Patent Application
20190255563
The present invention relates to methods for manufacturing coated substrates, coated substrates and the use of these coated substrates.
Metallic and non-metallic components are frequently coated in order to produce a smooth and/or shining surface. As a rule, this involves multilayer coating systems. As well as the desire of obtaining a surface with a high-quality attractive appearance, the intention with such coating systems is regularly also to achieve significant corrosion protection. Not unusually, long-term corrosion protection is brought to nothing by mechanical damage. In many cases, even very slight mechanical damage causes corrosion on coated surfaces. As well as discolouration, this can also result in infiltration phenomena. Not unusually, this in turn leads to the flaking away of areas of coating. There has been no lack of experiments aimed at rendering coated shining surfaces resistant to corrosion. DE 123 765 A1, for example, describes a method for producing a corrosion protection layer on a metallic surface, in which a sol based on silicon compounds, an aminoalkyl-functionalized alkoxysilane or a conversion product of the two aforesaid components is used.
According to DE 38 33 119 C2, a corrosion-protected chromatized metallic surface which adheres very well to a substrate is obtained by an electrodeposition coating being deposited directly onto the chromating layer, without intermediate drying.
Corrosion protection coatings for metallic substrates nevertheless still exhibit a substantial potential for improvement with regard to adherence and corrosion protection, in particular with mass-produced products, in particular those with complex geometries.
The production of coated metallic-appearance substrates with a matt or coloured appearance at low cost and at the same time in high quality has also been shown to be no triviality.
The present invention is therefore based on the object of providing coated substrates which are no longer impaired by the disadvantages of the prior art, and which, in particular with regard to mass production, provide coated products with good corrosion protection and/or very good adherence properties, and which also have a matt or coloured appearance. Here, it is also intended to provide such coated products which do not immediately exhibit infiltration phenomena in the event of mechanical surface damage, in particular not associated with the flaking away of layers.
Accordingly, a method has been found for manufacturing a coated non-metallic substrate, in particular a plastic substrate, comprising
With the method described, the metallic layer, in particular the aluminium layer, is preferably applied in step k) in a thickness, in particular vapour deposited or sputtered on, so that the metallic layer, in particular also in accordance with steps l), m), n), and/or o), is not transparent and not translucent for visible light. It has surprisingly been shown that although the metallic layer is applied in a thickness that is not translucent or even not transparent for visible light, the final product obtained according to this method nevertheless provides a matt appearance. The matt character is accordingly transferred to the applied metallic layer. As a result, the non-metallic substrate obtains according to this method, in particular coated plastic products, are given a very elegant appearance. Here, it is also advantageous that they not only stand out for a high degree of corrosion protection, but also, as is otherwise frequently the case among products with matt surfaces, mechanical influences on the surface do not impair the appearance of this surface. For example, no abrasion or no change to the matt appearance is observed in the places where mechanical influence was made. In a corresponding manner, through the use of a glossy coating, the gloss of the metallic layer applied over it can again be intensified. Any colours required can be used for the creation of a matt or glossy coating. If the metallic layer is applied opaquely, in other words such that it is not transparent for visible light and also not translucent, only the matt or glossy character of the coating is transferred onto the applied metallic layer, but not also the colour of this coating. Persons skilled in the art are familiar with matt and glossy coatings. Matt coatings can for example be obtained using a so-called matting paste.
In the sense of the present invention, such a metallic layer, which is in particular applied using vapour deposition or sputtering technology, is not transparent or translucent, which has a thickness of at least 60, for example in the region of 60 nm to 120 nm, preferably in the range of 75 nm to 110 nm.
Alternatively, in a further, albeit not preferred embodiment, it is possible to apply the metallic layer, in particular the aluminium layer, in step k) in a thickness, in particular using vapour deposition or sputtering, such that said layer is transparent or translucent for visible light. The transparent or translucent metallic layer here preferably has an average, in particular absolute, thickness in the range of 1 nm to 50 nm, preferably in the range of 10 nm to 40 nm, and particularly preferred in the range of 15 nm to 30 nm.
The object that forms the basis of the invention is further attained by use of a method for producing a coated, non-metallic substrate, in particular a plastic substrate, comprising
The transparent or translucent metallic layer in step k′) here preferably has an average, in particular absolute, thickness in the range of 1 nm to 50 nm, preferably in the range of 10 nm to 40 nm, and particularly preferred in the range of 15 nm to 30 nm.
With the method described above, in a preferred embodiment, steps m) and n) are conducted prior to step o).
Adjacent to the transparent or translucent metallic layer (layer k′), on the other side of the overcoat, preferably, the colour layer (layer jj-kk), the colour or coloured polysiloxane layer, the colour or coloured primer layer or the colour or coloured non-metallic substrate are placed. In this manner, very high-quality appearance coating systems are obtained. For example, through the use of a black colour layer or a black coloured non-metallic substrate, which are placed on the transparent or translucent metallic layer, the impression of a black chromium layer can be created.
With the two method variants described above for producing coated non-metallic substrates, e.g. steps d), e) and f) are only optional. In individual cases, they can contribute to improved adherence and increased corrosion protection. The same applies to the optional step i). It has shown for some applications that it is of advantage if a polysiloxane layer is present on both sides of the metallic layer, in particular a plasma-generated polysiloxane layer, which in each case has preferably been subjected to a plasma treatment and/or a corona treatment, in particular plasma treatment.
The optional method variant of applying a primer layer is particularly well-suited for non-metallic substrates, in particular plastic substrates, with a surface which exhibits uneven areas or which is of inferior quality.
With the two methods described above for coating non-metallic substrate, in particular plastic substrates, such method variants have been shown to be advantageous in which
steps g), h), j-k), k), m), n) and o) or g), h), k′), m), n) and o) or g), h), jj-kk), k′), m), n) and o) respectively, in particular directly, follow on from each other, in particular excluding steps d), e) and/or f) or using step d) and excluding step e) and f), or
steps g), h), i), j-k), k), m), n) and o) or g), h), i), k′) m), n) and o) or g), h), i), k!), m), n) and o) respectively, in particular directly, follow on from each other, in particular excluding steps d), e) and/or f) or using step d) and excluding step e) and f), or
steps d), e), f), j-k), k), m), n) and o) or d), e), f), k′), m), n) and o) or d), e), f), jj-kk), k′), m), n) and o) respectively, in particular directly, follow each other or steps d), e), f), i), j-k), k), m), n) and o) or d), e), f), i), k′), m), n) and o) or d), e), f), i), jj-kk), k′), m), n) and o) respectively, in particular directly, follow each other, or steps d), e), f), g), j-k), k), m), n) and o) or d), e), f), g), k′), m), n) and o) or d), e), f), g), jj-kk), k′), m), n) and o) respectively, in particular directly, follow each other, or
steps d), e), t), g), i), j-k), k), m), n) and o) or d), e), f), g), i), k′), m), n) and o) or d), e), f), g), i), jj-kk), k′), m), n) and o) respectively, in particular directly, follow each other.
In a preferred embodiment, it is provided that in each case, before the step of applying the metallic layer k) or k′), the application of an in particular plasma-generated polysiloxane layer (step i)) can be provided. The method variant described heretofore can be applied, in particular, with faultless non-metallic substrates, in particular plastic substrates with faultless smooth surfaces.
In a particularly purposeful embodiment, in particular as specified heretofore, the layer onto which the metallic layer is applied in accordance with step k) or k′), is subjected to a plasma treatment with the plasma generator and/or a corona treatment (e.g. steps j), f) or d)).
It has proved to be of advantage for the method steps referred to heretofore to be applied essentially immediately after one another. This means, in particular, that an extended dwell period after the plasma treatment steps should be avoided. Rather, it is of advantage if the subsequent method step follows directly. It has also shown that it is not generally necessary for further method steps to be interspersed between the method steps referred to heretofore.
In one preferred embodiment, it has also proved to be advantageous, in particular with regard to good adherence and corrosion protection, if the non-metallic substrate, in particular the plastic substrate, is subjected to a plasma treatment and/or corona treatment, in particular plasma treatment (step d)).
Suitable non-metallic substrates comprise glass, ceramic, composite fibre materials, carbon materials, plastic, in particular a preferably coloured plastic, moulded part or a preferably coloured plastic, coating, or wood, in particular wood material panels. Suitable wood material panels comprise e.g. plywood or sandwich panels, chip material panels, OSB panels, MDF panels, fibre material panels, wood material panels made of solid wood or minerally-bonded wood material panels. MDF panels have been shown to be particularly advantageous, such as also in a coloured form. This can for example be achieved by mixing coloured synthetic polymer materials. Wood substrates such as wood material panels, e.g. MDF panels, can stand out through surface restructuring, e.g. in the form of a grain pattern. Non-metallic substrates in the sense of the invention accordingly also comprise coloured non-metallic substrates.
The method according to the invention described here is particularly well-suited for coating plastic substrates for the purpose of obtaining durable high-gloss products. Suitable plastic substrates comprise or consist of, for example, PVC, polyurethanes, polyacrylates, polyesters, e.g. PBT and PET, polyolefins, in particular polypropylene, polycarbonates, polyamides, polyphenylene ethers, polystyrene, styrene (co)polymers, such as ABS, SAN, ASA or MABS, polyoxyalkylenes, e.g. POM, teflon and polymer blends, in particular ABS/PPE, ASA/PPE, SAN/PPE and/or ABS/PC blends. Plastic substrates in the sense of the invention also comprise coatings made of a plastic material, such as MDF panels coated with a plastic material.
The object on which the invention is based is further achieved by a method for manufacturing a coated metallic substrate, comprising
With the method described, the metallic layer, in particular the aluminium layer, is preferably applied in step Q) in a thickness, in particular vapour deposited or sputtered on, so that the metallic layer, in particular also in accordance with steps l), m), n), and/or o), is not transparent and not translucent for visible light. It has surprisingly been shown that although the metallic layer is applied in a thickness that is not translucent or even not transparent for visible light, the final product obtained according to this method nevertheless provides a matt appearance. The matt character is accordingly transferred to the applied metallic layer. As a result, the non-metallic substrate obtains according to this method, in particular coated plastic products, are given a very elegant appearance. Here, it is also advantageous that they not only stand out for a high degree of corrosion protection, but also, as is otherwise frequently the case among products with matt surfaces, mechanical influences on the surface do not impair the appearance of this surface. For example, no abrasion or no change to the matt appearance is observed in the places where mechanical influence was made. In a corresponding manner, through the use of a glossy coating, the gloss of the metallic layer applied over it can again be intensified. Any colours required can be used for the creation of a matt or glossy coating. If the metallic layer is applied opaquely, in other words such that it is not transparent for visible light and also not translucent, only the matt or glossy character of the coating is transferred onto the applied metallic layer, but not also the colour of this coating. Persons skilled in the art are familiar with matt and glossy coatings. Matt coatings can for example be obtained using a so-called matting paste.
With the method described above, in a preferred embodiment, steps S) and T) are conducted prior to step U).
The object on which the invention is based is further achieved by a method for manufacturing a coated metallic substrate, comprising
The transparent or translucent metallic layer in step Q′) here preferably has an average, in particular absolute, thickness in the range of 1 nm to 50 nm, preferably in the range of 10 nm to 40 nm, and particularly preferred in the range of 15 nm to 30 nm.
With the method described above, in a preferred embodiment, steps S) and T) are conducted prior to step U).
Adjacent to the transparent or translucent metallic layer (layer Q′), on the other side of the overcoat, preferably, the colour layer (layer PP-QQ), the colour or coloured polysiloxane layer, the colour or coloured primer layer or the colour or coloured non-metallic substrate are placed. In this manner, very high-quality appearance coating systems are obtained. For example, through the use of a black colour layer or a black coloured primer layer, which are placed on the transparent or translucent metallic layer, the impression of a black chromium layer can be created.
With the method described above for coating non-metallic substrates, in particular plastic substrates, those method variants have been shown to be advantageous, in particular for obtaining highly satisfactory results with regard to adhesion, gloss and/or corrosion resistance, in which
steps D), M), N), P-Q), Q), S), T) and U) or D), M), N), Q′), S), T) and U) or D), M), N), PP-QQ), Q′), S), T) and U) respectively, in particular directly, follow each other, or
steps D), M), N), P-Q), Q), S), T) and U) or D), M), N), O), Q′), S), T) and U) or D), M), N), O), PP-QQ), Q′), S), T) and U) respectively, in particular directly, follow each other, or
steps D), E), F,), M), P-Q), Q), S), T) and U) or D), E), F), M), Q′), S), T) and U) or D), E), F,), M), PP-QQ), Q′), S), T) and U) respectively, in particular directly, follow each other, or
steps D), E), F,), M), O), P-Q), Q), S), T) and U) or D), E), F,), M), O), Q′), S), T) and U) or D), E), F,), M), O), PP-QQ), Q′), S), T) and U) respectively, in particular directly, follow each other, or
steps D), G), H), M), P-Q), Q), S), T) and U) or D), G), H), M), Q′), S), T) and U) or D), G), H), M), PP-QQ), Q′), S), T) and U) respectively, in particular directly, follow each other, or
steps D), O), H), M), O), P-Q), Q), S), T) and U) or D), G), H), M), O), Q′), S), T) and U) or D), G), H), M), O), PP-QQ), Q′), S), T) and U) respectively, in particular directly, follow each other, or
steps D), E), G), H), M), P-Q), Q), S), T) and U) or D), E), G), H), M), Q′), S), T) and U) or D), E), G), H), M), PP-QQ), Q′), S), T) and U) respectively, in particular directly, follow each other, or
steps D), E), G), H), M), O), P-Q), Q), S), T) and U) or D), E), G), H), M), O), Q′), S), T) and U) or D), E), G), H), M), O), PP-QQ), Q′), S), T) and U) respectively, in particular directly, follow each other, or
steps D), M), P-Q), Q), S), T) and U) or D), M), Q′), S), T) and U) or D), M), PP-QQ), Q′), S), T) and U) respectively, in particular directly, follow each other, or steps D), M), O), P-Q), Q), S), T) and U) or D), M), O), Q′), S), T) and U) or D), M), O), PP-QQ), Q′), S), T) and U) respectively, in particular directly, follow each other, or
steps D), G), H), P-Q), Q), S), T) and U) or D), G), H), Q′), S), T) and U) or D), G), H), PP-QQ), Q′), S), T) and U) respectively, in particular directly, follow each other, or
steps D), G), H), O), P-Q), Q), S), T) and U) or D), G), H), O), Q′), S), T) and U) or D), G), H), PP-QQ), O), Q′), S), T) and U) respectively, in particular directly, follow each other.
It has shown for some applications that it is also of advantage in the manufacture of coated metallic substrates if a polysiloxane layer, in particular a plasma-polymerized polysiloxane layer, is present on both sides of the metallic layer, i.e. method step O) is interspersed, preferably with subsequent plasma treatment and/or corona treatment, in particular plasma treatment. It is therefore possible, for example, for the method variant described heretofore also to be provided with step O).
A particularly significant corrosion protection is also obtained with the metallic substrate which is obtainable in accordance with the method according to the invention, if at least one metallic layer is applied onto the metallic substrate cleaned in accordance with step D), or onto the cleaned coatable surface of the metallic substrate, this metallic layer containing or consisting of a second metal, selected from the group consisting of titanium, hafnium and zirconium, in particular zirconium, or of a second metal alloy, selected from the group consisting of alloys of titanium, hafnium and zirconium, with the application system, in particular by use of vapour deposition and/or sputtering technology (step E)). It is particularly advantageous if this metallic layer is subsequently subjected to a plasma treatment step (step F)).
In one particularly purposeful embodiment, the layer onto which the metallic layer is applied in accordance with step Q) or Q′) is subjected to a plasma treatment with the plasma generator and/or a corona treatment (for example, steps P), N), L), J), H), F) or D)) before the step Q) or Q′). This also applies, in particular, to the polysiloxane layer.
It has also proved advantageous, in a preferred embodiment, in particular in relation to good adherence and corrosion protection, if the metallic substrate, in particular the cleaned metallic substrate, is subjected to a plasma treatment and/or a corona treatment, in particular a plasma treatment (step F)).
In many cases, it has therefore proved advantageous if a polysiloxane layer is applied, this layer is then subjected to a plasma treatment and/or a corona treatment, in particular a plasma treatment. The same applies to the application of a primer layer. Here, too, it has proved advantageous when the primer layer obtained is first subjected to a plasma treatment and/or a corona treatment, in particular a plasma treatment.
It has accordingly also proved advantageous in the manufacture of coated metallic substrates according to the inventive method if the method steps referred to heretofore are carried out essentially immediately following one another. This means, in particular, that an extended dwell period after the plasma treatment steps should be avoided. Rather, it is of advantage if the subsequent method step follows directly. It has also shown that it is not necessary for further method steps to be interspersed between the method steps referred to heretofore.
For the metallic substrates, recourse can be made to metals and metal alloys, wherein particularly suitable metallic substrates can be selected from the group consisting of aluminium, aluminium alloys, iron, iron alloys, in particular steel or special 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, die-cast nickel, diecast zinc and die-cast aluminium, or any mixtures thereof.
Suitable methods for cleaning metallic substrates are known to the person skilled in the art. Such cleaning methods (step D)) comprise degreasing, pickling, phosphating, in particular iron phosphating and/or zinc phosphating, polishing, grinding, in particular finish grinding, and/or treating with dry ice. These methods can be used both individually as well as in any desired combination. For many applications it had proved sufficient for the metallic substrates to be cleaned by treating them with dry ice. During cleaning with dry ice, in general, dry ice particles in the form of pellets or in the form of crystals, which have been shaved off an appropriate block of dry ice, are accelerated with the aid of compressed air and directed onto the metallic surface which is to be cleaned. The cleaning effect is assumed to be attributable to thermal, kinetic, and phase transformation effects. Devices and methods for the cleaning of metallic surfaces with dry ice can be found, for example, in DE 195 44 906 A1 and EP 2 886 250.
The surface of metallic substrates can be degreased, for example, with alkaline or acidic reagents. Commercial degreasing steps are also known under the terms of hot alkaline cleaning or pickling cleaning. As an alternative, a metallic surface can be degreased by anode effect in an electrolytic degreasing bath.
For a number of variant embodiments it is advantageous for the metallic substrate surface, in particular the degreased metallic substrate surface, to be subjected to at least one pickling step. For pickling the metallic substrate surface, use is made, for example, of an acidic flushing bath. A suitable pickling solution is provided, for example, by dilute hydrochloric acid (1:10 vol/vol). As a result of pickling, as a rule, a metallic surface is obtained which is essentially free of oxides. Like the degreasing step, the pickling step is, in general, concluded by a flushing step. If the metallic substrate surface is polished and/or ground or finish-ground, it is frequently possible to do without the degreasing step and/or pickling step. With this form of surface treatment, sufficient material is usually removed from this surface for any contamination or other constituents adhering to the surface to be removed together with it. If the surface is polished or ground, it is frequently also possible to omit the application of a first and, optionally, second primer layer. In most cases, polishing or grinding already provides a surface which is sufficiently flat or smooth for further smoothing by the application of a primer layer to be no longer necessary. It may, however, be recommendable for a first and possibly also a second primer step to be added if the metallic substrate has a considerable number of angles and corners, which cannot simply be adequately polished or ground without further ado.
Following or instead of the degreasing step, the metallic substrate surface can be phosphated and/or passivated. This is preferred, in particular, with substrates made of or containing aluminium.
In a further embodiment of the method according to the invention for manufacturing coated metallic substrates, substrates with very particular corrosion resistance can be attained if, in the step of the application of the metallic layer, a first metal, in particular aluminium, or a first metal alloy, in particular an aluminium alloy, is co-vapour deposited in the application system for the application of a metallic layer, in particular the vacuum vapour deposition system or the sputtering system, overlapping in time with a second metal, which is different from the first metal, in particular selected from the group consisting of titanium, zirconium and hafnium, in particular zirconium, or with a second metal alloy, in particular a zirconium alloy, which is different from the first metal alloy. This takes place, for example, in the form that metal pellets or rods of the first metal or the first metal alloy are introduced into an appropriate first reception container, in particular a first boat element or a first helical shaft, and the metal pellets or rods of the second metal or the second metal alloy are introduced into an appropriate second reception container, second boat element or a second helical shaft, and that the first and the second reception container are heated in such a way that the melting points of the first and second metals or of the first and second metal alloys or of the first metal and second metal alloy or of the first metal alloy and second metal are attained and/or maintained essentially simultaneously or within an overlapping period of time.
Suitable aqueous conversion systems, with the aid of which conversion layers are obtained, are familiar to the person skilled in the art. By way of example, reference may be made to the disclosures of U.S. Pat. No. 2,825,697 and U.S. Pat. No. 2,928,763.
For the application of the primer layer, generally known methods are at the disposal of the person skilled in the art. Accordingly, in a preferred embodiment, the primer layer may be based in particular on UV-curing powdery polyester resin compounds or to epoxy/polyester powder. Examples which may be referred to include the wet-coating process, the powder-coating process, or application by use of UV-curing coating systems. It is, of course, also possible, to carry out a mechanical smoothing of the metallic substrate surface, for example by grinding and/or polishing or finish-grinding, before the application of a primer layer, as described heretofore.
Suitable organosilicon compounds are known to the person skilled in art. In one purposeful embodiment, recourse is made for this purpose to at least one amino-containing silane, in particular aminopropyltriethoxysilane, hexamethyldisiloxane, tetramethyldisiloxane, or any mixtures thereof. It is particularly preferred that use is made of hexamethyldisiloxane and tetramethyldisiloxane, wherein hexamethyldisiloxane is regularly particularly well-suited.
Suitable organosilicon compounds likewise comprise, as monomer or as co-monomer structural units, compounds of the following formula (I):
X-Rj-Si(R2)3-m(R3)m (I),
wherein the substituents and indices have the following meaning:
Particularly suitable residues X comprise, for example, vinyl, alkylvinyl, in particular methyl, ethyl or propyl vinyl, (meth)acryloxyalkyl, in particular (meth)acryloxymethyl, (meth)acryloxyethylene or (meth)acryloxypropyl, in particular (meth)acryloxypropyl.
In a further development of the method according to the invention, provision is made for a first organosilicon compound to be delivered to the application system, in particular vacuum chamber, via a feed line from a first container located outside the application system for the application of a metallic layer, in particular outside the vacuum chamber of the vacuum vapour deposition system, and for a second organosilicon compound, which is different from the first organosilicon compound, to be delivered to the application system, in particular vacuum chamber, via a feed line from a second container located outside the application system for the application of a metallic layer, in particular outside the vacuum chamber of the vacuum vapour deposition system. As an alternative, the same organosilicon compound can be present in the first and second container. In particular, it is possible, that, if the same organosilicon compounds are used, one of these organosilicon compounds can be present mixed with a further, different organosilicon compound and/or with a colouring agent, in particular a dye. Accordingly, the methods according to the invention are also characterized in that, together with the at least one organosilicon compound, in particular for the plasma polymerization, at least one colouring agent, in particular a dye, is introduced into the application system for the application of a metallic layer, preferably in the form of a mixture. This latter method variant, comprising the use of a colouring agent, naturally is also successful if only one container is used.
An application system suitable for the implementation of the method according to the invention, for the application of a metallic layer, comprising at least one first container, located in particular outside the application system for the application of a metallic layer, in particular outside the vacuum chamber of the vacuum vapour deposition system, for holding a first organosilicon compound, with a feed line to the application system, in particular to the vacuum chamber, and at least one second container, located in particular outside the application system for the application of a metallic layer, in particular outside the vacuum chamber of the vacuum vapour deposition system, for holding a second organosilicon compound, with a feed line to the application system, in particular to the vacuum chamber.
Particularly good adherence without restrictions with regard to corrosion resistance is also achieved in particular due to the fact that the step of treatment with at least one organosilicon compound, such as hexamethyldisiloxane, in particular by use of plasma polymerization, thus forming a polysiloxane layer, takes place in the presence of at least one reactive gas, such as oxygen, nitrogen, carbon dioxide, hydrogen, carbon monoxide, hydrogen peroxide gas, water vapour, ozone and/or air, in particular in the presence of oxygen or air. By way of the integration of reactive gases, in particular air or oxygen, into the polymerization process, in particular plasma-generated, harder polysiloxane layers are obtained than with the conventional manufacture of such polysiloxane layers, without the concomitant use of the reactive gases described. These harder polysiloxane layers are also characterized by greater diffusion consistency. In this context, in a particularly purposeful embodiment, provision can be made for the at least one organosilicon compound, in particular hexamethyldisiloxane, and the at least one reactive gas, in particular oxygen or air, to be used as a mixture for the treatment step. The embodiment described heretofore of the concomitant use of reactive gases in the production, in particular plasmagenerated, of the polysiloxane layer, is used preferably in at least one step of the treatment with at least one organosilicon compound, in particular by use of plasma polymerization, thus forming a polysiloxane layer, or also with each step for the production of a polysiloxane layer. It is particularly preferred that this method variant is used in the manufacture of coated non-metallic substrates, in particular of plastic substrates, in method step m) and in the manufacture of coated metallic substrates in method step S). In the method steps following those referred to, namely method steps n) and T) respectively, the plasma treatment is preferably carried out with the aid of a plasma gas, formed from an inert gas, in particular argon, and oxygen or air or nitrogen, in particular oxygen, or with the aid of a plasma gas formed from oxygen, air or nitrogen. This procedure again contributes to a better adherence of the total system, including the overcoat.
For the step of the plasma treatment with the plasma generator, there are in principle a number of method variants available for selection. According to a first variant, the plasma can be formed using at least one inert gas, in particular argon. As an alternative, for the generation of a suitable plasma, recourse can also be made to 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 gas, water vapour, ozone and/or air. Use is made here preferably of oxygen and nitrogen, in particular oxygen. Finally, it is also possible to exclude inert gases and to use exclusively reactive gases, such as oxygen, nitrogen, hydrogen, carbon dioxide, carbon monoxide, hydrogen peroxide gas, water vapour, ozone and/or air for the production of the plasma. In this situation, recourse is made preferably to oxygen. With the aid of a plasma treatment with the plasma generator, the surface to be coated of the substrate is activated. In a plasma process, an energy-rich plasma regularly takes effect on the surface of the shaped part such that active centres are formed on this surface. This can involve, for example, hydroxyl groups and/or carbonyl groups. In the same way, an activation of the surface of the substrate surface which is to be coated can be put into effect by flame treatment. In a preferred embodiment, a volatile silane or a compound containing titanium and aluminium can be added to a flame, such as a propane gas flame, which burns in an air atmosphere. Due to the flame application, the surface of the substrate, in particular of a plastic substrate, can be changed in a similar manner as in the plasma process, thus forming hydroxyl groups, for example.
The methods according to the invention provide the great advantage that almost all method steps can be carried out in the application system for the application of a metallic layer. As well as the application of the metallic layers, this also relates to the activation of surfaces by use of the plasma treatment with the plasma generator, as well as to the application of the polysiloxane layer, in particular by use of plasma polymerization. Only the cleaning step, the application of a primer layer, the application of a conversion layer, and the application of the overcoat are regularly carried out outside the application system referred to. Provision can therefore be made that the plasma treatment, in particular each plasma treatment, is carried out with the plasma generator and/or the application, in particular each application, of the metallic layer, and/or the application, in particular each application, of the polysiloxane layer is carried out within the application system for the application of a metallic layer, in particular in the vacuum vapour deposition system or in the sputtering system, and/or that the application of the primer layer and/or the application of the conversion layer and/or the application of the overcoat takes place outside the application system for the application of a metallic layer, in particular of the vacuum vapour deposition system or of the sputtering system.
For the overcoat, for example, recourse can also be made to water-dilutable coating compositions. The overcoat can be formed from polyacrylate resins, polyester resins, aminoplast resins, or polyurethane compounds. Preferably, in the methods according to the invention, such overcoats are applied as are based on a UV-curing coating material. Accordingly, a preferred overcoat is a UV-cured overcoat. The overcoat can be obtained, for example, by use of a clear lacquer or a transparent powder. The overcoat is preferably applied by a wet-lacquer process or a powder coating process. The overcoat can accordingly be, for example, a single-component, two-component, or multi-component lacquer, wherein clear lacquers are preferred. These clear lacquers can be, for example, chemically cross-linking two-component lacquers, single-component heat-curing lacquers, or UV-curing lacquers. In addition, 1K or 2K stoving lacquer can be used for the overcoat.
As a rule, the overcoat has a thickness in the range from 10 to 50 μm, preferably in the range from 20 to 30 μm. Of inventive importance to the method according to the invention is the fact that the material forming the overcoat is applied onto a polysiloxane layer which has been previously activated by use of plasma treatment and/or corona treatment and which was preferably obtained by a plasma polymerization, and preferably essentially without any time delay.
The plasma treatment with the plasma generator is sometimes also described by the term glowing.
For the application of the metallic layers, recourse can be made, for example, to the technologies of Physical Vapor Deposition (PVD), Chemical Vapor Deposition (CVD), vapour deposition by use of an electron beam evaporator, vapour deposition by use of a resistance evaporator, induction vapour deposition, ARC evaporation, or cathode or anode atomization (sputter coating). Accordingly, application systems for the application of a metallic layer preferably include, for example, vacuum vapour deposition systems or sputtering systems. Suitable vacuum vapour deposition systems purposefully comprise PVD systems (Physical Vapor Deposition), CVD systems (Chemical Vapor Deposition), electron beam evaporators, resistance evaporators, induction evaporators, and ARC evaporators. Suitable sputtering systems comprise, for example, cathode atomizers and anode atomizers. As the person skilled in the art knows, a metallic layer consists predominantly of metal. This does not entirely exclude additives, such as are used, for example, with stainless steel in the form of carbon. Preferably, the metal content of the metallic layer in this situation is greater than 90% by weight, in particular 95% by weight, and more particularly 98% by weight.
Preferably, the metallic layer is a vapour-deposited or sputter-applied metallic layer, in particular a PVD metallic layer. In the PVD method, in general, resistance-heated metal helical shaft or metal boat element evaporators are used, wherein tungsten chutes of the most widely differing forms are preferred. In the PVD method, in general, an evaporator is fitted with helical shafts which can be clamped onto evaporator rails which are insulated from one another. Preferably, a precisely determined quantity of metal to be deposited is introduced into each chute. After the PVD system has been closed and evacuated, the evaporation can be started by switching on the power supply, as a result of which the evaporation rails cause the chutes to be brought to a glow. The solid metal begins to melt, and thoroughly wets the chutes, which in most cases are twisted in form. By the further application of energy, the liquid metal is transformed into the gas phase, so that it can then be deposited on the substrate which is to be coated. By way of the quantity of metal transformed into the gas phase, and/or the duration of the coating phase, the thickness of the metallic layer, and therefore also its appearance, can be specifically adjusted.
A further preferred method for depositing the metallic layer onto the substrate is cathode atomization (sputtering). Here, a cathode is arranged in an evacuated container and connected to the negative pole of a current supply. The coating material which is to be atomized is arranged directly in front of the cathode, and the substrates which are to be coated are arranged opposite the coating material which is to be atomized. In addition, argon can be conveyed, as the process gas, through the container, which also comprises an anode which is connected to the positive pole of a current supply. Once the container has been pre-evacuated, the cathode and anode are connected to the current supply. Due to the targeted and controlled intake of argon, the average free path length of the charge carriers is significantly reduced. Argon atoms are ionised in the electrical field between the cathode and anode. The positively charged particles are accelerated with high energy towards the negatively charged cathode. On impinging, and due to particle impacts in the coating material, this material is transformed into the vapour phase, accelerates with high energy into the free space, and then condenses on the substrates which are to be coated. Sputtering allows for different metallic layer thicknesses to be specifically adjusted.
A colouring of the coating present on the non-metallic and metallic substrates can also be accomplished with the methods according to the invention, if a coating material is used for the application of the overcoat which contains at least one colouring agent, e.g. at least one pigment and/or at least one dye. Glazes, which are known to the person skilled in the art, can also be used in order to colour the overcoat, such as to obtain, for example, brass, titanium and gold colour shades, or individual colour shades such as red, blue, yellow, green, etc., or anodized colour shades. For example, effect pigments can also be introduced into the overcoat, such as pearl gloss pigments, LCP (liquid crystal polymer) pigments or OV (optical variable) pigments.
The object that forms the basis of the invention is further attained by a coated, non-metallic substrate, in particular a coated plastic substrate, preferably obtained or obtainable according to a method according to the invention, comprising, in this order,
The metallic layer advantageously has a thickness that is not transparent and not translucent for visible light. Such a metallic layer can also be described as opaque. A metallic layer is not transparent in the sense of the present invention when, applied onto the substrate or onto a layer present on the substrate, details of the substrate or the layer are not recognisable, i.e. the metallic layer is not vision permeable. A metallic layer is not translucent in the sense of the present invention when, applied onto the substrate or onto a layer present on the substrate, details of the substrate or the layer are not recognisable, i.e. the metallic layer is not light impermeable. In other words, a translucent metallic layer is light permeable, but not vision permeable. With a translucent metallic layer, e.g. the colour of the substrate or the coating lying underneath can be recognised.
The object that forms the basis of the invention is further attained by a coated, non-metallic substrate, in particular a coated plastic substrate, preferably obtained or obtainable according to a method according to the invention, comprising, in this order,
The transparent or translucent metallic layer advantageously has an average, in particular absolute, thickness in the range of 1 nm to 50 nm, preferably in the range of 10 nm to 40 nm, and particularly preferred in the range of 15 nm to 30 nm.
With the coated non-metallic substrate described above, such an embodiment is preferred in which a polysiloxane layer is present between the metallic layer and the coating layer which is obtained by use of plasma polymerisation of at least one organosilicon compound, which has also been plasma and/or corona-treated.
Additionally, such an embodiment variant is preferred in which adjacent to the metallic layer obtained by use of the vapour deposition and/or sputtering technology, the colour layer, the colour or coloured polysiloxane layer, the colour or coloured primer layer of the colour or coloured non-metallic substrate is present.
Particularly attractive, in particular elegant, surfaces can here also be achieved in that the non-metallic substrate, at least one polysiloxane layer, the primer layer, the matt or glossy coat, the colour layer, the metallic layer and/or the coating layer, in particular the matt or glossy coating or the colour layer, have a structured surface.
The object that forms the basis of the invention is further attained by a coated metallic substrate, in particular obtained or obtainable according to a method according to the invention, comprising, in this order,
The metallic layer adjacent to the cover layer, in particular the aluminium layer, is advantageously not transparent and not translucent for visible light.
With the coated metallic substrate described above, such an embodiment is preferred in which a polysiloxane layer is present between the metallic layer and the coating layer which is obtained by use of plasma polymerisation of at least one organosilicon compound, which has also been plasma and/or corona-treated.
The object that forms the basis of the invention is finally also attained by a coated metallic substrate, in particular obtained or obtainable according to a method according to the invention, comprising, in this order,
The metallic layer adjacent to the cover layer here, in particular the aluminium layer, is here preferably present in an average, in particular absolute, thickness in the range of 1 nm to 50 nm, preferably in the range of 10 nm to 40 nm, and particularly preferred in the range of 15 nm to 30 nm.
With the coated metallic substrate described above, such an embodiment is preferred in which a polysiloxane layer is present between the metallic layer and the coating layer which is obtained by use of plasma polymerisation of at least one organosilicon compound, which has also been plasma and/or corona-treated.
Additionally, such an embodiment variant is preferred in which adjacent to the metallic layer obtained by use of the vapour deposition and/or sputtering technology, the colour layer, the colour or coloured polysiloxane layer, the colour or coloured primer layer of the colour or coloured conversion layer is present.
Here, in an advantageous design, the metallic substrate, the at least one metallic layer, the at least one polysiloxane layer, the conversion layer, the primer layer, the matt or glossy coating, the colour layer and/or the overcoat, in particular the matt or glossy layering or the colour layer, has a structured surface.
For the colour layer, such as the one that could be used in method steps jj-kk and PP-QQ and as can be found in the coated substrates obtainable in accordance with the method according to the invention, recourse can be made to 2K lacquer systems, 1K lacquer systems and UV lacquer systems.
An application system for the application of a metallic layer is comprised or represented by a vacuum vapour deposition system with a vacuum chamber, and at least one, in particular a plurality of, first heatable reception units, in particular trays, boat elements or helical shafts, in each case operatively coupled with a first heating device or comprising or representing a first heating device, in each case configured and suitable for the reception of a first metal or a first metal alloy with a first melting point or melting range, and at least one, in particular a plurality of, second heatable reception units, in particular trays, boat elements, or helical shafts, in each case operatively coupled with a second heating device or comprising or representing a second heating device, in each case configured and suitable for the reception of a second metal or a second metal alloy with a second melting point or melting range, wherein the first melting point or the first melting range are different from the second melting point or second melting range, and, in addition, a control device for the adjustment of first and second temperatures in such a way that the first and the second metal or the first and second metal alloy evaporate essentially simultaneously or overlapping in time (co-evaporation).
Here, provision can be made in one embodiment variant that the application system for the application of a metallic layer comprises at least one first container, located in particular outside the vacuum chamber of the vacuum vapour deposition system, for receiving a first organosilicon compound, with a feed line to the vacuum chamber, and at least one second container, located in particular outside the vacuum chamber of the vacuum vapour deposition system for receiving a second organosilicon compound, with a feed line to the vacuum chamber.
It has proved particularly purposeful for the application system for the application of a metallic layer to be also equipped with at least one frame, in particular arranged within the vacuum chamber, with a longitudinal orientation and with at least one support, in particular in the form of a shaft, which is aligned essentially along the longitudinal orientation of the frame, designed and configured to receive at least one, in particular a plurality of, non-metallic and/or metallic substrates, wherein the frame and/or the at least one support is/are capable of being rotated about an axis. Suitable frames which can be used with the application system can be found, for example, in EP 2 412 445 and DE 20 2007 016 072.
The non-metallic and metallic substrates which are obtainable with the method according to the invention can be used, for example, as accessories for automobile manufacture, motorcycle manufacture, bicycle manufacture or shipbuilding, for rims, in particular light metal alloy rims, wheels, in particular light metal alloy wheels, or as a constituent part thereof, for sanitary installation objects, in particular as a tap or mixer, or as a constituent part thereof, for automobile body internal or external components or as a constituent part thereof, for handles or handle components, in particular door handles, or as a constituent part thereof, for profiles or frames, in particular window frames, or as a constituent part thereof, for fittings systems or as a constituent part thereof, in particular signs and door signs, for housings or as packing or as a constituent part thereof, for internal or external components of ships or as a constituent part thereof, for jewellery items or as a constituent part thereof, for high-quality structural components or as a constituent part thereof, for indoor or outdoor furniture items, such as kitchen, office or home furniture, for domestic appliances, in particular coffee-making machines, or as a constituent part thereof, for internal or external components of aircraft or as a constituent part thereof, for internal or external components of buildings or as a constituent part thereof, for heating elements or pipes or as a constituent part thereof, for elevator components or as a constituent part thereof, for parts of electronic components or devices or as a constituent part thereof, for components of kitchen appliances, for example coffee-making machines, or as a part of communications components or devices, in particular mobile telephones, or as a constituent part thereof.
Additionally, the object that forms the basis of the invention is attained by a method for producing a coated non-metallic substrate, in particular a plastic substrate, comprising
The method described above differs from the corresponding method according to the invention in that step k) has been replaced by step k″) (opaque application of at least one effect lacquer with a metallic colour impression). In the same manner, the coated non-metallic substrates obtainable according to the method described above differ from those coated non-metallic substrates obtainable according to the corresponding method, containing step k), by the replacement of the metallic layer by the effect lacquer which is opaquely applied, with a metallic colour impression. The general and preferred specific features and embodiment variants, which have been described above for the method containing step k) and the coated products obtainable according to this method, apply in the same manner to the method containing step k″) or the coated products obtainable according to this method.
Additionally, the object that forms the basis of the invention is attained by a method for producing a coated non-metallic substrate, in particular a plastic substrate, comprising
The method described above differs from the corresponding method according to the invention in that step k′) has been replaced by step k′″) (application of at least one effect lacquer such that the obtained coating is transparent or translucent for visible light). In the same manner, the coated non-metallic substrates obtainable according to the method described above differ from those coated non-metallic substrates obtainable according to the corresponding method, containing step k′), by the replacement of the metallic layer by the effect lacquer which is applied with a metallic colour impression such that it is transparent or translucent for visible light. The general and preferred specific features and embodiment variants, which have been described above for the method containing step k′) and the coated products obtainable according to this method, apply in the same manner to the method containing step k′″) or the coated products obtainable according to this method.
Additionally, the object that forms the basis of the invention is attained by a method for producing a coated metallic substrate, comprising
The method described above differs from the corresponding method according to the invention in that step Q) has been replaced by step Q″) (opaque application of at least one effect lacquer with a metallic colour impression). In the same manner, the coated non-metallic substrates obtainable according to the method described above differ from those coated metallic substrates obtainable according to the corresponding method, containing step Q), by the replacement of the metallic layer by the effect lacquer which is opaquely applied, with a metallic colour impression. The general and preferred specific features and embodiment variants, which have been described above for the method containing step Q) and the coated products obtainable according to this method, apply in the same manner to the method containing step Q″) or the coated products obtainable according to this method.
Finally, the object that forms the basis of the invention is attained by a method for producing a coated metallic substrate, comprising
The method described above differs from the corresponding method according to the invention in that step Q′) has been replaced by step Q′″) (application of at least one effect lacquer such that the obtained coating is transparent or translucent for visible light). In the same manner, the coated metallic substrates obtainable according to the method described above differ from those coated metallic substrates obtainable according to the corresponding method, containing step Q′), by the replacement of the metallic layer by the effect lacquer which is applied with a metallic colour impression such that it is transparent or translucent for visible light. The general and preferred specific features and embodiment variants, which have been described above for the method containing step Q′) and the coated products obtainable according to this method, apply in the same manner to the method containing step Q′″) or the coated products obtainable according to this method.
Effect lacquers that provide a metallic appearance are known to a person skilled in the art. Such effect lacquers regularly use so-called metallic effect pigments or metal pigments, e.g. based on aluminium. Suitable effect lacquers or effect pigments are described e.g. in DE 10 2007 007908, WO 2004/026971, WO 2004/026972, DE 4422287 and DE 19505161. A further example of effect and chromium lacquers by Endlendt Color, D-16775 Sonnenberg, is e.g. disclosed in WO 2008/046567 A 1, and reference is made to HS effect lacquers by Holtmann & Stierle Chemie GmbH, D-32130 Enger.
The invention is based on the surprising finding that with the substrates obtainable in accordance with the method according to the invention, surfaces with a matt metallic appearance can equally be obtained as colourful metallic surfaces, and in a simple and reliable, i.e. low-cost, manner. The methods according to the invention are easily suitable for mass production. They make it possible to develop entirely new fields of application for plastic and metallic substrates. Furthermore, with the method according to the invention or with the products according to the invention, a high-quality coloured glossy coating can be provided that permanently retains its gloss. In addition, the coated non-metallic and metallic substrates obtainable with the method according to the invention are provided with excellent corrosion resistance. The coated substrates obtainable with the methods according to the invention are further characterized by very good adherence. Accordingly, these coated substrates exhibit outstanding resistance to corrosion even when the surfaces have suffered mechanical damage, for example by stone impact or scratching. It is also advantageous that with the substrates according to the invention with a matt appearance, no impairment to the surface can be detected with mechanical stress. A further advantage which is inherent with the method according to the invention is that only very short changeover times are required in order to coat new substrate batches. Furthermore, the method according to the invention allows the scope of the entire system for manufacturing coated substrates with a colourful or matt appearance, starting from the substrate which has not yet been cleaned and is to be coated, to be substantially reduced, such that a significantly reduced space is required in relation to conventional systems. In addition, it is possible with the methods according to the invention to substantially reduce the processing time up to completion of the coated substrate ready for sale. Reduced cycle times are necessarily inherent with this.
The features of the invention disclosed in the foregoing description and in the claims can be essential for the implementation of the invention in its different embodiments, both individually as well as in any combination.
| Number | Date | Country | Kind |
|---|---|---|---|
| 16163054.6 | Mar 2016 | EP | regional |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/EP2017/057484 | 3/30/2017 | WO | 00 |
