator and/or at least one corona system, in particular in the application system for the application of a metal layer, such as a vacuum vaporizer or a sputter system, or as a component thereof, where appropriate;(e) where applicable, treatment of the substrate or coated surface of the substrate obtained in accordance with step (d) with at least one silicon-organic compound, in particular by means of plasma polymerisation, in particular by forming a polysiloxane layer;(h) where applicable, application of the metallic substrate with the base layer or the non-metallic substrate with the base layer, in particular the plastic substrate, with a vacuum (h1) and/or plasma treatment with the plasma generator and/or corona treatment, in particular the plasma treatment, the base layer as described in step (g) in vacuum (h2); (i) where applicable, treatment of the silicon base layer with at least one organic compound of aluminium obtained after step (g) or (h), in particular h1) and h2), in particular by means of plasma polymerisation, in particular formation under a polysiloxane layer, in particular in vacuum; (j) where applicable, treatment of the plasma and/or corona treatment, in particular the base layer, in particular the treatment, in particular, consisting of at least one metallic group, in particular, containing polysiloxane, in particular, in accordance with step (i), in particular, the vacuum treatment; or (i) where applicable, treatment of the plasma and/or corona treatment, in particular, with a polysiloxane layer, in particular, in particular, containing at least one metallic group, in particular, in particular, in accordance with step (i)Silver, gold, lead, vanadium, manganese, magnesium, iron, cobalt, nickel, copper, chromium, palladium, molybdenum, tungsten, platinum, titanium, zirconium and zinc, in particular aluminium, or containing or consisting of an alloy metal selected from the group consisting of brass, bronze, steel, in particular stainless steel, aluminium, magnesium and titanium alloys, with the application equipment, in particular by evaporation and/or sputtering techniques, in particular directly to a layer obtained after step d2), with the previous step d1), step or step j) obtained, (l) if applicable, plasma treatment with the plasma generator and/or corona treatment, in particular plasma treatment, according to step k), step g) or step h2), or (l) obtained with at least one layer of silicon, silicon or silicon, (d) obtained by step l2), or (l) obtained with a layer of silicon, silicon or silicon, (h), or (l) obtained by step l2), or (l) obtained with at least one step of organic compounds, (l)(n) plasma treatment with the plasma generator and/or corona treatment, in particular plasma treatment, the layer, in particular the polysiloxane layer, as specified in step (m), in particular in vacuum, undo (d) application of at least one coating, in particular transparent and/or coloured, on the treated layer, in particular the polysiloxane layer, as specified in step (n).

In the case of the designs of the methods of the invention specified above, the underlying task is also particularly well solved by those in which steps d1), d2), m), n) and o), in particular omitting steps d), e) to l), or steps d1), d2), k), m), n) and o), in particular omitting steps e) to j) and l), follow each other, in particular directly.

A coated substrate not in accordance with the invention, in particular obtained or available by the process described above, is also disclosed, in particular in this order, preferably in immediate succession, (M) at least one, in particular one, of at least one silicon-organic compound, in particular by means of plasma polymerisation, formed and in particular plasma-treated and/or corona-treated in vacuum, layer, in particular a polysiloxane layer,O) at least one, in particular one, in particular, transparent and/or coloured, coating layer; or

The method of the invention may also be implemented by means of an application system for the application of a metal layer, comprising or constituting a vacuum evaporation system with a vacuum chamber, and at least one, in particular a number of first heatable reception units, in particular bowls, vessels or windings, each comprising or constituting a heating device or a heating device, each designed and suitable for the reception of a metal or metal alloy, and a control device for adjusting the melting or melting temperature.

A variant may be provided that the application system for the application of a metal layer shall include at least one container, in particular outside the vacuum chamber of the vacuum evaporator, for the reception of a silicon-organic compound with a supply line to the vacuum chamber.

It has proved particularly useful to equip the application system for the application of the metal layer also with at least one longitudinally oriented rack, particularly in the vacuum chamber, and with at least one support, in particular in the form of a shaft, oriented essentially along the longitudinal orientation of the rack, designed and equipped to accommodate at least one, in particular a large number of non-metallic and/or metallic substrates, with the support and/or support rotated around an axis, in particular one oriented essentially horizontally.

The coated substrates of the invention or the coated substrates available by the methods of the invention shall regularly pass the vapour jet test, e.g. according to DIN EN ISO 16925:2014-06, the condensed water constant climate test, e.g. according to DIN EN ISO 6270-2, the hydrolysis test, e.g. according to BMW standard AA-0203 or AA-P 308, the salt spray test, e.g. according to DIN EN ISO 9227 and/or the lattice cross section test, e.g. according to DIN EN ISO 2-409:2013-06.

The substrates coated in accordance with the invention, obtained or obtained by the process described in the invention, are used as accessories for automotive, motorcycle, bicycle or shipbuilding, for rims, especially light metal rims, wheels, especially light metal wheels, or as components thereof, for medical devices, especially fittings, or as components thereof, for body or exterior components or as components thereof, for handles or components thereof, especially door handles or as parts thereof, for profiles or frames, especially window frames or as parts thereof, for building systems or components thereof, especially door frames and panels, for machinery or components thereof, for household or household goods, for buildings or parts of buildings, especially for buildings or parts of buildings, as components thereof, or as components thereof, for machinery or components thereof, for buildings or parts thereof, for buildings or parts thereof, or for buildings or parts thereof, or for buildings or parts thereof, or for buildings or parts thereof, or for buildings or parts thereof, or for buildings or parts thereof, or for buildings or parts thereof, or for buildings or parts thereof, or for buildings or parts thereof, or for buildings or parts thereof, or for buildings or parts thereof, or for buildings or parts thereof, or for buildings or parts thereof, or for buildings or parts thereof, or for buildings or parts thereof, or for buildings or parts thereof, or parts thereof, or for buildings or parts thereof, or parts thereof, or parts thereof, or parts or parts thereof, or parts thereof, or parts or parts thereof, or parts thereof, or parts or parts thereof, or parts or parts thereof, or parts thereof, or parts or parts thereof, or parts thereof, or parts or parts thereof, or parts or parts thereof, or parts or parts thereof, or parts thereof, or parts or parts thereof, or parts or parts thereof, or parts or parts thereof, or parts or parts thereof, or parts or parts or parts thereof, or parts or parts thereof, or parts or parts or parts thereof, or parts or parts or parts thereof, or parts or parts thereof, or parts or parts or parts of such parts or parts or parts or parts or parts or parts or parts of such parts or parts or parts or parts, or parts, or parts, or parts, or parts, or parts, or parts, or parts, or parts, or parts, or parts,

The invention is based on the surprising finding that the substrates obtained by the inventive processes provide a high-quality gloss coating that retains its gloss permanently. Moreover, it was found that the coated non-metallic and metallic substrates obtained by the inventive process are equipped with excellent corrosion resistance. The coated substrates obtained by the inventive processes are characterised by a high degree of adhesion. Moreover, these coated substrates show significantly reduced corrosion resistance even when the surface has undergone mechanical damage, for example by coating the surface with a coating that is too thin or too thin. The coating process is so extensive that it is not necessary to produce the coating in the new process to achieve a significant reduction in the surface area.

A particularly surprising advantage is that the coated substrates produced by the method of the invention do not show edge build-up or edge leakage, while also resulting in a significantly reduced proportion of waste products in mass production. Even high-quality chrome surfaces can be reproduced in a reliable and reproducible manner without the use of chromium or other heavy metals.

The features of the invention disclosed in the foregoing description and claims may be essential, either individually or in any combination, for the realization of the invention in its various embodiments.

Claims (12)

1. A method for producing a coated metallic substrate or a coated non-metallic substrate, in particular a plastic substrate, comprising

   a) providing a metallic substrate or non-metallic substrate, in particular plastic substrate, with at least one surface that can be coated at least in certain areas,

   b) providing an application system for the application of a metal layer, in particular a vacuum vapor deposition system or sputter system, and providing at least one plasma generator and/or at least one corona system, in particular in the application system for the application of a metal layer, such as a vacuum vapor deposition system or sputter system, or as part thereof,

   c) optionally cleaning the at least one surface that can be coated at least in certain areas,

   d) subjecting the metallic substrate or non-metallic substrate, in particular plastic substrate, or the surface of the metallic substrate or the non-metallic substrate, in particular plastic substrate, that can be coated, to a vacuum (d1)) and plasma treatment of the metallic substrate or non-metallic substrate, in particular plastic substrate, or the surface of the non-metallic substrate, in particular plastic substrate, or metallic substrate, that can be coated, in a vacuum (d2)) with the plasma generator,

   e) treating the metallic substrate or non-metallic substrate, in particular plastic substrate, obtained after step d), or the surface of the metallic substrate or non-metallic substrate, in particular plastic substrate, that can be coated, with at least one organosilicon compound by means of plasma polymerization, in particular with the formation of a polysiloxane layer,

   f) optionally plasma treatment, preferably in a vacuum, with the plasma generator and/or corona treatment, in particular plasma treatment, of the layer, in particular polysiloxane layer, according to step e),

   g) applying at least one primer layer to the metallic substrate or non-metallic substrate, in particular plastic substrate, or to the surface of the metallic substrate or non-metallic substrate, in particular plastic substrate, that can be coated, according to step e) or f),

   h) subjecting the metallic substrate provided with the primer layer or the non-metallic substrate, in particular plastic substrate, provided with the primer layer, to a vacuum (h1)) and plasma treatment of the primer layer according to step g) in a vacuum (h2)) with the plasma generator,

   i) optionally treating the primer layer obtained after step g) or h), in particular h1) and h2), with at least one organosilicon compound, in particular by means of plasma polymerization, in particular with the formation of a polysiloxane layer, in particular in a vacuum,

   j) optionally plasma treatment, preferably in a vacuum, with the plasma generator and/or corona treatment, in particular plasma treatment, of the layer, in particular polysiloxane layer, according to step i), in particular in a vacuum,

   k) applying at least one metal layer containing or consisting of a metal selected from the group consisting of aluminum, silver, gold, lead, vanadium, manganese, magnesium, iron, cobalt, nickel, copper, chromium, palladium, molybdenum, tungsten, platinum, titanium, zirconium and zinc, in particular aluminum, or containing or consisting of a metal alloy selected from the group consisting of brass, bronze, steel, in particular stainless steel, aluminum, magnesium and titanium alloys, with the application system, by means of vapor deposition and/or sputtering technology, directly on the treated primer layer according to step h2), or i) or j),

   l) optionally plasma treatment, preferably in a vacuum, with the plasma generator and/or corona treatment, in particular plasma treatment, of the metal layer according to step k),

   m) treating the metal layer obtained after step k) or 1) with at least one organosilicon compound by means of plasma polymerization, in particular with the formation of a polysiloxane layer, in a vacuum,

   n) plasma treatment of the layer, in particular polysiloxane layer according to step m), in a vacuum, with the plasma generator, and

   o) applying at least one, in particular transparent and/or colored, top layer to the treated layer, in particular polysiloxane layer, according to step n).
2. The method according to claim 1, characterized in that steps g), h1) and h2), k), m), n) and o), or steps d1) and d2), k), m), n) and o), or steps g), h), j), k), 1), m), n) and o), or steps d1) and d2), g), h1) and h2), k), m), n) and o), or steps d1) and d2), k), m), n) and o), or steps d1) and d2), e), f), g), h1) and h2), k), m), n) and o), in particular omitting steps i) and j), in each case, are consecutive, in particular immediately consecutive.
3. The method according to claim 1 or 2, characterized in that the metal substrate comprises or consists of metals or metal alloys or in that the non-metallic substrate comprises or consists of glass, ceramic, stone materials, composite fiber materials, carbon materials, plastic or wood, in particular composite fiber materials, carbon materials and/or plastic.
4. The method according to any one or more of the preceding claims, characterized in that the organosilicon compound comprises at least one amino-containing silane, in particular aminopropyltriethoxysilane, hexamethyldisiloxane, tetramethyldisiloxane or any mixtures thereof, in particular hexamethyldisiloxane.
5. The method according to any one or more of the preceding claims, characterized in that the step of plasma treatment is carried out with the plasma generator using at least one inert gas, in particular argon, or using at least one inert gas, in particular argon, and oxygen, nitrogen, carbon dioxide, hydrogen, carbon monoxide, hydrogen peroxide gas, water vapor, ozone and/or air, in particular oxygen, or using oxygen, nitrogen, hydrogen, carbon dioxide, carbon monoxide, hydrogen peroxide gas, water vapor, ozone and/or air, in particular oxygen, preferably with the exclusion of inert gases.
6. The method according to any one or more of the preceding claims, characterized in that the, in particular each, plasma treatment with the plasma generator and/or the, in particular each, application of the metal layer and/or the, in particular each, application of the layer obtained by plasma treatment of organosilicon compounds, in particular polysiloxane layer, is made in the vacuum vapor deposition system or in the sputter system.
7. The method according to any one or more of the preceding claims, characterized in that

   the top layer and/or the primer layer comprise(s) or consist(s) of polyacrylate resins, polyester resins, aminoplast resins or polyurethane compounds and/or

   in that the top layer and/or the primer layer is formed from a UV-curing coating material or a 1K - or 2K stoving varnish, in particular represents a UV-cured top layer or a 1K or 2K stoving varnish top layer and/or

   in that the primer layer and/or the top layer, in particular the top layer, is applied by means of electrostatic painting.
8. The method according to any one or more of the preceding claims, characterized in that the metal layer is applied by means of Physical Vapor Deposition (PVD), Chemical Vapor Deposition (CVD), vapor deposition by means of an electron beam vaporizer, vapor deposition by means of a resistance vaporizer, induction vaporization, ARC vaporization or cathode or anode atomization (sputter coating).
9. The method according to any one or more of the preceding claims, characterized in that the plasma treatment with the plasma generator and/or the treatment with at least one organosilicon compound by means of plasma polymerization, in particular with the formation of a polysiloxane layer, and/or the application of the at least one metal layer with the application system are made under vacuum.
10. The method according to any one or more of the preceding claims, characterized in that the plasma treatment according to step d2) and/or f), in particular d2) is carried out using argon and/or in that the plasma treatment according to step h2) and/or j), in particular j), is carried out using oxygen.
11. A coated metallic or non-metallic substrate, obtained or obtainable by a method according to any one or more of claims 1 to 10, comprising, in this order, preferably immediately consecutive,

    A) a, in particular cleaned, preferably degreased, metallic or non-metallic substrate,

    E) at least one, in particular one, layer formed from at least one organosilicon compound by means of plasma polymerization, in particular a polysiloxane layer,

    G) at least one, in particular one, primer layer, optionally I) at least one, in particular one, layer formed from at least one organosilicon compound, in particular by means of plasma polymerization, in particular a polysiloxane layer,

    K) at least one, in particular one, metal layer applied with an application system by means of vapor deposition and/or sputtering technology,

    M) at least one, in particular one, layer formed from at least one organosilicon compound by means of plasma polymerization, in particular a polysiloxane layer,

    O) at least one, in particular one, in particular transparent and/or colored top layer.
12. Use of the coated metallic or non-metallic substrate according to claim 11 as an accessory for automobile manufacture, motorcycle manufacture, bicycle manufacture or shipbuilding, for rims, in particular light metal rims, wheels, in particular light metal wheels or as a component thereof, for sanitary fixtures, in particular as fittings, or as a component thereof, for interior or exterior body parts 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 housings or as packaging or as a component thereof, for interior or exterior parts of ships or as a component thereof, for household appliances, in particular coffee machines, or components thereof, for jewelry or as a component thereof, for precious parts or as a component thereof, for interior or exterior furniture or for components thereof, for interior or exterior parts of aircraft or as a component thereof, for interior or exterior parts of buildings or as a component thereof, for radiators or pipes or as a component thereof, for parts of elevators or as a component thereof, for parts of electronic components or devices or as a component thereof, for parts of kitchen appliances, for example coffee machines, or as a part of communication components or devices, in particular cell phones, or as a component thereof.