EP1266048B1 - Dyed conversion layer - Google Patents

Dyed conversion layer Download PDF

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Publication number
EP1266048B1
EP1266048B1 EP01929258A EP01929258A EP1266048B1 EP 1266048 B1 EP1266048 B1 EP 1266048B1 EP 01929258 A EP01929258 A EP 01929258A EP 01929258 A EP01929258 A EP 01929258A EP 1266048 B1 EP1266048 B1 EP 1266048B1
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EP
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Prior art keywords
radicals
layer coating
carbon atoms
coating according
layer
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German (de)
French (fr)
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EP1266048A2 (en
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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 multi-layer coating of a conversion layer disposed 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 by chemical conversion (conversion) of this metallic surface and various constituents of an aqueous passivating electrolyte (compare 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 methods 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 described) and the chromating, chromitizing or phosphating iron-containing metals.
  • DE 729 723 discloses the blackening of phosphate surfaces by applying a solution to a phosphated steel layer, wherein the solution contains as dye a soluble in organic solvents, organic dye and as a binder polyvinyl acetate and synthetic shellac. Furthermore, from DE 800 200, the application of a protective layer by treating a conversion layer having a magnesium object with a dye solution is known, which additionally contains dissolved in trichlorethylene or alcohol resin or synthetic resin.
  • EP 0 488 280 describes a multi-layer coating consisting of a steel sheet as a metallic support, a first zinc-containing layer applied to the steel surface, a second chromate-obtained layer and a third and last layer obtainable by thermal crosslinking of a non-aqueous solution of a binder based on polymer and a dye. Investigations have shown, however, that in such cases the adhesion of the protective layer to the colored conversion layer is much worse than on a comparable, non-colored conversion layer. A possible explanation for this is to be seen in the effect of the dye as a "release agent".
  • the object of the present invention is to provide a colored multi-layer coating on metals, this coating should have no worse properties in terms of corrosion resistance and mechanical abrasion than a conventional, non-colored conversion layer.
  • the dye is present in dissolved form in the solution comprising at least one alkoxysilane compound;
  • the dye should be soluble in tetraethoxysilane.
  • a homogeneous solution and thus a homogeneous structure of the polymer layer is achieved.
  • the feature of solubility of the dye to be used in the present invention precludes the use of insoluble pigments (such as carbon black, titanium dioxide or iron oxide).
  • the formation of the polymer layer takes place by known per se, familiar to the expert polymerization (eg air drying, heating or UV irradiation):
  • 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 the dye.
  • the solution may additionally contain a polar solvent, the like it should be chosen that the dye is dissolved and the solvent does not react with the alkoxysilane compound (eg ethanol).
  • a corresponding alkoxysilane compound may be a tetraalkoxysilane, epoxyalkoxysilane or aminoalkoxysilane. Very good results were obtained with tetraethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane and 3- (aminoethylamine) propyltrimethoxysilane as the alkoxysilane compound.
  • a compound capable of forming a titanium complex refers to compounds that form TiO 2 -SiO 2 systems bridged with the alkoxysilane compound and the conversion layer via complex bonding.
  • a particularly suitable compound is an alkoxy titanium compound, a titanic 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 of methyl, ethyl , n-propyl, i-propyl and butyl radicals. Very good results were achieved with tetraethoxy titanate Ti (OC 2 H 5 ) 4 .
  • 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, for example described in DE 41 38 218 A1, and can be obtained from various companies (eg 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, for example, under the trade designation Neozapon ® by the company. BASF, Orasol ® by the company. Ciba-Geigy, Savinyl ® by the company. Sandoz or Lampronol ® sold by the company. ICI.
  • all metals which are capable of forming a conversion layer can be used as the metal.
  • light metals in particular aluminum, magnesium or an aluminum and / or magnesium-containing alloy, which displace steel and its alloys in many areas due to their low specific gravity.
  • conversion layers which are available in particular as electrochemically conversion layers are used.
  • the invention further relates to the use of a solution for producing a multi-layer coating according to the invention, this solution containing at least one of the above-described alkoxysilane compounds and a dye soluble in a polar solvent.
  • the invention further relates to the use of the above-described multi-layer coating as a corrosion and abrasion resistant protective coating for parts of the automotive industry, electrical and electronics industry, mechanical engineering industry, aerospace and parts of sports equipment. Particular mention should be made of parts of engines and transmission housings, instrument panels, doors and parts thereof, steering gear housings, motorcycle wheel housings, throttle bodies, milling cutters, rotors or compressor displacers, sealing jaws for packaging machines, parts for power strips and electrical connectors, lamp holders, lamp housings, Rotor housings of helicopters, housings for electrical equipment and parts of sports bows.

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

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 multi-layer coating of a conversion layer disposed 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).
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.Metal conversion layers 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 by chemical conversion (conversion) of this metallic surface and various constituents of an aqueous passivating electrolyte (compare H. Simon, M Thoma "Applied Surface Technology for Metallic Materials", Carl Hanser Verlag, Munich (1985) p. 4).
Depending on the type of metal and the method for generating 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 methods 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 described) and the chromating, chromitizing or phosphating iron-containing metals.

Des weiteren ist es bekannt, diese Konversionsschichten zur Herstellung dekorativer Überzüge einzufärben.
Eine solche Möglichkeit ist durch Verwendung eines Passivierungselektrolyts offenbart, der bereits einen entsprechenden Farbstoff enthält.
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 A1 beschrieben sind.
Ein wesentlicher Nachteil bei diesem Verfahren ist, dass sich durch die Einlagerung des Farbstoffes in die Konversionsschicht deren chemische und mechanische Eigenschaften verschlechtern.Furthermore, it is known to color these conversion layers for the production of decorative coatings.
Such a possibility is disclosed by using a passivation electrolyte which already contains a corresponding dye.
In particular, for coloring anodized aluminum surfaces, this method is still very often used today. The dyes are usually salt compounds based on metal complex compounds, as described for example in DE 35 14 387 A1.
A significant disadvantage of this method is that deteriorate their chemical and mechanical properties by the incorporation of the dye in the conversion layer.

Eine weitere vorbekannte Möglichkeit ist die Herstellung einer Konversionsschicht, gefolgt von einem Färben dieser Konversionsschicht.Another previously known possibility is the production of a conversion layer, followed by a coloring of this conversion layer.

Ein wesentliches Problem ist aber die unzureichende Abriebbeständigkeit des Farbstoffes auf der Konversionsschicht.However, a significant problem is the insufficient abrasion resistance of the dye on the conversion layer.

Schon lange hat es Versuche gegeben, diese mangelnde Abriebbeständigkeit entweder durch Aufbringen einer weiteren Schutzschicht auf die gefärbte Konversionsschicht oder durch Aufbringen einer gefärbten Schutzschicht auf die nicht gefärbte Konversionsschicht zu verbessern.
So offenbart die DE 729 723 die Schwärzung von Phosphatoberflächen durch Aufbringen einer Lösung auf eine phosphatierte Stahlschicht, wobei die Lösung als Farbstoff einen in organischen Lösemitteln löslichen, organischen Farbstoff sowie als Bindemittel Polyvinylacetat und Kunstschellack enthält.
Ferner ist aus der DE 800 200 die Aufbringung einer Schutzschicht durch Behandlung eines eine Konversionsschicht aufweisenden Magnesiumgegenstands mit einer Farblösung bekannt, die zusätzlich ein in Trichlorethylen oder Alkohol gelöstes Harz oder Kunstharz enthält.
Die EP 0 488 280 beschreibt einen Mehrschichtüberzug, bestehend aus einem Stahlblech als metallischem Träger, einer auf der Stahloberfläche aufgebrachten ersten zinkhaltigen Schicht, einer zweiten durch Chromatierung erhaltenen Schicht und einer dritten und letzten Schicht, erhältlich durch thermische Vernetzung einer nicht wässrigen Lösung aus einem Bindemittel auf Polymerbasis und einem Farbstoff.
Untersuchungen haben aber gezeigt, dass in solchen Fällen die Haftung der Schutzschicht auf der gefärbten Konversionsschicht viel schlechter ist, als auf einer vergleichbaren, nicht gefärbten Konversionsschicht. Eine mögliche Erklärung hierfür ist in der Wirkung des Farbstoffes als "Trennmittel" zu sehen.For a long time there have been attempts to improve this lack of abrasion resistance 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.
Thus, DE 729 723 discloses the blackening of phosphate surfaces by applying a solution to a phosphated steel layer, wherein the solution contains as dye a soluble in organic solvents, organic dye and as a binder polyvinyl acetate and synthetic shellac.
Furthermore, from DE 800 200, the application of a protective layer by treating a conversion layer having a magnesium object with a dye solution is known, which additionally contains dissolved in trichlorethylene or alcohol resin or synthetic resin.
EP 0 488 280 describes a multi-layer coating consisting of a steel sheet as a metallic support, a first zinc-containing layer applied to the steel surface, a second chromate-obtained layer and a third and last layer obtainable by thermal crosslinking of a non-aqueous solution of a binder based on polymer and a dye.
Investigations have shown, however, that in such cases the adhesion of the protective layer to the colored conversion layer is much worse than on a comparable, non-colored conversion layer. A possible explanation for this is to be seen in the effect of the dye as a "release agent".

Aufgabe der vorliegenden Erfindung ist die Bereitstellung eines farbigen Mehrschichtüberzugs auf Metallen, wobei dieser Überzug hinsichtlich Korrosionsbeständigkeit und mechanischem Abrieb keine schlechteren Eigenschaften aufweisen soll als eine herkömmliche, nicht gefärbte Konversionsschicht.The object of the present invention is to provide a colored multi-layer coating on metals, this coating should have no worse properties in terms of corrosion resistance and mechanical abrasion than a conventional, non-colored conversion layer.

Diese Aufgabe wird erfindungsgemäß gelöst durch einen Mehrschichtüberzug 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 in der mindestens eine Alkoxysilanverbindung enthaltenden Lösung in gelöster Form vorliegenden Farbstoff enthält, wobei
  • der Farbstoff in Tetraethoxysilan löslich ist,
gefolgt von einer anschließenden Polymerisierung und/oder Vernetzung der Alkoxysilanverbindung.
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.
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.
Durch das Eindringen der Alkoxysilanverbindung in die Poren wird die Kontaktfläche und damit die Chemisorption zwischen Konversionsschicht und Polymerschicht wesentlich erhöht.
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 A1 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.This object is achieved according to the invention by a multi-layer coating having at least two layers, the first layer being a metal-based, voided conversion layer and the second layer located on the conversion layer being obtainable by applying a solution to the conversion layer, wherein the solution
  • at least one alkoxysilane compound; and
  • contains a present in at least one alkoxysilane compound containing solution in dissolved form dye, wherein
  • the dye is soluble in tetraethoxysilane,
followed by subsequent polymerization and / or crosslinking of the alkoxysilane compound.
Decisive for the good adhesion of the layer according to the invention in comparison with multilayer coatings of the prior art are two factors: First, the conversion layer must have pores. On the other hand, the layer containing the dye must imperatively have an alkoxysilane compound as the compound to be polymerized and / or crosslinked.
This is the only way to ensure that the coloring layer on the conversion layer is connected to the surface of the conversion layer as a result of chemisorption via Si-O bonds, but also due to chemisorption in the interior of the pores.
The penetration of the alkoxysilane compound into the pores substantially increases the contact area and thus the chemisorption between the conversion layer and the polymer layer.
The size and frequency of the pores in a conversion layer depends essentially on the metal and the conversion method used.
Thus, the size of the pores, for example, of a magnesium oxide layer, prepared by the process described in EP 0 333 048 A1, is between 200 and 1000 nm; the pore size of an aluminum oxide layer (corresponding 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.
Erfindungsgemäß liegt der Farbstoff in gelöster Form in der mindestens eine Alkoxysilanverbindung enthaltenden Lösung vor; insbesondere sollte der Farbstoff in Tetraethoxysilan löslich sein.
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.
Die Bildung der Polymerschicht erfolgt durch an sich bekannte, dem Fachmann geläufige Polymerisationsverfahren (z.B. Lufttrocknung, Erhitzen oder UV-Bestrahlung):Another important influence on a sufficient adhesion between conversion and polymer layer has the choice of the dye.
According to the invention, the dye is present in dissolved form in the solution comprising at least one alkoxysilane compound; In particular, the dye should be soluble in tetraethoxysilane.
In this way, a homogeneous solution and thus a homogeneous structure of the polymer layer is achieved. There is thus no accumulation of the dye in the polymer layer, which could act as a "breaking point" between conversion and polymer layer. The feature of solubility of the dye to be used in the present invention precludes the use of insoluble pigments (such as carbon black, titanium dioxide or iron oxide).
The formation of the polymer layer takes place by known per se, familiar to the expert polymerization (eg air drying, heating or UV irradiation):

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 the dye. Depending on the required viscosity, the solution may additionally contain a polar solvent, the like it should be chosen 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 Formel

        R1 aR2 bSiX(4-a-b)

in der

  • 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;
  • R1 und R2, gleich oder verschieden voneinander, ausgewählt sind aus der Gruppe der
    • Amino-, Monoalkylamino- oder Dialkylaminoreste;
    • 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;
    • 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;
    • Arylreste, insbesondere der Arylreste mit 6 bis 10 Kohlenstoffatomen, vorzugsweise Phenyl- oder Naphtenylreste;
    • Epoxyreste, insbesondere der Epoxyreste mit 3 bis 16 Kohlenstoffatomen, vorzugsweise der Glycidyl-, Glycidylether-, Glycidylester- oder Glycidyloxyalkylreste; 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.
According to a particularly preferred embodiment of the present invention, the alkoxysilane compound corresponds to the general formula

R 1 a R 2 b SiX (4-ab)

in the
  • X represents an alkoxy, an aryloxy or an acyloxy group having 1 to 12 carbon atoms, preferably having 1 to 4 carbon atoms, and in particular is selected from the group of methoxy, ethoxy, n-propoxy, i-propoxy, butoxy -, phenoxy, acetoxy and propionyloxy groups;
  • R 1 and R 2 , the same or different from each other, are selected from the group of
    • Amino, monoalkylamino or dialkylamino radicals;
    • Alkyl radicals, in particular of 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 radicals, in particular the alkenyl radicals having 2 to 6 carbon atoms, preferably the vinyl, 1-propenyl, 2-propenyl or butenyl radicals;
    • Alkynyl radicals, in particular the alkenyl radicals having 2 to 6 carbon atoms, preferably the acetylenyl or propargyl radicals;
    • Aryl radicals, in particular the aryl radicals having 6 to 10 carbon atoms, preferably phenyl or naphthenyl radicals;
    • Epoxy radicals, in particular the epoxy radicals having 3 to 16 carbon atoms, preferably the glycidyl, glycidyl ether, glycidyl ester or glycidyloxyalkyl radicals; or
    • previously described group X; and
  • a and b, the same or different from each other, represent the value 0, 1, 2 or 3, wherein the sum of a and b does not exceed the value 3.

Eine entsprechende Alkoxysilanverbindung kann ein Tetraalkoxysilan, Epoxyalkoxysilan oder Aminoalkoxysilan sein.
Sehr gute Ergebnisse wurden mit Tetraethoxysilan, 3-Glycidyloxypropyl-trimethoxysilan, 3-Aminopropyl-trimethoxysilan und 3-(Aminoethylamin)propyl-trimethoxysilan als Alkoxysilanverbindung erhalten.A corresponding alkoxysilane compound may be a tetraalkoxysilane, epoxyalkoxysilane or aminoalkoxysilane.
Very good results were obtained with tetraethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane and 3- (aminoethylamine) propyltrimethoxysilane as the alkoxysilane compound.

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 verbrückte TiO2-SiO2-Systeme bilden. Durch die Reaktion zwischen Alkoxysilanverbindung und Titanverbindung wird darüber hinaus eine vernetzte Polymerschicht erhalten.
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(OC2H5)4 erzielt.
Das molare Verhältnis der Alkoxysilanverbindung zur Titanverbindung ist nicht kritisch und liegt im allgemeinen zwischen 1 und 20.In order to further improve the adhesion between conversion and polymer layer, it is advisable to additionally add a 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" refers to compounds that form TiO 2 -SiO 2 systems bridged with the alkoxysilane compound and the conversion layer via complex bonding. By the reaction between alkoxysilane compound and titanium compound, moreover, a crosslinked polymer layer is obtained.
A particularly suitable compound is an alkoxy titanium compound, a titanic 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 of methyl, ethyl , n-propyl, i-propyl and butyl radicals.
Very good results were achieved with tetraethoxy titanate Ti (OC 2 H 5 ) 4 .
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 A1 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, for example described in DE 41 38 218 A1, and can be obtained from various companies (eg 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 Neozapon® 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, for example, under the trade designation Neozapon ® by the company. BASF, Orasol ® by the company. Ciba-Geigy, Savinyl ® by the company. Sandoz or Lampronol ® sold by the company. 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.
Im Hinblick auf eine hohe Abriebbeständigkeit werden als Konversionsschichten insbesondere elektrochemisch erhältlich Konversionsschichten verwendet.In principle, all metals which are capable of forming a conversion layer can be used as the metal. But particularly preferred are light metals, in particular aluminum, magnesium or an aluminum and / or magnesium-containing alloy, which displace steel and its alloys in many areas due to their low specific gravity.
With regard to a high abrasion resistance, conversion layers which are available in particular as electrochemically conversion layers are used.

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 multi-layer coating according to the invention, this solution containing at least one of the above-described alkoxysilane compounds and a dye 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.
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.The invention further relates to the use of the above-described multi-layer coating as a corrosion and abrasion resistant protective coating for parts of the automotive industry, electrical and electronics industry, mechanical engineering industry, aerospace and parts of sports equipment.
Particular mention should be made of parts of engines and transmission housings, instrument panels, doors and parts thereof, steering gear housings, motorcycle wheel housings, throttle bodies, milling cutters, rotors or compressor displacers, sealing jaws for packaging machines, parts for power strips and electrical connectors, lamp holders, lamp housings, Rotor housings of helicopters, housings for electrical equipment and parts of sports bows.

Claims (12)

  1. Multi-layer coating with at least two layers, the first layer being a conversion coat present on a metal and exhibiting pores and the second layer present on the conversion coat being obtainable by applying a solution onto the conversion coat, the solution containing
    • at least one alkoxysilane compound; and
    • a dye present in the solute form in the solution containing at least one alkoxysilane compound,
    • the dye being soluble in tetraethoxysilane,
    followed by a subsequent polymerisation and/or crosslinking of the alkoxysilane compound.
  2. Multi-layer coating according to claim 1 characterised in that the alkoxysilane compound corresponds to the general formula

            R1 aR2 bSiX(4-a-b)

    in which
    • X represents an alkoxy group, an aryloxy group or an acyloxy group with 1 to 12 carbon atoms, preferably with 1 to 4 carbon atoms and is in particular selected from the group of methoxy, ethoxy, n-propoxy, i-propoxy, butoxy, phenoxy, acetoxy and propionyl groups;
    • R1 and R2 are identical or different from each other and selected from the group of
    - amino radicals, monoalkylamino radicals or dialkylamino radicals;
    - alkyl radicals, in particular the alkyl radicals with 1 to 6 carbon atoms, preferably the methyl, ethyl, n-propyl, isopropyl, n-butyl-, s-butyl, t-butyl, pentyl, hexyl or cyclohexyl radicals;
    - alkenyl radicals, in particular the alkenyl radicals with 2 to 6 carbon atoms, preferably the vinyl, 1-propenyl, 2-propenyl or butenyl radicals;
    - alkinyl radicals, in particular the alkenyl radicals with 2 to 6 carbon atoms, preferably the acetylenyl radicals or propargyl radicals;
    - aryl radicals, in particular the aryl radicals with 6 to 10 carbon atoms, preferably phenyl radicals or naphthenyl radicals;
    - epoxy radicals, in particular the epoxy radicals with 3 to 16 carbon atoms, preferably the glycidyl, glycidyl ether, glycidyl ester or glycidyl oxyalkyl radicals; or
    - the previously described group X; and
    • a and b, identically or differently from each other, represent the value 0, 1, 2 or 3, the sum of a and b not exceeding the value 3.
  3. Multi-layer coating according to claim 1 or 2 characterised in that the alkoxysiloxane compound is tetraalkoxysilane, epoxyalkoxysilane or aminoalkoxysilane.
  4. Multi-layer coating according to one of the preceding claims characterised in that the alkoxysilane compound is selected from the group of tetraethoxysilane, 3-glycidyloxypropyl trimethoxysilane, 3-aminopropyl trimethoxysilane and 3-(aminoethylamine)propyl trimethoxysilane.
  5. Multi-layer coating according to one of the preceding claims characterised in that the solution additionally contains a compound capable of forming a titanium complex.
  6. Multi-layer coating accord to claim 5 characterised in that the compound capable of forming a titanium complex is an alkoxytitanium compound, a titanic acid ester or a titanium chelate and corresponds in particular to the formula Ti(OR)4, in which R represents an alkyl radical with 1 to 6 carbon atoms, which is preferably selected from the group of methyl radicals, ethyl radicals, n-propyl radicals, i-propyl radicals and butyl radicals.
  7. Multi-layer coating according to claim 6 characterised in that the compound capable for forming a titanium complex is tetraethoxytitanate Ti(OC2H5)4.
  8. Multi-layer coating according to one of the preceding claims characterised in that the dye is a metal complex dye.
  9. Multi-layer coating according to one of the preceding claims characterised in that the metal is a light metal, in particular aluminium, magnesium or an alloy containing aluminium and/or magnesium
  10. Multi-layer coating according to one of the preceding claims characterised in that the conversion coat is obtainable by the electrochemical route.
  11. Use of a solution for the production of a multi-layer coating according to one of claims 1 to 10 characterised in that the solution contains at least one alkoxysilane compound according to one of claims 2 to 7 and a dye soluble in a polar solvent.
  12. Use of a multi-layer coating according to one of the preceding claims as corrosion and abrasion resistant protective coating for components in the vehicle industry, electrical and electronics industry, engineering industry, aeronautics and aerospace and for parts of sports equipment.
EP01929258A 2000-03-22 2001-03-22 Dyed conversion layer Expired - Lifetime EP1266048B1 (en)

Applications Claiming Priority (3)

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DE10014035 2000-03-22
DE10014035A DE10014035B4 (en) 2000-03-22 2000-03-22 Colored conversion layer, a solution for their preparation and their use
PCT/DE2001/001125 WO2001071060A1 (en) 2000-03-22 2001-03-22 Dyed conversion layer

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EP1266048B1 true EP1266048B1 (en) 2006-12-06

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DE10328633A1 (en) * 2003-06-26 2005-01-20 Aluminium Féron GmbH & Co. KG A method of producing a metal layer provided with a protective varnish layer, metal layer produced by such a method, a method of producing a composite material, and a composite material produced by such a method
US7413777B2 (en) 2004-06-12 2008-08-19 Allfast Fastening Systems, Inc. Coating composition and methods of coating
WO2006016825A1 (en) * 2004-08-12 2006-02-16 Magnesium Technology Limited Improvements in or relating to the surface treatment of magnesium and its alloys
US20060166013A1 (en) * 2005-01-24 2006-07-27 Hoden Seimitsu Kako Kenyusho Co., Ltd. Chromium-free rust inhibitive treatment method for metal products having zinc surface and metal products treated thereby
DE102021133647A1 (en) 2021-12-17 2023-06-22 Alanod Gmbh & Co. Kg Process for producing a highly abrasion-resistant, paint-coated material with a conversion layer on an aluminum carrier, in particular in the form of a strip

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DE729723C (en) * 1939-06-06 1942-12-22 Metallgesellschaft Ag Black for post-treatment of phosphate surface layers
DE800200C (en) * 1948-11-28 1950-10-14 Mahle Kg Process for applying colored protective layers to objects made of magnesium or magnesium alloys
US4208223A (en) * 1978-06-27 1980-06-17 Superior Industries Method of painting aluminum surfaces
JPS5613065A (en) * 1979-07-12 1981-02-07 Sankyo Alum Ind Co Ltd Surface treating method for patterning and coloring of aluminum plate
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JP2844953B2 (en) * 1991-03-29 1999-01-13 日本鋼管株式会社 Weldable colored steel plate
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JP3171027B2 (en) * 1994-10-25 2001-05-28 松下電器産業株式会社 Aluminum oxide film and method for producing the same
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DE10014035A1 (en) 2001-10-04
DE10014035B4 (en) 2006-07-13
ATE347625T1 (en) 2006-12-15
CZ20023495A3 (en) 2003-09-17
HUP0204415A2 (en) 2003-04-28
EP1266048A2 (en) 2002-12-18
WO2001071060B1 (en) 2001-12-13
DE50111587D1 (en) 2007-01-18
WO2001071060A1 (en) 2001-09-27

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