DE10103460B4 - Multilayer plasma polymer coating, process for its preparation and its use - Google Patents

Abstract

Multilayered plasma polymer coating on a substrate, containing one after the other in the order indicated:
(A) at least one layer located on at least one surface of the substrate, which can be produced by treating the metallic surface of the substrate or at least one layer comprising at least one metal oxide with a plasma containing water and / or carbon dioxide on the metallic surface of the substrate; and
(B) at least one layer of at least one plasma polymer preparable by plasma polymerization of the following starting compounds in the order given:
(B1) at least one elemental organic compound,
(B2) at least one mixture of at least one elemental organic compound (B1) and at least one organic compound (B3) and
(B3) at least one organic compound.

Description

The The present invention relates to a novel multilayer plasma polymer coating on a substrate. Furthermore The present invention relates to a novel process for the preparation multilayer plasma polymer coatings. Furthermore it concerns the present invention the use of the new multilayered Plasma polymer coating as anticorrosion coatings and adhesive layers.

reactive Use metals such as steel, zinc, aluminum, magnesium, titanium, copper and the alloys of at least two of these metals draw through a thinnest oxide skin or cover layer formed in the air from, the z. B. the corrosion behavior of the metal both in the uncoated as well as in the coated state significantly affected. exemplary will be referred to the dissertation by A. Leng, "Investigations on the Delamination of polymer-coated Iron surfaces ", progress reports VDI, Series 5, No. 416, VDI-Verlag, Dusseldorf, 1995, the dissertation by W. Furbeth, "Investigations to the Delamination of polymer coatings on galvanized steel surfaces ", progress reports VDI, Series 5, No. 512, VDI-Verlag, Dusseldorf, 1995, or the article by W. Fürbeth, G. Grundmeier and M. Stratmann, "Enthaftung Organic Coatings of Metal Surfaces ", Paint + Varnish, Volume 102, Issue 11, pages 78 to 84, 1996.

By a targeted thickening or transformation of this oxide skin or cover layer novel properties of the metal surface in terms of paint adhesion, Corrosion properties, conductivity or usability. It could in investigations be shown that the method of glow discharge or the plasma technology an advantageous method for such a modification of the cover layer represents on the metals. So far, however, have been in plasma technology mainly Oxygen, argon or hydrogen plasmas for cleaning the metal surface and used to thicken or reduce the natural oxide layer. For example, reference is made to the articles by W. J. van Ooji, A. Sabata, D.B. Zeik, C.E. Taylor, F.F. Boerio and S.J. Clarson, "Metal Surface Preparation by Plasma-Polymerized Films ", Journal of Testing and Evaluation, Vol. 23, pages 33 to 40, W.J. van Ooji and K. D. Conners, "Corrosion Performance of Electrocoated Cold-Rolled Steels Pretreated with Plasma Polymerized Organic Films ", Proceedings of the Electrochemical Society, 95, No. 13, pages 229 to 242, 1995, T.F. Wang, T.J. Lin, D.J. Yang, J.A. Antonelli and H. K. Yasuda, "Corrosion Protection of Cold-Rolled Steel by Low Temperature Plasma Interface Engineering, 1st Enhancement of E-Coat Adhesion, Progress in Organic Coatings, Volume 28, pages 291 to 297, 1996, H.K. Yasuda, T.F. Wang, D.L. Choj. J. Lin and J.A. Antonelli, "Corrosion Protection of Cold-Rolled Steel by Low Temperature Plasma Interface Engineering, II. Effects of Oxides on Corrosion Perfomance of E-Coated Steels, "Progress in Organic Coatings, Volume 30, pages 31 to 38, 1997, and G. Grundmeier and M. Stratmann, "Influence of Oxygen and Argon Plasma Treatments on the Chemical Structure and Redox State of Oxide Covered Iron ", Applied Surface Science, Volume 141, Pages 43 to 56, 1999. A targeted attitude of chemical structure of the surface layer and its electronic properties, the above the mere Cleaning, thickening or reduction of the oxide layer goes, but has not been done yet.

• (A) mindestens eine auf mindestens einer Stahloberfläche befindliche Schicht aus Eisenoxid und
• (B) mindestens eine Schicht mindestens eines Plasmapolymeren, herstellbar durch Plasmapolymerisation der folgenden Ausgangsverbindungen in der angegebenen Reihenfolge: (B1) Hexamethyldisilazan, (B2) ein Gemisch aus Hexamethyldisilazan und Cyclohexen sowie (B3) Cyclohexen;

ist aus der Dissertation von G. Grundmeier, "Grenzflächenchemische und korrosionsanalytische Untersuchungen von Plasmapolymerbeschichtungen auf Stahl", Technische Fakultät der Universität Erlangen-Nürnberg, 1997, bekannt. Diese bekannte mehrschichtige Plasmapolymerbeschichtung weist bereits gute Korrosionsschutzeigenschaften auf und verbessert die Haftung zwischen der Stahloberfläche und einer hierauf befindlichen Lackierung. Die bekannte mehrschichtige Plasmapolymerbeschichtung muss aber noch weiterentwickelt werden, damit sie auch auf anderen reaktiven Gebrauchsmetallen als Eisen oder Stahl mit Vorteil verwendet werden kann.A multi-layered plasma polymer coating on steel, overlaid in the order given:

• (A) at least one located on at least one steel surface layer of iron oxide and
• (B) at least one layer of at least one plasma polymer preparable by plasma polymerization of the following starting compounds in the order indicated: (B1) hexamethyldisilazane, (B2) a mixture of hexamethyldisilazane and cyclohexene and (B3) cyclohexene;

is known from the dissertation of G. Grundmeier, "Interface Chemical and Corrosion Analytical Investigations of Plasma Polymer Coatings on Steel", Faculty of Engineering of the University of Erlangen-Nürnberg, 1997. This known multilayer plasma polymer coating already has good anti-corrosion properties and improves the adhesion between the steel surface and a coating thereon. However, the known multilayer plasma polymer coating must be further developed so that it can also be used with advantage on other reactive use metals than iron or steel.

Object of the present invention is therefore to provide a new multi-layered plasma polymer coating, which is tailored to the reactive metal used in each case, so that the Kor anti-corrosion properties and adhesion on both the respective metal surfaces and on a further plasma polymer layer, adhesive layer, coating, film or foam layer located on the plasma polymer coating can be further improved. The substrates coated with the new multilayer plasma polymer coating are said to be particularly suitable for the manufacture of moldings used in such technically demanding fields as the manufacture of automobiles, aircraft, ships, furniture, doors, windows, linings for interior structures. and outdoor, components and housings are used for machines of any kind or containers and Emballagen.

• (A) mindestens eine auf mindestens einer Oberfläche des Substrats befindliche Schicht, die durch die Behandlung der metallischen Oberfläche des Substrats oder mindestens einer auf der metallischen Oberfläche des Substrats befindlichen Schicht aus mindestens einem Metalloxid mit einem Wasser und/oder Kohlendioxid enthaltenden Plasma herstellbar ist, und
• (B) mindestens eine Schicht mindestens eines Plasmapolymeren, herstellbar durch Plasmapolymerisation der folgenden Ausgangsverbindungen in der angegebenen Reihenfolge: (B1) mindestens eine elementorganische Verbindung, (B2) mindestens ein Gemisch aus mindestens einer elementorganischen Verbindung (B1) und mindestens einer organischen Verbindung (B3) und (B3) mindestens eine organische Verbindung.

Accordingly, the novel multilayer plasma polymer coating, found on a substrate, was superposed in the order given:

• (A) at least one layer located on at least one surface of the substrate, which can be produced by treating the metallic surface of the substrate or at least one layer comprising at least one metal oxide with a plasma containing water and / or carbon dioxide on the metallic surface of the substrate; and
• (B) at least one layer of at least one plasma polymer preparable by plasma polymerization of the following starting compounds in the order given: (B1) at least one elemental organic compound, (B2) at least one mixture of at least one elemental organic compound (B1) and at least one organic compound (B3 ) and (B3) at least one organic compound.

in the The following is the new multilayer plasma polymer coating on a substrate for the sake of brevity referred to as "plasma polymer coating according to the invention".

• (I) mindestens eine metallische Oberfläche eines Substrats oder eine auf mindestens einer metallischen Oberfläche eines Substrats befindliche Schicht mindestens eines Metalloxids mit einem Wasser und/oder Kohlendioxid enthaltenden Plasma behandelt, wodurch die Schicht (A) resultiert, wonach man auf der Oberfläche dieser Schicht (A)
• (II) mindestens eine Schicht (B) mindestens eines Plasmapolymeren durch Plasmapolymerisation der folgenden Ausgangsverbindungen in der angegebenen Reihenfolge abscheidet: (B1) mindestens eine elementorganische Verbindung, (B2) mindestens ein Gemisch aus mindestens einer elementorganischen Verbindung (B1) und mindestens einer organischen Verbindung (B3) und (B3) mindestens eine organische Verbindung.

In addition, the novel process for the preparation of a multilayer plasma polymer coating by plasma (pre) treatment and plasma polymerization was found in which

• (I) treating at least one metallic surface of a substrate or a layer of at least one metal oxide of a substrate containing at least one metal oxide with a plasma containing water and / or carbon dioxide, whereby the layer (A) results, after which on the surface of this layer ( A)
• (II) at least one layer (B) of at least one plasma polymer deposited by plasma polymerization of the following starting compounds in the order given: (B1) at least one elemental organic compound, (B2) at least one mixture of at least one elemental organic compound (B1) and at least one organic compound (B3) and (B3) at least one organic compound.

in the Following is the new process for making a multilayer Plasma polymer coating by plasma (pre) treatment and plasma polymerization of brevity half referred to as "inventive method".

Further Go according to the invention from the description.

in the In view of the prior art, it was surprising and for the expert unpredictable that in the context of the method according to the invention the addition of water and / or carbon dioxide to glow discharges or plasmas, as they usually do for cleaning the metal surface before the plasma polymerization of organometallic compounds and / or organic compounds are used, especially stable Coatings on the respective metal surfaces led, in particular in their anti-corrosion properties and their adhesion properties on the one hand, and the metal substrate on the other On the other hand, plasma polymer layers were excellently tuned. Especially surprising was that these valuable properties also apply to other plasma polymer layers, Emitting adhesive layers, coatings, foils or foam layers, the with the outer surface of the Plasma polymer coating according to the invention could be connected particularly adherent. The corresponding composite materials or laminates were therefore for the use in the most different technological fields excellent. Even more surprised the excellent Deformability of the substrates with the new multilayer Plasma polymer coating were coated, as well as the corresponding Composite materials or laminates.

The Plasma polymer coating according to the invention is on a substrate.

The Substrate can be made of different metals or metallized Materials exist. Preferably, it consists of reactive use metals or from metals metallized with reactive utility metals.

Examples suitable reactive utility metals are iron, steel, zinc, aluminum, Magnesium, titanium and the alloys of at least two of these metals. Zinc is particularly suitable as such or in the form of a galvanized steel surface.

Examples suitable materials that have a metallized surface, are natural occurring or synthetic, organic and inorganic materials such as plastics, glass, ceramics, wood, paper, leather and composites of these materials.

The Substrates can represent the most varied three-dimensional moldings, such as car bodies or parts thereof, ship hulls, aircraft parts, Furniture, doors, Windows, panels for Structures, components and housings for machines, Containers or packaging. Preferably, however, the moldings are plate-shaped or band-shaped (Coils).

The Plasma polymer coating according to the invention contains at least one layer (A).

According to the invention is at least a surface of the substrate covered with this layer (A). Especially in the case of plate or band-shaped Substrates can be covered on both sides.

To In a first variant, the layer (A) can be produced by the metallic surface the substrate containing a water and / or carbon dioxide Plasma treated, creating a layer (A) of the relevant Metal hydroxides, Metallcarbona th or a mixture of metal hydroxides and metal carbonates is built up. If the plasma is still oxygen contains For example, layer (A) may also contain the corresponding metal oxides. As the metals, preferably, the reactive ones described above Use metals, but especially zinc used.

To A second variant, which is preferred according to the invention, is the layer (A) preparable by at least one, in particular one, layer from at least one, especially one, metal oxide with the water and / or plasma containing carbon dioxide. Here can the metal that makes up the metal oxide differs from that of the substrate be; It is according to the invention however advantageous if the same metal is used. In addition, can the metal oxide layer is the "natural" surface layer of the metal or alloy in question, such as it arises when the metallic surface comes into contact with air. Or but the metal oxide layer is made by the treatment of metallic surface built up with an oxygen-containing plasma. As metal oxides preferably the oxides of the reactive use metals described above, but especially zinc oxide, used. The layers (A) exist of metal oxide and metal hydroxide, metal oxide and metal carbonate or metal oxide, metal hydroxide and metal carbonate.

The Thickness of the layer (A) is preferably 1 to 10, preferably 1.5 to 9, more preferably 2 to 8 and especially 2.5 to 6 nm.

For the plasma treatment can the usual and known methods are used, as described in the beginning cited references are described in detail.

The Plasma polymer coating according to the invention contains furthermore, at least one layer (B) of at least one plasma polymer.

The Plasma polymer layer (B) can be prepared by adding at least one organometallic compound, (B1), at least one mixture (B2) from at least one elemental organic compound (B1) and at least an organic compound (B3) and at least one organic Compound (B3) plasma-polymerized in the order given.

It is according to the invention beneficial to the outer surface of the resulting plasma polymer layer (B) with a plasma that at least contains a non-plasma polymerizable compound (C) to treat causing the outer surface with is provided with reactive functional groups.

As elemental organic compounds (B1) are all customary and known organometallic Compounds of main group and subgroup elements which are volatile enough to be subjected to plasma polymerization.

Preferably the elemental organic compounds (B1) are selected from the group consisting of organosilicon and organophosphorus, preferably organosilicon compounds, selected. In particular, the elemental organic compounds (B1) from the group consisting selected from trialkylsilanes and hexaalkyldisilanes. she preferably contain alkyl groups having 1 to 4 carbon atoms, in particular methyl groups. Accordingly, trimethylsilane and hexamethyldisilane, in particular hexamethyldisilane, according to the invention particularly preferred as organometallic Compounds (B1) used.

When Organic compound (B2) are all organic compounds considering that fleeting are enough to be subjected to plasma polymerization. Preferably the organic compounds (B2) are selected from the group consisting from aliphatics, cycloaliphatic, olefins and cycloolefins and their halogenated, preferably perhalogenated and in particular perfluorinated Derivatives selected.

Examples suitable aliphatics are methane, ethane or propane and their perfluorinated ones Derivatives.

Examples suitable cycloaliphatic compounds are cyclopropane, cyclobutane, cyclopentane or cyclohexane and its perfluorinated derivatives.

Examples suitable olefins are ethylene, propylene, butene, pentene or hexene and their perfluorinated derivatives.

Examples suitable cycloolefins are cyclopentene or cyclohexene and their perfluorinated derivatives.

From Cyclohexene offers particular advantages and is therefore particularly preferred according to the invention preferably used.

The non-plasma polymerizable compounds (C) are preferably from the group consisting of oxygen, nitrogen and water and their mixtures.

Examples for reactive functional groups obtained by the treatment of the outer surface of the plasma polymer layer (B) resulting in the plasma containing the compounds (C), are peroxide groups, hydroperoxide groups, carbonyl groups, carboxyl groups, Peroxocarbonsäuregruppen, Amino and imino groups and amide groups.

The Plasma polymer layer (B) may vary depending on its method of preparation be constructed.

So can in it, starting from the layer boundary between the layers (A) and (B), the concentration of the elemental organic compounds (B1) continuously decrease plasma polymers and the Concentration of the prepared from the organic compounds (B3) Plasma polymers increase continuously.

In addition, starting from the layer boundary between the layers (A) and (B), the concentration of organometallic compounds (B1) plasma polymers gradually decrease and the concentration the plasma polymers prepared from the organic compounds (B3) in stages increase. In the simplest case, a layer results from a evenly or largely uniformly composed Plasma polymers produced from organometallic compounds (B1) is a layer of a uniform or largely evenly composite Plasma polymers, which can be prepared from the mixture (B2), and a Layer of a uniform or largely uniformly composed Plasma polymers which can be prepared from organic compounds (B3).

The gradual concentration gradient and the continuous concentration gradient may overlap. Thus, for example, within the layer (B2), the concentrations of the plasma polymers which can be prepared from the organometallic compounds (B1) and from the organic compounds (B3) can change from "bottom to top" in the manner described above. Furthermore, the boundaries between the layers (B1) and (B2) and / or the layers (B2) and (B3) may be fluid, that is, transition zones exist in which the concentrations change continuously until a uniform or wide going even composition of the layer (B2) and / or (B3) sets.

The relationship the thicknesses of the layers (B1), (B2) and (B3) can vary widely. Preferably, the layers of in about the same or the same thickness.

Similarly Thickness of the plasma polymer layer (B) may vary widely. Preferably it is 3 to 100, preferably 4 to 80, particularly preferred 5 to 60, most preferably 6 to 50 and especially 7 to 40 nm.

methodical seen, the preparation of the plasma polymer layer (B) offers no Specifics, but takes place according to the usual and known plasma polymerization and devices as described in the cited prior Technology will be described in detail. Preference is given to the plant, as described in the article by G. Grundmeier - and M. Stratmann, "Plasma Polymerization - a New and Promising Way for the Corrosion Protection of Steel ", Materials and Corrosion, Volume 49, pages 150 to 160, 1998, and the method as described in the dissertation by G. Grundmeier, "Grenzflächenchemische und korrosionsanalytische Investigation of Plasma Polymer Coatings on Steel ", Faculty of Engineering, University Erlangen-Nürnberg, 1997, pages 140 and 141.

• (I) mindestens eine metallische Oberfläche des Substrats oder eine auf mindestens einer metallischen Oberfläche des Substrats befindliche Schicht mindestens eines Metalloxids mit einem Wasser und/oder Kohlendioxid enthaltenden Plasma behandelt, wodurch die Schicht (A) resultiert, wonach man auf der Oberfläche dieser Schicht (A)
• (II) mindestens eine Schicht (B) mindestens eines Plasmapolymeren durch Plasmapolymerisation der folgenden Ausgangsverbindungen in der angegebenen Reihenfolge abscheidet: (B1) mindestens eine elementorganische Verbindung, (B2) mindestens ein Gemisch aus mindestens einer elementorganischen Verbindung (B1) und mindestens einer organischen Verbindung (B3) und (B3) mindestens eine organische Verbindung.

The plasma polymer coating of the invention can be prepared by a variety of methods of plasma (pre) treatment and plasma polymerization. Preferably, it is prepared by the process according to the invention. This will be

• (I) at least one metallic surface of the substrate or a layer of at least one metal oxide of the substrate located on at least one metal oxide with a plasma containing water and / or carbon dioxide treated, whereby the layer (A) results, after which on the surface of this layer ( A)
• (II) at least one layer (B) of at least one plasma polymer deposited by plasma polymerization of the following starting compounds in the order given: (B1) at least one elemental organic compound, (B2) at least one mixture of at least one elemental organic compound (B1) and at least one organic compound (B3) and (B3) at least one organic compound.

there are the starting compounds and methods given above the plasma polymerization and plasma (pre) treatment used.

The inventive method can be carried out continuously or discontinuously.

In a first preferred variant of the method according to the invention can the starting compounds (B1), (B2) and (B3) by sequential Plasma polymerization are deposited so that a gradual Gradient results. This variant of the method according to the invention is preferably carried out continuously.

In a further preferred variant of the method according to the invention become in the course of the process, the concentration of the starting compounds (B1) lowered and the concentration of the starting compounds (B3) raised. It can the concentrations are changed gradually or continuously. This variant of the method according to the invention is especially suitable for the discontinuous preparation of the plasma polymer coating according to the invention in a reactor. The adjustment of the concentrations can thereby by suitable gas guidance respectively.

Preferably becomes the method according to the invention by treating the outer surface of the inventive polymer coating with a plasma that is at least one of those described above contains non-plasma polymerizable reactive compounds (C), modified.

For the inventive method it is further advantageous if, before the production of the layer (s) (A) at least one surface of the substrate and / or the layer located thereon of at least a metal oxide purified by pretreatment with a plasma becomes. Preferably, an argon plasma is used for this purpose.

In addition, it is advantageous for the process according to the invention if the layer of at least one metal oxide is treated by treating the surface of the substrate with an oxygen-containing plasma ma builds up.

Preferably be in the inventive method band-shaped Substrates used, which are coated on one side or both sides can. It can which applied on the two sides of the band-shaped substrates Plasma polymer coatings according to the invention of materially different composition and / or of different Be layered structure.

Preferably becomes the sequential method according to the invention with band-shaped substrates applied, wherein the above-described gradual concentration gradients result.

For the sequential inventive method can the most diverse devices are used. It is according to the invention beneficial to use a device that has a modification cell and at least three successive coating cells includes. The outward gastight cells are protected by or transport rollers separated gas tightly from each other. Should the band-shaped Substrates are coated on both sides, the cells respectively two opposing reaction spaces, the gas-tight through the continuously continuous substrate from each other are separated.

In In the apparatus, the modification cell may include at least one cleaning cell upstream, wherein at least one surface of the substrate or the on at least one surface of the substrate located layer of at least one metal oxide is purified by plasma pretreatment.

In addition, can the cleaning cell or the first coating cell at least an oxidation cell upstream, wherein at least one surface of the substrate at least one layer of at least one metal oxide by treating the substrate surface with an oxygen-containing Plasma is generated.

Of the Oxidation cell may further comprise at least one cleaning cell upstream, wherein the substrate surface by plasma pretreatment is cleaned.

The Coating cells may further comprise at least one aftertreatment cell in which the surface of the layer (B) with a Plasma containing at least one non-plasma polymerizable reactive Contains compound (C), is treated.

The Device contains furthermore usual and known feeder devices and discharge devices for the output connections the plasma polymerization and for other substances such as inert gases, devices for generating vacuum, Heat, cold and plasma, gas-tight locks, mechanical and electrical motors, conveyors for the Substrate and the starting compounds as well as the other substances, mechanical, pneumatic magnetic and electronic measuring and Control devices, sealing devices and calender rolls, presses and winders and possibly cutting devices for with the plasma polymer coatings according to the invention coated substrates and optionally their derivatives, the laminates according to the invention described below.

• (1) in der Modifizierungszelle mindestens eine Oberfläche des Substrats oder die auf mindestens einer Oberfläche des Substrats befindliche Oxidschicht mit einem Wasser und/oder Kohlendioxid enthaltenden Plasma behandelt, wodurch die Schicht (A) resultiert,
• (2) in der ersten Beschichtungszelle auf der Schicht (A) eine Schicht (B1) durch Plasmapolymerisation mindestens einer elementorganischen Verbindung (B1) erzeugt,
• (3) in der zweiten Beschichtungszelle auf der Schicht (B1) eine Schicht (B2) durch Plasmapolymerisation mindestens eines Gemischs (B2) aus mindestens einer elementorganischen Verbindung (B1) und mindestens einer organischen Verbindung (B3) erzeugt und
• (4) in der dritten Beschichtungszelle auf der Schicht (B2) eine Schicht (B3) durch Plasmapolymerisation mindestens einer organischen Verbindung (B3) erzeugt.

In the method according to the invention is in the device

• (1) treating in the modifying cell at least one surface of the substrate or the oxide layer on at least one surface of the substrate with a plasma containing water and / or carbon dioxide, whereby the layer (A) results,
• (2) in the first coating cell on the layer (A) produces a layer (B1) by plasma polymerization of at least one elemental organic compound (B1),
• (3) in the second coating cell on the layer (B1) produces a layer (B2) by plasma polymerization of at least one mixture (B2) of at least one elemental organic compound (B1) and at least one organic compound (B3) and
• (4) in the third coating cell on the layer (B2) generates a layer (B3) by plasma polymerization of at least one organic compound (B3).

• (5) die Nachbehandlung der erfindungsgemäßen Plasmapolymerbeschichtung in der Nachbehandlungszelle abgeschlossen.

Preferably, the inventive method is

• (5) completing the post-treatment of the plasma polymer coating of the invention in the post-treatment cell.

According to the invention, it is advantageous to plasma polymer coatings according to the invention, esp in particular the aftertreated plasma polymer coatings according to the invention, immediately after their production with a further plasma polymer layer, an adhesive layer, a coating, a film or a foam layer adherent to connect.

suitable Further plasma polymer layers can, for example, from above-described starting compounds (B1) and / or (B3) getting produced.

suitable Adhesive layers can for example, from the usual and known one- or multi-component adhesives are produced.

suitable Paintings can for example, from usual and known, pigmented and unpigmented, physically curable, thermally self-crosslinking curable, thermally externally curable, radiation-curable or thermal and radiation-curable (Dual cure) electrocoating, conventional or aqueous Single or multi-component paints, essentially or completely and solvent-free liquid Single or multi-component paints (100% systems), essentially or completely water and solventless solid one- or multi-component powder coatings or aqueous Dispersions of the solid in or Mehrkornponentenpulflacke (powder slurries) are produced.

Examples of suitable films are from the German patent applications DE 195 35 934 A1 . DE 195 17 069 A1 . DE 195 17 067 A1 or DE 195 17 068 A1 or the European patent applications EP 0 352 298 A1 . EP 0 285 071 A1 or EP 0 266 109 A1 known.

suitable Foam layers are made of foams i. S. of DIN 7726: 198205. These are materials with distributed throughout their mass open and / or closed cells and a bulk density lower is that of the scaffold substance. Preferably, elastic and soft elastic foams i. S. of DIN 53580 (see also Römpp Lexicon Chemistry, CD-ROM: Version 2.0, Georg Thieme Verlag, Stuttgart, New York, 1999, "Foams").

The laminates according to the invention from the substrates, the plasma polymer coatings of the invention and the other plasma polymer layers, adhesive layers, coatings, Films, and foam layers, but especially the laminates of the invention from substrates, plasma polymer coatings according to the invention and coatings, have excellent performance properties, in particular excellent corrosion resistance even after mechanical Injury and excellent intercoat adhesion. Besides, they are the laminates according to the invention deformable without being mechanically damaged and their excellent corrosion resistance and interlayer adhesion can be reduced.

The laminates according to the invention are therefore to a great extent for the Production of moldings suitable, as in the production of automobiles, aircraft, ships, furniture, doors, windows, panels for buildings indoors and outdoors, Components and housings for machines any kind or container and packaging are used.

Examples and Comparative Experiments

Production Example 1

The production of a zinc hydroxide-containing layer (A1) on a zinc surface

An argon plasma cleaned zinc surface was exposed to a microwave glow discharge generated by a linear source in a pure water atmosphere. The presence of the hydroxide groups was detected by FTIR spectroscopy using the characteristic signals of the HO groups and the Zn (OH) ₂ groups in addition to the ZnO group signal.

The measurement of the electronic properties of the layer (A) by means of the raster Kelvin probe according to the article by G. Grundmeier and M. Stratmann, "Influence of Oxygen and Argon Plasma Treatments on the Chemical Structure and Redox State of Oxide Coated Iron", Applied Surface Science, Vol. 141, pages 43 to 56, 1999, found that their electronic structure (measured potential E: -200 mV) differs from that in the CD state before the plasma treatment (measured potential E: -1000 mV) and that in the Condition significantly lower after treatment with an oxygen-containing plasma (measured potential E: +100 mV) difference.

Production Example 2

The production of a zinc carbonate-containing layer (A2) on a zinc surface

An argon plasma-cleaned zinc surface was exposed to a microwave glow discharge generated by a linear source in a carbon dioxide atmosphere. The presence of the carbonate groups could be detected by FTIR spectroscopy on the basis of the characteristic signal of the ZnCO ₃ groups in addition to the signals of the Zn (OH) ₂ groups and the ZnO groups. Photoelectron spectra (ESCA) of layer (A2) showed the characteristic signal of carbon in carbonate (CO ₃ ^2- ), corresponding to a binding energy of 290.5 eV.

The Measurement of the electronic properties of the layer (A2) by means of the grid Kelvin probe according to the article by G. Grundmeier and M. Stratmann, "Influence of Oxygen and Argon Plasma Treatments on the Chemical Structure and Redox State of Oxide Covered Iron ", Applied Surface Science, Volume 141, pages 43 to 56, 1999, found that their electronic structure (measured potential E: ± 0 mV) from that in the state before the plasma treatment (measured Potenti al E: -1,000 mV) and in the state after treatment with a oxygen-containing plasma (measured potential E: + 100 mV) substantially difference.

Production Example 3 (Comparison)

The production of a Zinc oxide layer on a zinc surface

An argon plasma-cleaned zinc surface was exposed to a microwave glow discharge generated by a linear source in a pure oxygen atmosphere. This resulted in a zinc oxide layer with a thickness of 5 nm. The oxidic nature of the layer could be detected by means of FTIR spectroscopy on the basis of the characteristic signal of the ZnO groups. Signals from HO groups and Zn (OH) ₂ groups were not observed.

The Measurement of the electronic properties of the zinc oxide layer by means of the raster Kelvin probe according to the article by G. Grundmeier and M. Stratmann, "Influence of Oxygen and Argon Plasma Treatments on the Chenücal Structure and Redox State of Oxide Covered Iron ", Applied Surface Science, Volume 141, Pages 43 to 56, 1999, revealed that their electronic structure (measured potential E: +100 MV) from that of the layer (A1) (measured Potential E: -200 mV) and of the layer (A2) (measured potential E: ± 0 mV) significantly different.

Examples 1 and 2 and Comparative experiment V 1

The preparation of plasma polymer coatings according to the invention (Examples 1 and 2) and a non-inventive plasma polymer coating (Comparative experiment V 1)

For the example 1 became the substrate with the layer (A1) of the preparation example 1 used.

For the example 2 became the substrate with the layer (A2) of the preparation example 2 used.

For the comparative experiment V 1 became the substrate with the layer (A3) of the preparation example 3 used.

The Plasma polymer layers (B) of Examples 1 and 2 and the comparative experiment V 1 were used under the same conditions in the plant as in the article by G. Grundmeier and M. Stratmann, "Plasma Polymerization - a New and Promising Way For The Corrosion Protection Of Steel ", Materials And Corrosion, Vol 49, pages 150 to 160, 1998. It was the plasma polymer according to the thesis by G. Grundmeier, "Interface Chemical and corrosion analysis of plasma polymer coatings on steel ", Technical Faculty the University Erlangen Nuremberg, 1997, pages 140 and 141. The process parameters are to see Table 1.

Table 1: Separation of plasma polymers (B) and their functionalization with oxygen plasma (C)

It resulted plasma polymer coatings according to the invention (Examples 1 and 2) and a non-inventive plasma polymer coating (Comparative experiment V 1) with plasma polymer layers (B) of a thickness of 20 nm.

Examples 3 and 4 and Comparative experiment V 2

The production of laminates according to the invention (Examples 3 and 4) and non-inventive laminates (Comparative Experiments V 2 and V 3)

For the example 3 became the substrate with the plasma polymer coating according to the invention, used in Example 1.

For the example 4 became the substrate with the plasma polymer coating according to the invention used in Example 2.

For the comparative experiment V 2 became the substrate with the plasma polymer coating not according to the invention of Comparative Experiment V 3 used.

For the comparative experiment V 3 used a substrate that was not coated with a plasma polymer was provided.

Plasma polymer coatings of Examples 3 and 4 and Comparative Experiments V 2 and V 3 were partially covered with an adhesive tape immediately after their preparation, after which the adhesive tape and the free surface of the polymer coatings (Examples 3 and 4 and Comparative Experiment V 2) and the free metal surface (Comparative Experiment V 3) were coated with a two-component clearcoat based on epoxy-amine. After curing of the paint layers, the adhesive tapes were peeled off. Since the coatings did not adhere to the adhesive tapes, defined defects resulted at the boundary between plasma polymer coating and coating (Examples 3 and 4 and Comparative Experiment V 2) or between the metal surface and the coating (Comparative Experiment V 3). After filling the defects with 0.5 M saline, the delamination of the coatings was measured by spatially resolved measurements of the respective undercrossing speed using the raster Kelvin probe. The lower the sub-migration speed was, the higher the anticorrosion effect and the inter-layer adhesion. For details, the dissertation by A. Leng, "Studies on the Delamination of polymer-coated iron surface" Progress Reports VDI, Series 5, No. 416, VDI-Verlag, Dusseldorf, 1995, especially pages 18 to 28, the dissertation of W. Fürbeth, "Studies on the Delamination of Polymer Coatings on Galvanized Steel Surfaces", Progress Reports VDI, Series 5, No. 512, VDI-Verlag, Dusseldorf, 1995, especially pages 36 to 38, or the article by W. Furbeth, G. Grundmeier and M. Stratmann, "Enthaftung organic coatings of metal surfaces", paint + paint, Volume 102, Issue 11, pages 78 to 84, 1996, referenced.

This resulted in the following order of sub-migration speed:
Laminate V 3 >> Laminate V 2> Laminates Examples 3 and 4.
In addition, the laminates of Examples 3 and 4 could be deformed without damage by deep drawing.

Claims (38)

Multilayer plasma polymer coating on a substrate containing, in order, superimposed: (A) at least one located on at least one surface of the substrate Layer caused by the treatment of the metallic surface of the Substrate or at least one on the metallic surface of the substrate layer of at least one metal oxide with a water and / or plasma containing carbon dioxide can be produced, and (B) at least one layer of at least one plasma polymer, can be produced by plasma polymerization of the following starting compounds in the order given: (B1) at least one organoelement Connection, (B2) at least one mixture of at least one organometallic compound (B1) and at least one organic Compound (B3) and (B3) at least one organic compound. Plasma polymer coating according to claim 1, characterized characterized in that the outer surface of the Layer (B) with a plasma containing at least one non-plasma polymerizable contains reactive compound (C), has been modified. A plasma polymer coating according to claim 1 or 2, characterized in that the metal oxide of the layer (A) is the oxide of a reactive utility metal. Plasma polymer coating according to one of claims 1 to 3, characterized in that the layer (A) on a metallic surface of the substrate is located. Plasma polymer coating according to claim 4, characterized characterized in that it is the surface of at least one reactive Use metal acts. Plasma polymer coating according to one of claims 3 to 5, characterized in that the utility metal is selected from the group consisting of steel, iron, zinc, aluminum, magnesium, Titanium and the alloys of at least two of these metals. Plasma polymer coating according to claim 6, characterized characterized in that the functional metal is zinc. Plasma polymer coating according to one of claims 1 to 7, characterized in that the organometallic compound (s) (B1) from the group consisting of organosilicon and organophosphorus Connections selected will or will. Plasma polymer coating according to claim 8, characterized characterized in that at least one organosilicon compound (B1) from the group consisting of trialkylsilanes and hexaalkyldisilanes, is used. Plasma polymer coating according to one of claims 1 to 9, characterized in that the organic compound (s) (B2) from the group consisting of aliphatics, cycloaliphatic, olefins and cycloolefins and their halogenated derivatives or will. Plasma polymer coating according to claim 10, characterized in that as organic compound (B2) at least one Cycloolefin is used. Plasma polymer coating according to one of claims 1 to 11, characterized in that the non-plasma-polymerizable reactive compound (C) from the group consisting of oxygen, Nitrogen and water and mixtures thereof, is selected. Plasma polymer coating according to claim 12, characterized characterized in that the non-plasma polymerizable reactive compound Oxygen is. Plasma polymer coating according to one of claims 1 to 13, characterized in that, starting from the layer boundary between the layers (A) and (B), within the layer (B) the Concentration of the organometallic compounds (B1) produced Plasma polymers decreases continuously and the concentration of from the organic compounds (B3) produced plasma polymers continuously increases. Plasma polymer coating according to one of claims 1 to 13, characterized in that, starting from the layer boundary between the layers (A) and (B), within the layer (B) the Concentration of the organometallic compounds (B1) produced Plasma polymers gradually decreases and the concentration of plasma polymers prepared from the organic compounds (B3) gradually increases. Plasma polymer coating according to one of claims 1 to 15, characterized in that the layer (A) 1 to 10 nm thick is. Plasma polymer coating according to one of claims 1 to 16, characterized in that the layer (B) 3 to 100 nm thick is. Plasma polymer coating according to one of claims 1 to 17, characterized in that the substrate is plate-shaped or band-shaped. Process for producing a multilayered Plasma polymer coating according to a the claims 1 to 18 by plasma (pre) treatment and plasma polymerization, thereby marked that one (I) at least one surface of the Substrate or a located on at least one surface of the substrate Layer of at least one metal oxide with a water and / or Carbon dioxide-containing plasma is treated, causing the layer (A) results after which, on the surface of this layer (A) (II) at least one layer (B) of at least one plasma polymer Plasma polymerization of the following starting compounds in the specified Sequence separates: (B1) at least one organoelement Connection, (B2) at least one mixture of at least one organometallic compound (B1) and at least one organic Compound (B3) and (B3) at least one organic compound. Method according to claim 19, characterized that the starting compounds (B1), (B2) and (B3) by sequential Plasma polymerization are deposited. Method according to claim 19 or 20, characterized in the course of the plasma polymerization, the concentration of the starting compounds (B1) lowered and the concentration of the starting compounds (B3) be raised. Method according to claim 21, characterized that the concentrations change gradually or continuously. Method according to one of claims 19 to 22, characterized that the outer surface of the Layer (s) (B) with a plasma containing at least one non-plasma polymerizable contains reactive compound (C), is modified. Method according to one of claims 19 to 23, characterized in that at least one prior to the preparation of the layer (s) (A) surface of the substrate and / or a layer of at least a metal oxide by pretreatment with a plasma cleans. Method according to one of claims 19 to 24, characterized that the layer of at least one metal oxide by treatment the surface of the substrate builds up with an oxygen-containing plasma. Method according to one of claims 19 to 25, characterized in that one is a band-shaped Substrate (coil) used. Method according to claim 26, characterized in that that the substrate by at least one gas-tight to the outside Modification cell and at least three consecutive, outward gas-tight coating cells by guide or transport rollers are gas-tight separated from each other, leads and one-sided or double-sided with a plasma polymer coating, wherein (1) in the modification cell at least one metallic surface of the Substrate or on at least one metallic surface of the Substrate located layer of at least one metal oxide with treated plasma containing a water and / or carbon dioxide which results in layer (A), (2) in the first Coating cell on the layer (A) a layer (B1) by plasma polymerization at least one elemental organic compound (B1) is produced, (3) in the second coating cell on the layer (B1) a layer (B2) by plasma polymerization of at least one mixture (B2) at least one elemental organic compound (B1) and at least an organic compound (B3) is generated and (4) in the third coating cell on the layer (B2) a layer (B3) by plasma polymerization of at least one organic compound (B3) is generated. Method according to Claim 27, characterized that the substrate on both sides with a plasma polymer coating provides, wherein the substrate, the respective opposite reaction spaces of the Modification cell and the first to third coating cells separated gas-tight from each other. Method according to Claim 28, characterized that on both sides of the substrate plasma polymer coatings are generated, which differ materially from each other. Method according to one of claims 27 to 29, characterized that the modification cell upstream of at least one cleaning cell wherein is located on at least one surface of the substrate Layer of at least one metal oxide by plasma pretreatment is cleaned. Method according to one of claims 27 to 30, characterized that the first coating cell or the cleaning cell at least an oxidation cell is connected upstream, wherein at least one surface of the substrate at least one layer of at least one metal oxide by treating the substrate surface with an oxygen-containing Plasma is generated. Method according to claim 30, characterized in that that the oxidation cell upstream of at least one cleaning cell where is the substrate surface is purified by plasma pretreatment. Method according to one of claims 27 to 32, characterized that the coating cells at least one post-treatment cell downstream is where the surface is the layer (B) with a plasma, the at least one non-plasma polymerizable Contains compound (C), is treated. Use of the multilayer plasma polymer coating according to one the claims 1 to 18 and / or according to the method according to any one of claims 19 to 33 produced multilayer plasma polymer coating as Korossionsschutzschicht for the Substrate and / or as an adhesive layer between the substrate and a another plasma polymer layer, an adhesive layer, a coating, a film or a foam layer. Use according to claim 34, characterized in that the substrate is molded parts made from reactive use metals and metals metallized with reactive utility metals is. Use according to claim 35, characterized that the metallized materials are plastics, Glass, ceramics, wood, paper, leather and composites of these materials is. Use according to one of claims 34 to 36, characterized that the molded parts are plates or strips (coils) is. Use according to claim 37, characterized that the moldings of the production of automobiles, aircraft, Ships, furniture, Doors, Windows, panels for Buildings in the interior and exterior, Components and housings for machines serve any kind or container and packaging.