EP1266048A2 - Dyed conversion layer - Google Patents

Dyed conversion layer

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Publication number
EP1266048A2
EP1266048A2 EP01929258A EP01929258A EP1266048A2 EP 1266048 A2 EP1266048 A2 EP 1266048A2 EP 01929258 A EP01929258 A EP 01929258A EP 01929258 A EP01929258 A EP 01929258A EP 1266048 A2 EP1266048 A2 EP 1266048A2
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EP
European Patent Office
Prior art keywords
radicals
coating according
layer
carbon atoms
dye
Prior art date
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Granted
Application number
EP01929258A
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German (de)
French (fr)
Other versions
EP1266048B1 (en
Inventor
Peter Kurze
Marco Kohler
Ulrike KRÜGER
Dora Banerjee
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Electro Chemical Engineering GmbH
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Electro Chemical Engineering GmbH
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/50—Multilayers
    • B05D7/51—One specific pretreatment, e.g. phosphatation, chromatation, in combination with one specific coating
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/82—After-treatment
    • C23C22/84—Dyeing
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/18—After-treatment, e.g. pore-sealing
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/30—Anodisation of magnesium or alloys based thereon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2202/00—Metallic substrate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2202/00—Metallic substrate
    • B05D2202/20—Metallic substrate based on light metals
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
    • C23C2222/20—Use of solutions containing silanes

Definitions

  • the present invention relates to a multilayer coating comprising a conversion layer arranged on a metal and a coloring layer located on this conversion layer, and to the use thereof.
  • conversion layer is understood here and below to mean a layer which is not formed by application to a metallic surface, but rather by chemical conversion (conversion) of this metallic surface and various constituents of an aqueous passivation electrolyte (cf. H. Simon, M Thoma "Applied surface technology for metallic materials", Carl Hanser Verlag, Kunststoff (1985) p. 4).
  • the conversion layer has different functions. For example, it protects the metal from chemical or mechanical influences such as Corrosion or abrasion.
  • the industrially best-known processes for producing conversion layers are the electrolytic formation of oxide layers on light metals, in particular on aluminum, magnesium and titanium (as for example in EP 0 333 048, DD 289 065, DE 41 24 730, DE 41 39 006, DE 196 80 596, DE 197 50 836 or DE 197 51 256) and the chromating, chromitizing or phosphating of ferrous metals.
  • the dyes are mostly salt compounds based on metal complex compounds, as described for example in DE 35 14 387 AI.
  • a major disadvantage of this method is that the chemical and mechanical properties deteriorate as a result of the dye being incorporated into the conversion layer.
  • Another previously known possibility is the production of a conversion layer, followed by a color of this conversion layer
  • DE 729 723 discloses the blackening of phosphate surfaces by applying a solution to a phosphated steel layer, the solution containing as a dye an organic dye soluble in organic solvents and as a binder polyvinyl acetate and synthetic shellac
  • DE 800 200 discloses the application of a protective layer by treating a magnesium object having a conversion layer with a color solution which additionally contains a resin or synthetic resin dissolved in t ⁇ chlorethylene or alcohol
  • EP 0 488 280 describes a multi-layer coating consisting of a steel sheet as a metallic carrier, a first zinc-containing layer applied to the steel surface, a second layer obtained by chromating and a third and last layer, obtainable by thermal crosslinking of a non-aqueous solution from a polymer-based binder and a dye
  • the object of the present invention is to provide a colored multilayer coating on metals, this coating should not have any worse properties in terms of corrosion resistance and mechanical abrasion than a conventional, non-colored conversion layer
  • a multilayer coating with at least two layers, the first layer being a conversion layer located on a metal and having pores and the second layer located on the conversion layer being obtainable by applying a solution to the conversion layer, the solution being at least an alkoxysilane compound and a dye contains, followed by subsequent polymerization and / or crosslinking of the alkoxysilane compound.
  • the conversion layer must have pores.
  • the layer containing the dye must have an alkoxysilane compound as the compound to be polymerized and / or crosslinked.
  • the size and frequency of the pores in a conversion layer essentially depends on the metal and the conversion process used.
  • the size of the pores of a magnesium oxide layer, produced by the process described in EP 0 333 048 AI is between 200 and 1,000 nm; the pore size of an aluminum oxide layer (according to DE 41 39 006), however, is between 50 and 100 nm.
  • the choice of the dye has a further, essential influence on adequate adhesion between the conversion and polymer layers.
  • the dye is in dissolved form in the solution containing at least one alkoxysilane compound; in particular, the dye should be soluble in tetraethoxysilane.
  • the solubility characteristic of the dye to be used according to the invention precludes the use of insoluble pigments (such as, for example, carbon black, titanium dioxide or iron oxide).
  • the polymer layer is formed by polymerization processes known per se and familiar to the person skilled in the art (e.g. air drying, heating or UV radiation):
  • the amount of alkoxysilane compound and dye in the solution to be applied can vary within wide limits.
  • the solution contains 5 to 45 wt .-%, in particular 10 to 30 wt .-% of the alkoxysilane compound and 2 to 15 wt .-% of Dye.
  • the solution can also contain a polar solvent, which should be selected so that the dye is dissolved and the solvent does not react with the alkoxysilane compound (eg ethanol).
  • the alkoxysilane compound corresponds to the general formula
  • X represents an alkoxy, an aryloxy or an acyloxy group with 1 to 12 carbon atoms, preferably with 1 to 4 carbon atoms, and is particularly selected from the group of methoxy, ethoxy, n-propoxy, i-propoxy, Butoxy, phenoxy, acetoxy and propionyloxy groups;
  • R 1 and R 2 are selected from the group of
  • Alkyl radicals in particular the alkyl radicals having 1 to 6 carbon atoms, preferably the methyl, ethyl, n-propyl, isopropyl, n-butyl, s-butyl, t-butyl, pentyl, hexyl or cyclohexyl radicals;
  • Alkenyl residues in particular alkenyl residues with 2 to 6 carbon atoms, preferably vinyl, 1-propenyl, 2-propenyl or butenyl residues;
  • Alkynyl radicals in particular the alkenyl radicals having 2 to 6 carbon atoms, preferably the acetylenyl or propargyl radicals;
  • Aryl radicals in particular aryl radicals having 6 to 10 carbon atoms, preferably phenyl or naphtenyl radicals;
  • Epoxy residues in particular the epoxy residues with 3 to 16 carbon atoms, preferably the glycidyl, glycidyl ether, glycidyl ester or glycidyl oxyalkyl residues; or group X described above; and
  • a and b represent the value 0, 1, 2 or 3, the sum of a and b not exceeding 3.
  • a corresponding alkoxysilane compound can be a tetraalkoxysilane, epoxyalkoxysilane or aminoalkoxysilane.
  • a particularly suitable compound is an alkoxytitanium compound, a titanium acid ester or a titanium chelate, in particular a compound of the formula Ti (OR) 4 , in which R represents an alkyl radical having 1 to 6 carbon atoms, which is preferably selected from the group consisting of methyl, ethyl , n-propyl, i-propyl and butyl radicals.
  • R represents an alkyl radical having 1 to 6 carbon atoms, which is preferably selected from the group consisting of methyl, ethyl , n-propyl, i-propyl and butyl radicals.
  • Very good results have been achieved with tetraethoxytitanate Ti (OC, H,) ( The molar ratio of the alkoxysilane compound to the titanium compound is not critical and is generally between 1 and 20.
  • Solutions containing both an alkoxysilane and contain a group capable of forming a titanium complex compound are described for example in DE 41 38 218 Al and are available from various companies (for example Deltacoll ® 80 from the company. Dörken).
  • An especially in the context of the present invention to be used dye is a metal complex dye as pon, for example, under the trade designation Neoza- ® by the company. BASF, Orasol "from Messrs. Ciba-Geigy, Savinyl ® by the company. Sandoz or Lampronol ® is sold by ICI.
  • all metals which are capable of forming a conversion layer can be used as the metal.
  • particularly preferred are light metals, in particular aluminum, magnesium or an alloy containing aluminum and / or magnesium, which displace steel and its alloys in many areas due to their low specific weight.
  • conversion layers in particular electrochemically obtainable, are used as conversion layers.
  • the invention further relates to the use of a solution for producing a multilayer coating according to the invention, this solution comprising at least one of the alkoxysilane compounds described above and a dye which is soluble in a polar solvent.
  • the invention further relates to the use of the multilayer coating described above as a corrosion and abrasion-resistant protective coating for parts of the motor vehicle industry, electrical and electronics industry, mechanical engineering industry, aerospace and for parts of sports equipment.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electrochemistry (AREA)
  • Wood Science & Technology (AREA)
  • Mechanical Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Paints Or Removers (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Laminated Bodies (AREA)
  • Control Of El Displays (AREA)
  • Magnetic Heads (AREA)
  • Electroluminescent Light Sources (AREA)
  • Optical Filters (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Coloring (AREA)

Abstract

The invention relates to a multilayer coating consisting of a conversion layer which is located on a metal and a layer with a dyeing effect which is located on said conversion layer; and to the use thereof. According to the invention, the conversion layer has pores and the second layer located on the conversion layer is obtained by applying a solution containing at least one alkoxysilane compound and a dye which is soluble in a polar solvent, then polymerising and/or cross-linking the alkoxysilane compound.

Description

"Gefärbte Konversionsschicht' 'Colored Conversion Layer'
Die vorliegende Erfindung betrifft einen Mehrschichtüberzug aus einer auf einem Metall angeordneten Konversionsschicht und einer auf dieser Konversionsschicht befindlichen, farbgebenden Schicht sowie dessen Verwendung.The present invention relates to a multilayer coating comprising a conversion layer arranged on a metal and a coloring layer located on this conversion layer, and to the use thereof.
Auf Metallen befindliche Konversionsschichten sind weit verbreitet. Unter dem Begriff "Konversionsschicht" wird hier und im folgenden eine Schicht verstanden, die nicht durch Auftrag auf eine metallische Oberfläche, sondern durch chemische Umwandlung (Konversion) dieser metallischen Oberfläche und verschiedenen Bestandteilen eines wäßrigen Passivierungselektrolyten gebildet wird (vgl. H. Simon, M. Thoma "Angewandte Oberflächentechnik für metallische Werkstoffe", Carl Hanser Verlag, München (1985) S. 4).Conversion layers on metals are widespread. The term “conversion layer” is understood here and below to mean a layer which is not formed by application to a metallic surface, but rather by chemical conversion (conversion) of this metallic surface and various constituents of an aqueous passivation electrolyte (cf. H. Simon, M Thoma "Applied surface technology for metallic materials", Carl Hanser Verlag, Munich (1985) p. 4).
Je nach Art des Metalls und des Verfahrens zur Erzeugung der Konversionsschicht hat die Konversionsschicht unterschiedliche Funktionen. So schützt sie beispielsweise das Metall vor chemischen oder mechanischen Einflüssen wie z.B. Korrosion oder Abrieb. Die industriell bekanntesten Verfahren zur Erzeugung von Konversionsschichten sind die elektrolytische Bildung von Oxidschichten auf Leichtmetallen, insbesondere auf Aluminium, Magnesium und Titan (wie beispielsweise in der EP 0 333 048, DD 289 065, DE 41 24 730, DE 41 39 006, DE 196 80 596, DE 197 50 836 oder DE 197 51 256 beschrieben) sowie das Chromatieren, Chromitieren oder auch das Phosphatieren von eisenhaltigen Metallen.Depending on the type of metal and the method for producing the conversion layer, the conversion layer has different functions. For example, it protects the metal from chemical or mechanical influences such as Corrosion or abrasion. The industrially best-known processes for producing conversion layers are the electrolytic formation of oxide layers on light metals, in particular on aluminum, magnesium and titanium (as for example in EP 0 333 048, DD 289 065, DE 41 24 730, DE 41 39 006, DE 196 80 596, DE 197 50 836 or DE 197 51 256) and the chromating, chromitizing or phosphating of ferrous metals.
Des weiteren ist es bekannt, diese Konversionsschichten zur Herstellung dekorativer Überzüge einzufärben.It is also known to color these conversion layers for the production of decorative coatings.
Eine solche Möglichkeit ist durch Verwendung eines Passivierungselektrolyts offenbart, der bereits einen entsprechenden Farbstoff enthält.Such a possibility is disclosed by using a passivation electrolyte which already contains a corresponding dye.
Insbesondere zum Einfärben von eloxierten Aluminiumoberflächen wird dieses Verfahren heute noch sehr oft angewendet. Bei den Farbstoffen handelt es sich meistens um Salzverbindungen auf Basis von Metallkomplexverbindungen, wie sie beispielsweise in der DE 35 14 387 AI beschrieben sind.This process is still very often used today, particularly for coloring anodized aluminum surfaces. The dyes are mostly salt compounds based on metal complex compounds, as described for example in DE 35 14 387 AI.
Ein wesentlicher Nachteil bei diesem Verfahren ist, dass sich durch die Einlagerung des Farbstoffes in die Konversionsschicht deren chemische und mechanische Eigenschaften verschlechtern. Eine weitere vorbekannte Möglichkeit ist die Herstellung einer Konversionsschicht, gefolgt von einem Farben dieser KonversionsschichtA major disadvantage of this method is that the chemical and mechanical properties deteriorate as a result of the dye being incorporated into the conversion layer. Another previously known possibility is the production of a conversion layer, followed by a color of this conversion layer
Ein wesentliches Problem ist aber die unzureichende Abnebbestandigkeit des Farbstoffes auf der KonversionsschichtA major problem, however, is the insufficient resistance to fading of the dye on the conversion layer
Schon lange hat es Versuche gegeben, diese mangelnde Abnebbestandigkeit entweder durch Aufbringen einer weiteren Schutzschicht auf die gefärbte Konversionsschicht oder durch Aufbringen einei gef rbten Schutzschicht auf die nicht gefärbte Konversionsschicht zu verbessernAttempts have long been made to improve this lack of resistance to abrasion either by applying a further protective layer to the colored conversion layer or by applying a colored protective layer to the non-colored conversion layer
So offenbart die DE 729 723 die Schwärzung von Phosphatoberflachen durch Aufbringen einer Losung auf eine phosphatierte Stahlschicht, wobei die Losung als Farbstoff einen in organischen Losemitteln löslichen, organischen Farbstoff sowie als Bindemittel Polyvinylacetat und Kunstschellack enthaltFor example, DE 729 723 discloses the blackening of phosphate surfaces by applying a solution to a phosphated steel layer, the solution containing as a dye an organic dye soluble in organic solvents and as a binder polyvinyl acetate and synthetic shellac
Ferner ist aus der DE 800 200 die Aufbringung einer Schutzschicht durch Behandlung eines eine Konversionsschicht aufweisenden Magnesiumgegenstands mit einer Farblosung bekannt, die zusätzlich ein in Tπchlorethylen oder Alkohol gelöstes Harz oder Kunstharz enthaltFurthermore, DE 800 200 discloses the application of a protective layer by treating a magnesium object having a conversion layer with a color solution which additionally contains a resin or synthetic resin dissolved in tπchlorethylene or alcohol
Die EP 0 488 280 beschreibt einen Mehrschichtuberzug, bestehend aus einem Stahlblech als metallischem Tr ger, einer auf der Stahloberflache aufgebrachten ersten zinkhaltigen Schicht, einer zweiten durch Chromatierung erhaltenen Schicht und einer dritten und letzten Schicht, erhaltlich durch thermische Vernetzung einer nicht wassπ- gen Losung aus einem Bindemittel auf Polymerbasis und einem Farbstoff Untersuchungen haben aber gezeigt, dass in solchen Fallen die Haftung der Schutzschicht auf der gefärbten Konveisionsschicht viel schlechter ist, als auf einer vergleichbaren, nicht gefärbten Konversionsschicht Eine mögliche Erklärung hierfür ist in der Wirkung des Farbstoffes als "Trennmittel" zu sehenEP 0 488 280 describes a multi-layer coating consisting of a steel sheet as a metallic carrier, a first zinc-containing layer applied to the steel surface, a second layer obtained by chromating and a third and last layer, obtainable by thermal crosslinking of a non-aqueous solution from a polymer-based binder and a dye However, studies have shown that in such cases the adhesion of the protective layer to the colored convection layer is much worse than to a comparable, non-colored conversion layer. One possible explanation for this is the effect of the dye as a "release agent "to see
Aufgabe der vorliegenden Erfindung ist die Bereitsstellung eines farbigen Mehrschicht- uberzugs auf Metallen, wobei dieser Überzug hinsichtlich Korrosionsbeständigkeit und mechanischem Abrieb keine schlechteren Eigenschaften aufweisen soll als eine herkömmliche, nicht gefärbte KonversionsschichtThe object of the present invention is to provide a colored multilayer coating on metals, this coating should not have any worse properties in terms of corrosion resistance and mechanical abrasion than a conventional, non-colored conversion layer
Diese Aufgabe wird erfindungsgemaß gelost durch einen Mehrschichtuberzug mit mindestens zwei Schichten, wobei die erste Schicht eine auf einem Metall befindliche, Poren aufweisende Konversionsschicht ist und die zweite, auf der Konversionsschicht befindliche Schicht durch Aufbringen einer Losung auf die Konversionsschicht erhältlich ist, wobei die Losung mindestens eine Alkoxysilanverbmdung und einen Farbstoff enthält, gefolgt von einer anschließenden Polymerisierung und/oder Vernetzung der Alkoxysilanverbindung.This object is achieved according to the invention by a multilayer coating with at least two layers, the first layer being a conversion layer located on a metal and having pores and the second layer located on the conversion layer being obtainable by applying a solution to the conversion layer, the solution being at least an alkoxysilane compound and a dye contains, followed by subsequent polymerization and / or crosslinking of the alkoxysilane compound.
Maßgeblich für die gute Haftung der erfindungsgemäßen Schicht im Vergleich mit Mehrschichtüberzügen des Standes der Technik sind zwei Faktoren: Zum einen muss die Konversionsschicht Poren aufweisen. Zum anderen muss die den Farbstoff enthaltende Schicht zwingend eine Alkoxysilanverbindung als zu polymerisierende und/oder zu vernetzende Verbindung aufweisen.Two factors are decisive for the good adhesion of the layer according to the invention in comparison with multilayer coatings of the prior art: firstly, the conversion layer must have pores. On the other hand, the layer containing the dye must have an alkoxysilane compound as the compound to be polymerized and / or crosslinked.
Nur so ist gewährleistet, dass die auf der Konversionsschicht befindliche farbgebende Schicht zum einen infolge einer Chemisorption über Si-O-Bindungen mit der Oberfläche der Konversionsschicht, zum anderen aber auch über eine Chemisorption im Inneren der Poren, verbunden ist.This is the only way to ensure that the coloring layer on the conversion layer is connected to the surface of the conversion layer on the one hand as a result of chemisorption via Si-O bonds, and on the other hand is also connected via chemisorption in the interior of the pores.
Durch das Eindringen der Alkoxysilanverbindung in die Poren wird die Kontaktfläche und damit die Chemisorption zwischen Konversionsschicht und Polymerschicht wesentlich erhöht.The penetration of the alkoxysilane compound into the pores significantly increases the contact area and thus the chemisorption between the conversion layer and the polymer layer.
Die Größe und Häufigkeit der Poren in einer Konversionsschicht hängt im wesentlichen von dem Metall und dem angewandten Konversionsverfahren ab. So liegt die Größe der Poren beispielsweise einer Magnesiumoxidschicht, hergestellt nach dem in der EP 0 333 048 AI beschriebenen Verfahren, zwischen 200 und 1.000 nm; die Porengröße einer Aluminiumoxidschicht (entsprechend der DE 41 39 006) liegt hingegen zwischen 50 und 100 nm.The size and frequency of the pores in a conversion layer essentially depends on the metal and the conversion process used. For example, the size of the pores of a magnesium oxide layer, produced by the process described in EP 0 333 048 AI, is between 200 and 1,000 nm; the pore size of an aluminum oxide layer (according to DE 41 39 006), however, is between 50 and 100 nm.
Einen weiteren, wesentlichen Einfluß auf eine ausreichende Haftung zwischen Konversions- und Polymerschicht hat die Wahl des Farbstoffs.The choice of the dye has a further, essential influence on adequate adhesion between the conversion and polymer layers.
Gemäß einer besonderen Ausführungsform liegt der Farbstoff in gelöster Form in der mindestens eine Alkoxysilanverbindung enthaltenden Lösung vor; insbesondere sollte der Farbstoff in Tetraethoxysilan löslich sein.According to a particular embodiment, the dye is in dissolved form in the solution containing at least one alkoxysilane compound; in particular, the dye should be soluble in tetraethoxysilane.
Auf diese Weise wird eine homogene Lösung und damit ein homogener Aufbau der Polymerschicht erreicht. Es findet sich somit keine Anreicherung des Farbstoffs in der Polymerschicht, die als "Sollbruchstelle" zwischen Konversions- und Polymerschicht wirken könnte. Das Merkmal der Löslichkeit des erfindungsgemäß zu verwendenden Farbstoffs schließt die Verwendung unlöslicher Pigmente (wie z.B. Ruß, Titandioxid oder Eisenoxid) aus.In this way, a homogeneous solution and thus a homogeneous structure of the polymer layer is achieved. There is therefore no accumulation of the dye in the polymer layer, which could act as a "predetermined breaking point" between the conversion and polymer layers. The solubility characteristic of the dye to be used according to the invention precludes the use of insoluble pigments (such as, for example, carbon black, titanium dioxide or iron oxide).
Die Bildung der Polymerschicht erfolgt durch an sich bekannte, dem Fachmann geläufige Polymerisationsverfahren (z.B. Lufttrocknung, Erhitzen oder UV-Bestrahlung):The polymer layer is formed by polymerization processes known per se and familiar to the person skilled in the art (e.g. air drying, heating or UV radiation):
Die Menge an Alkoxysilanverbindung und Farbstoff in der aufzubringenden Lösung kann in weiten Grenzen variieren. Im allgemeinen enthält die Lösung 5 bis 45 Gew.-%, insbesondere 10 bis 30 Gew.-% der Alkoxysilanverbindung und 2 bis 15 Gew.-% des Farbstoffes. Je nach erforderlicher Viskosität kann die Lösung zusätzlich ein polares Lösungsmittel enthalten, das so zu wählen ist, dass der Farbstoff gelöst ist und das Lösungsmittel nicht mit der Alkoxysilanverbindung reagiert (z.B. Ethanol).The amount of alkoxysilane compound and dye in the solution to be applied can vary within wide limits. In general, the solution contains 5 to 45 wt .-%, in particular 10 to 30 wt .-% of the alkoxysilane compound and 2 to 15 wt .-% of Dye. Depending on the required viscosity, the solution can also contain a polar solvent, which should be selected so that the dye is dissolved and the solvent does not react with the alkoxysilane compound (eg ethanol).
Gemäß einer besonders bevorzugten Ausführungsform der vorliegenden Erfindung entspricht die Alkoxysilanverbindung der allgemeinen FormelAccording to a particularly preferred embodiment of the present invention, the alkoxysilane compound corresponds to the general formula
R aR bSLX<4.a.b R a R b SLX <4 . a . b
in derin the
• X eine Alkoxy-, eine Aryloxy- oder eine Acyloxygruppe mit 1 bis 12 Kohlenstoffatomen, vorzugsweise mit 1 bis 4 Kohlenstoffatomen darstellt, und insbesondere ausgewählt ist aus der Gruppe der Methoxy-, Ethoxy-, n-Propoxy-, i- Propoxy-, Butoxy-, Phenoxy-, Acetoxy- und Propionyloxygruppen;X represents an alkoxy, an aryloxy or an acyloxy group with 1 to 12 carbon atoms, preferably with 1 to 4 carbon atoms, and is particularly selected from the group of methoxy, ethoxy, n-propoxy, i-propoxy, Butoxy, phenoxy, acetoxy and propionyloxy groups;
• R1 und R2, gleich oder verschieden voneinander, ausgewählt sind aus der Gruppe der• R 1 and R 2 , identical or different from one another, are selected from the group of
Amino-, Monoalkylamino- oder Dialkylaminoreste;Amino, monoalkylamino or dialkylamino residues;
Alkylreste, insbesondere der Alkylreste mit 1 bis 6 Kohlenstoffatomen, vorzugsweise der Methyl-, Ethyl-, n-Propyl-, Isopropyl-, n-Butyl-, s-Butyl-, t- Butyl-, Pentyl-, Hexyl- oder Cyclohexylreste;Alkyl radicals, in particular the alkyl radicals having 1 to 6 carbon atoms, preferably the methyl, ethyl, n-propyl, isopropyl, n-butyl, s-butyl, t-butyl, pentyl, hexyl or cyclohexyl radicals;
Alkenylreste, insbesondere der Alkenylreste mit 2 bis 6 Kohlenstoffatomen, vorzugsweise der Vinyl-, 1-Propenyl-, 2-Propenyl- oder Butenylreste; Alkinylreste, insbesondere der Alkenylreste mit 2 bis 6 Kohlenstoffatomen, vorzugsweise der Acetylenyl- oder Propargylreste;Alkenyl residues, in particular alkenyl residues with 2 to 6 carbon atoms, preferably vinyl, 1-propenyl, 2-propenyl or butenyl residues; Alkynyl radicals, in particular the alkenyl radicals having 2 to 6 carbon atoms, preferably the acetylenyl or propargyl radicals;
Arylreste, insbesondere der Arylreste mit 6 bis 10 Kohlenstoffatomen, vorzugsweise Phenyl- oder Naphtenylreste;Aryl radicals, in particular aryl radicals having 6 to 10 carbon atoms, preferably phenyl or naphtenyl radicals;
Epoxyreste, insbesondere der Epoxyreste mit 3 bis 16 Kohlenstoff atomen, vorzugsweise der Glycidyl-, Glycidylether-, Glycidylester- oder Glycidyl- oxyalkylreste; oder zuvor beschriebenen Gruppe X; undEpoxy residues, in particular the epoxy residues with 3 to 16 carbon atoms, preferably the glycidyl, glycidyl ether, glycidyl ester or glycidyl oxyalkyl residues; or group X described above; and
• a und b, gleich oder verschieden voneinander, den Wert 0, 1, 2 oder 3 darstellen, wobei die Summe von a und b den Wert 3 nicht überschreitet.A and b, the same or different from each other, represent the value 0, 1, 2 or 3, the sum of a and b not exceeding 3.
Eine entsprechende Alkoxysilanverbindung kann ein Tetraalkoxysilan, Epoxyalkoxy- silan oder Aminoalkoxysilan sein.A corresponding alkoxysilane compound can be a tetraalkoxysilane, epoxyalkoxysilane or aminoalkoxysilane.
Sehr gute Ergebnisse wurden mit Tetraethoxysilan, 3-Glycidyloxypropyl-trimethoxy- silan, 3-Aminopropyl-trimethoxysilan und 3-(Aminoethylamin)propyl-trimethoxysilan als Alkoxysilanverbindung erhalten. Um die Haftung zwischen Konversions- und Polymerschicht noch weiter zu verbessern empfiehlt es sich, der auf die Konversionsschicht aufzubringenden Lösung zusätzlich eine zur Bildung eines Titankomplexes fähige Verbindung zuzusetzen. Der Begriff "zur Bildung eines Titankomplexes fähige Verbindung" bezeichnet Verbindungen, die mit der Alkoxysilanverbindung und der Konversionsschicht über Komplexbindung verbrϋckte Ti02-Si02-Systeme bilden. Durch die Reaktion zwischen Alkoxysilanverbindung und Titanverbindung wird darüber hinaus eine vernetzte Polymerschicht erhalten.Very good results were obtained with tetraethoxysilane, 3-glycidyloxypropyl-trimethoxysilane, 3-aminopropyl-trimethoxysilane and 3- (aminoethylamine) propyl-trimethoxysilane as the alkoxysilane compound. In order to further improve the adhesion between the conversion and polymer layers, it is advisable to add an additional compound capable of forming a titanium complex to the solution to be applied to the conversion layer. The term “compound capable of forming a titanium complex” denotes compounds which form bridged Ti0 2 -Si0 2 systems with the alkoxysilane compound and the conversion layer via complex bonding. The reaction between the alkoxysilane compound and the titanium compound also results in a crosslinked polymer layer.
Eine besonders geeignete Verbindung ist eine Alkoxytitanverbindung, ein Titansäureester oder ein Titanchelat, insbesondere eine Verbindung der Formel Ti(OR)4, in der R einen Alkylrest mit 1 bis 6 Kohlenstoffatomen darstellt, der vorzugsweise ausgewählt ist aus der Gruppe der Methyl-, Ethyl-, n-Propyl-, i-Propyl- und Butylreste. Sehr gute Ergebnisse wurden mit Tetraethoxytitanat Ti(OC,H,)( erzielt. Das molare Verhältnis der Alkoxysilanverbindung zur Titanverbindung ist nicht kritisch und liegt im allgemeinen zwischen 1 und 20.A particularly suitable compound is an alkoxytitanium compound, a titanium acid ester or a titanium chelate, in particular a compound of the formula Ti (OR) 4 , in which R represents an alkyl radical having 1 to 6 carbon atoms, which is preferably selected from the group consisting of methyl, ethyl , n-propyl, i-propyl and butyl radicals. Very good results have been achieved with tetraethoxytitanate Ti (OC, H,) ( The molar ratio of the alkoxysilane compound to the titanium compound is not critical and is generally between 1 and 20.
Lösungen, die sowohl eine Alkoxysilanverbindung als auch eine zur Bildung eines Titankomplexes fähige Verbindung enthalten, sind beispielsweise in der DE 41 38 218 AI beschrieben und können von verschiedenen Firmen bezogen werden (z.B. Deltacoll® 80 von der Fa. Dörken).Solutions containing both an alkoxysilane and contain a group capable of forming a titanium complex compound, are described for example in DE 41 38 218 Al and are available from various companies (for example Deltacoll ® 80 from the company. Dörken).
Ein besonders im Sinne der vorliegenden Erfindung zu verwendender Farbstoff ist ein Metallkomplex-Farbstoff, wie er beispielsweise unter der Handelsbezeichnung Neoza- pon® von der Fa. BASF, Orasol" von der Fa. Ciba-Geigy, Savinyl® von der Fa. Sandoz oder Lampronol® von der Fa. ICI vertrieben wird.An especially in the context of the present invention to be used dye is a metal complex dye as pon, for example, under the trade designation Neoza- ® by the company. BASF, Orasol "from Messrs. Ciba-Geigy, Savinyl ® by the company. Sandoz or Lampronol ® is sold by ICI.
Als Metall können prinzipiell alle Metalle verwendet werden, die zur Bildung einer Konversionsschicht fähig sind. Besonders bevorzugt sind aber Leichmetalle, insbesondere Aluminium, Magnesium oder eine Aluminium und/oder Magnesium enthaltende Legierung, die in vielen Bereichen aufgrund ihres geringen spezifischen Gewichts Stahl und dessen Legierungen verdrängen.In principle, all metals which are capable of forming a conversion layer can be used as the metal. However, particularly preferred are light metals, in particular aluminum, magnesium or an alloy containing aluminum and / or magnesium, which displace steel and its alloys in many areas due to their low specific weight.
Im Hinblick auf eine hohe Abriebbeständigkeit werden als Konversionsschichten insbesondere elektrochemisch erhältlich Konversionsschichten verwendet.In view of a high abrasion resistance, conversion layers, in particular electrochemically obtainable, are used as conversion layers.
Die Erfindung betrifft des weiteren auch die Verwendung einer Lösung zur Herstellung eines erfindungsgemäßen Mehrschichtüberzugs, wobei diese Lösung mindestens eine der zuvor beschriebenen Alkoxysilanverbindungen und einen in einem polaren Lösemittel löslichen Farbstoff enthält.The invention further relates to the use of a solution for producing a multilayer coating according to the invention, this solution comprising at least one of the alkoxysilane compounds described above and a dye which is soluble in a polar solvent.
Die Erfindung betrifft ferner die Verwendung des zuvor beschriebenen Mehrschichtüberzugs als korrosions- und abriebbeständiger Schutzüberzug für Teile der Kraftfahrzeugindustrie, Elektro- und Elektronikindustrie, Maschinenbauindustrie, Luft- und Raumfahrt sowie für Teile von Sportgeräten.The invention further relates to the use of the multilayer coating described above as a corrosion and abrasion-resistant protective coating for parts of the motor vehicle industry, electrical and electronics industry, mechanical engineering industry, aerospace and for parts of sports equipment.
Zu nennen sind insbesondere Teile von Motoren und Getriebegehäusen, Instrumententafeln, Türen und Einzelteile hiervon, Lenkgetriebegehäuse, Radsterne für Motorräder, Drosselklappengehäuse, Aufnahmevorrichtungen für Fräser, Rotoren oder Verdrängergehäuse für Kompressoren, Siegelbacken für Verpackungsmaschinen, Teile für Steckerleisten und elektrische Verbinder, Lampenträger, Lampengehäuse, Rotorgehäuse von Helikoptern, Gehäuse für elektrische Geräte und Teile von Sportbögen. In particular, parts of engines and gearboxes, instrument panels, doors and individual parts thereof, steering gearboxes, wheel stars for motorcycles, throttle valve housings, holding devices for milling cutters, rotors or displacement housings for compressors, sealing jaws for packaging machines, parts for plug strips and electrical connectors, lamp holders, lamp housings, Rotor housings for helicopters, housings for electrical devices and parts for sports arches.

Claims

P a t e n t a n s p r ü c h e Patent claims
1. Mehrschichtuberzug mit mindestens zwei Schichten, wobei die erste Schicht eine auf einem Metall befindliche, Poren aufweisende Konversionsschicht ist und die zweite, auf der Konversionsschicht befindliche Schicht durch Aufbringen einer Lösung auf die Konversionsschicht erhältlich ist, wobei die Lösung mindestens eine Alkoxysilanverbindung und einen Farbstoff enthält, gefolgt von einer anschließenden Polymerisierung und/oder Vernetzung der Alkoxysilanverbindung.1. Multi-layer coating with at least two layers, the first layer being a conversion layer on a metal having pores and the second layer on the conversion layer being obtainable by applying a solution to the conversion layer, the solution being at least one alkoxysilane compound and a dye contains, followed by subsequent polymerization and / or crosslinking of the alkoxysilane compound.
2. Mehrschichtuberzug nach Anspruch 1, dadurch gekennzeichnet, dass der Farbstoff in der mindestens eine Alkoxysilanverbindung enthaltenden Lösung in gelöster Form vorliegt.2. Multi-layer coating according to claim 1, characterized in that the dye is present in dissolved form in the solution containing at least one alkoxysilane compound.
3. Mehrschichtuberzug nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass der Farbstoff in Tetraethoxysilan löslich ist.3. Multi-layer coating according to claim 1 or 2, characterized in that the dye is soluble in tetraethoxysilane.
4. Mehrschichtuberzug nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass die Alkoxysilanverbindung der allgemeinen Formel4. Multi-layer coating according to one of the preceding claims, characterized in that the alkoxysilane compound of the general formula
R aR bSiX( ..1.1)) R a R b SiX ( .. 1. 1))
entspricht, in dercorresponds in which
• X eine Alkoxy-, eine Aryloxy- oder eine Acyloxygruppe mit 1 bis 12 Kohlenstoffatomen, vorzugsweise mit 1 bis 4 Kohlenstoffatomen, darstellt, und insbesondere ausgewählt ist aus der Gruppe der Methoxy-, Ethoxy-, n-Propoxy-, i-Propoxy-, Butoxy-, Phenoxy-, Acetoxy- und Propionyloxygruppen;X represents an alkoxy, an aryloxy or an acyloxy group with 1 to 12 carbon atoms, preferably with 1 to 4 carbon atoms, and is particularly selected from the group of methoxy, ethoxy, n-propoxy, i-propoxy , Butoxy, phenoxy, acetoxy and propionyloxy groups;
• R1 und R2, gleich oder verschieden voneinander, ausgewählt sind aus der Gruppe der• R 1 and R 2 , identical or different from one another, are selected from the group of
Amino-, Monoalkylamino- oder Dialkylaminoreste;Amino, monoalkylamino or dialkylamino residues;
Alkylreste, insbesondere der Alkylreste mit 1 bis 6 Kohlenstoffatomen, vorzugsweise der Methyl-, Ethyl-, n-Propyl-, Isopropyl-, n-Butyl-, s-Butyl-, t- Butyl-, Pentyl-, Hexyl- oder Cyclohexylreste;Alkyl radicals, in particular the alkyl radicals having 1 to 6 carbon atoms, preferably the methyl, ethyl, n-propyl, isopropyl, n-butyl, s-butyl, t-butyl, pentyl, hexyl or cyclohexyl radicals;
Alkenylreste, insbesondere der Alkenylreste mit 2 bis 6 Kohlenstoff atomen, vorzugsweise der Vinyl-, 1-Propenyl-, 2-Propenyl- oder Butenylreste; WO 01/71060 g PCT/DEOl/01125Alkenyl radicals, in particular the alkenyl radicals having 2 to 6 carbon atoms, preferably the vinyl, 1-propenyl, 2-propenyl or butenyl radicals; WO 01/71060 g PCT / DEOl / 01125
Alkinylreste, insbesondere der Alkenylreste mit 2 bis 6 Kohlenstoffatomen, vorzugsweise der Acetylenyl- oder Propargylreste;Alkynyl radicals, in particular the alkenyl radicals having 2 to 6 carbon atoms, preferably the acetylenyl or propargyl radicals;
Arylreste, insbesondere der Arylreste mit 6 bis 10 Kohlenstoffatomen, vorzugsweise Phenyl- oder Naphtenylreste;Aryl radicals, in particular aryl radicals having 6 to 10 carbon atoms, preferably phenyl or naphtenyl radicals;
Epoxyreste, insbesondere der Epoxyreste mit 3 bis 16 Kohlenstoffatomen, vorzugsweise der Glycidyl-, Glycidylether-, Glycidylester- oder Glycidyl- oxyalkylreste; oder zuvor beschriebenen Gruppe X; und • a und b, gleich oder verschieden voneinander, den Wert 0, 1, 2 oder 3 darstellen, wobei die Summe von a und b den Wert 3 nicht überschreitet.Epoxy radicals, in particular the epoxy radicals having 3 to 16 carbon atoms, preferably the glycidyl, glycidyl ether, glycidyl ester or glycidyl oxyalkyl radicals; or group X described above; and • a and b, the same or different from each other, represent the value 0, 1, 2 or 3, the sum of a and b not exceeding 3.
5- Mehrschichtuberzug nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass die Alkoxysilanverbindung ein Tetraalkoxysilan, Epoxyalk- oxysilan oder Aminoalkoxysilan ist.5- multilayer coating according to one of the preceding claims, characterized in that the alkoxysilane compound is a tetraalkoxysilane, epoxyalkoxysilane or aminoalkoxysilane.
6. Mehrschichtuberzug nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass die Alkoxysilanverbindung ausgewählt ist aus der Gruppe von Tetraethoxysilan, 3-Glycidyloxypropyl-trimethoxysilan, 3-Aminopropyl-tri- methoxysilan und 3-(Aminoethylamin)propyl-trimethoxysilan.6. Multi-layer coating according to one of the preceding claims, characterized in that the alkoxysilane compound is selected from the group of tetraethoxysilane, 3-glycidyloxypropyl-trimethoxysilane, 3-aminopropyl-trimethoxysilane and 3- (aminoethylamine) propyl-trimethoxysilane.
7. Mehrschichtuberzug nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass die Lösung zusätzlich eine zur Bildung eines Titankomplexes fähige Verbindung enthält.7. Multi-layer coating according to one of the preceding claims, characterized in that the solution additionally contains a compound capable of forming a titanium complex.
8. Mehrschichtuberzug nach Anspruch 7, dadurch gekennzeichnet, dass die zur Bildung eines Titankomplexes fähige Verbindung eine Alkoxytitanverbindung, ein Titansäureester oder ein Titanchelat ist und insbesondere der Formel Ti(OR)/, entspricht, in der R einen Alkylrest mit 1 bis 6 Kohlenstoffatomen darstellt, der vorzugsweise ausgewählt ist aus der Gruppe der Methyl-, Ethyl- n-Propyl-, i-Propyl- und Butylreste.8. A multilayer coating according to claim 7, characterized in that the compound capable of forming a titanium complex is an alkoxytitanium compound, a titanium ester or a titanium chelate and in particular corresponds to the formula Ti (OR) / , in which R represents an alkyl radical having 1 to 6 carbon atoms , which is preferably selected from the group of methyl, ethyl, n-propyl, i-propyl and butyl radicals.
9. Mehrschichtuberzug nach Anspruch 8, dadurch gekennzeichnet, dass die zur Bildung eines Titankomplexes fähige Verbindung Tetraethoxytitanat Ti(OC H5)4 ist.9. Multi-layer coating according to claim 8, characterized in that the compound capable of forming a titanium complex is tetraethoxytitanate Ti (OC H 5 ) 4 .
10. Mehrschichtuberzug nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass der Farbstoff ein Metallkomplex-Farbstoff ist. 10. Multi-layer coating according to one of the preceding claims, characterized in that the dye is a metal complex dye.
11. Mehrschichtuberzug nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass das Metall ein Leichmetall, insbesondere Aluminium, Magnesium oder eine Aluminium und/oder Magnesium enthaltende Legierung ist.11. Multi-layer coating according to one of the preceding claims, characterized in that the metal is a light metal, in particular aluminum, magnesium or an alloy containing aluminum and / or magnesium.
12. Mehrschichtuberzug nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass die Konversionsschicht auf elektrochemischem Wege erhältlich ist.12. Multi-layer coating according to one of the preceding claims, characterized in that the conversion layer is obtainable by electrochemical means.
13- Verwendung einer Lösung zur Herstellung eines Mehrschichtüberzugs nach einem der Ansprüche 1 bis 12, dadurch gekennzeichnet, dass die Lösung mindestens eine Alkoxysilanverbindung nach einem der Ansprüche 2 bis 9 und einen in einem polaren Lösemittel löslichen Farbstoff enthält.13- Use of a solution for producing a multilayer coating according to one of claims 1 to 12, characterized in that the solution contains at least one alkoxysilane compound according to one of claims 2 to 9 and a dye soluble in a polar solvent.
14. Verwendung eines Mehrschichtüberzugs nach einem der vorhergehenden Ansprüche als korrosions- und abriebbeständiger Schutzüberzug für Teile der Kraftfahrzeugindustrie, Elektro- und Elektronikindustrie, Maschinenbauindustrie, Luft- und Raumfahrt sowie für Teile von Sportgeräten. 14. Use of a multilayer coating according to one of the preceding claims as a corrosion and abrasion-resistant protective coating for parts of the motor vehicle industry, electrical and electronics industry, mechanical engineering industry, aerospace and for parts of sports equipment.
EP01929258A 2000-03-22 2001-03-22 Dyed conversion layer Expired - Lifetime EP1266048B1 (en)

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