EP1266048B1 - Couche de conversion coloree - Google Patents

Couche de conversion coloree 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
Authority
EP
European Patent Office
Prior art keywords
radicals
layer coating
carbon atoms
coating according
layer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP01929258A
Other languages
German (de)
English (en)
Other versions
EP1266048A2 (fr
Inventor
Peter Kurze
Marco Kohler
Ulrike KRÜGER
Dora Banerjee
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Electro Chemical Engineering GmbH
Original Assignee
Electro Chemical Engineering GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
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First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=7635808&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP1266048(B1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Electro Chemical Engineering GmbH filed Critical Electro Chemical Engineering GmbH
Publication of EP1266048A2 publication Critical patent/EP1266048A2/fr
Application granted granted Critical
Publication of EP1266048B1 publication Critical patent/EP1266048B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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.

Landscapes

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

Claims (12)

  1. Recouvrement multicouches composé d'au moins deux couches, la première couche étant une couche de conversion présentant des pores placée sur un métal et la deuxième couche placée sur la couche de conversion pouvant être obtenue par application d'une solution sur la couche de conversion, cette solution contenant
    • au moins une composition d'alcoxysilane; et
    • un colorant se présentant sous forme dissoute dans la solution contenant au moins une composition d'alcoxysilane,
    • le colorant étant soluble dans le silane tétraéthoxy
    suivie ensuite d'une polymérisation et/ou d'une réticulation de la composition d'alcoxysilane.
  2. Recouvrement multicouches selon la revendication 1, caractérisé en ce que la composition d'alcoxysilane correspond à la formule générale

            R1 aR2 bSiX(4-a-b)

    dans laquelle
    • X représente un groupe alkoxy, aryloxy ou acyloxy contenant 1 à 12 atomes de carbone, de préférence 1 à 4 atomes de carbone, et est particulièrement choisi parmi les groupes méthoxy, éthoxy, n-propoxy, i-propoxy, butoxy, phénoxy, acétoxy et propionyloxy ;
    • R1 et R2, identiques ou différents, étant choisis parmi le groupe des
    - radicaux amino, monoalkylamino ou dialkylamino ;
    - radicaux alkyliques, notamment ceux contenant 1 à 6 atomes de carbone, de préférence les radicaux de méthyle, éthyle, n-propyle, isopropyle, n-butyle, s-butyle, t-butyle, pentyle, hexyle ou cyclohexyle ;
    - radicaux alcényliques, notamment ceux contenant 2 à 6 atomes de carbone, de préférence les radicaux de vinyle, propényle-1, propényle-2 ou butényle ;
    - radicaux alcinyliques, en particulier ceux contenant 2 à 6 atomes de carbone, de préférence les radicaux d'acétylényle ou de propargyle ;
    - radicaux aryliques, en particulier ceux contenant 6 à 10 atomes de carbone, de préférence les radicaux de phényle ou de naphtényle ;
    - radicaux époxy, en particulier ceux contenant 3 à 16 atomes de carbone, de préférence les radicaux de glycidyle, d'éther glycidylique, d'ester glycidylique ou de glycidyloxyalkyle ; ou
    - le groupe X décrit précédemment ; et
    • a et b, identiques ou différents, représentant la valeur 0, 1, 2 ou 3, la somme de a et de b ne dépassant pas la valeur 3.
  3. Recouvrement multicouches selon l'une des revendications 1 et 2, caractérisé en ce que la composition d'alcoxysilane est un tétraalcoxysilane, un époxyalcoxysilane ou un aminoalcoxysilane.
  4. Recouvrement multicouches selon l'une des revendications précédentes, caractérisé en ce que la composition d'alcoxysilane est choisie parmi le groupe du tétraéthoxysilane, du 3-glycidyloxypropyle-triméthoxysilane, 3-aminopropyle-triméthoxysilane et 3-(aminoéthylamine)propyle- triéthoxy-silane.
  5. Recouvrement multicouches selon l'une des revendications précédentes, caractérisé en ce que la solution contient en plus un composé capable de former un complexe titanique.
  6. Recouvrement multicouches selon la revendication 5, caractérisé en ce que le composé capable de former un complexe titanique est un composé d'alcoxytitane, un ester titanique ou un chélate de titane et correspond en particulier à la formule Ti(OR)4, dans laquelle R représente un radical alkyle contenant 1 à 6 atomes de carbone, choisi de préférence parmi le groupe des radicaux de méthyle, éthyle, n-propyle, i-propyle et de butyle.
  7. Recouvrement multicouches selon la revendication 6, caractérisé en ce que le composé capable de former un complexe titanique est le titanate tétraéthoxy Ti(OC2Hs)4.
  8. Recouvrement multicouches selon l'une des revendications précédentes, caractérisé en ce que le colorant est un colorant de complexe métallique.
  9. Recouvrement multicouches selon l'une des revendications précédentes, caractérisé en ce que le métal est un métal léger, notamment l'aluminium, le magnésium ou un alliage contenant de l'aluminium et/ou du magnésium.
  10. Recouvrement multicouches selon l'une des revendications précédentes, caractérisée en ce que la couche de conversion peut être obtenue par voie électrochimique.
  11. Utilisation d'une solution pour la fabrication d'un recouvrement multicouches selon l'une des revendications 1 à 10, caractérisée en ce que la solution contient au moins une composition d'alcoxysilane selon l'une des revendications 2 à 7 et un colorant soluble dans un solvant polaire.
  12. Utilisation d'un recouvrement multicouches selon l'une des revendications précédentes en tant que couche de protection résistante à la corrosion et à l'abrasion pour les pièces de l'industrie automobile, de l'industrie électrique et électronique, de l'industrie mécanique, de l'aéronautique et de l'astronautique ainsi que pour les pièces d'appareils de sport.
EP01929258A 2000-03-22 2001-03-22 Couche de conversion coloree Expired - Lifetime EP1266048B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10014035A DE10014035B4 (de) 2000-03-22 2000-03-22 Gefärbte Konversionsschicht, eine Lösung zu ihrer Herstellung sowie ihre Verwendung
DE10014035 2000-03-22
PCT/DE2001/001125 WO2001071060A1 (fr) 2000-03-22 2001-03-22 Couche de conversion coloree

Publications (2)

Publication Number Publication Date
EP1266048A2 EP1266048A2 (fr) 2002-12-18
EP1266048B1 true EP1266048B1 (fr) 2006-12-06

Family

ID=7635808

Family Applications (1)

Application Number Title Priority Date Filing Date
EP01929258A Expired - Lifetime EP1266048B1 (fr) 2000-03-22 2001-03-22 Couche de conversion coloree

Country Status (7)

Country Link
EP (1) EP1266048B1 (fr)
AT (1) ATE347625T1 (fr)
AU (1) AU2001256120A1 (fr)
CZ (1) CZ20023495A3 (fr)
DE (2) DE10014035B4 (fr)
HU (1) HUP0204415A2 (fr)
WO (1) WO2001071060A1 (fr)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10328633A1 (de) * 2003-06-26 2005-01-20 Aluminium Féron GmbH & Co. KG Verfahren zur Herstellung einer mit einer Schutzlackschicht versehenen Metallage, durch ein derartiges Verfahren hergestellte Metallage, Verfahren zur Herstellung eines Verbundmateriales und durch ein derartiges Verfahren hergestelltes Verbundmaterial
US7413777B2 (en) 2004-06-12 2008-08-19 Allfast Fastening Systems, Inc. Coating composition and methods of coating
WO2006016825A1 (fr) * 2004-08-12 2006-02-16 Magnesium Technology Limited Améliorations apportées ou liées au traitement de surface du magnésium et de ses alliages
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 (de) 2021-12-17 2023-06-22 Alanod Gmbh & Co. Kg Verfahren zur Herstellung eines hochabriebfesten, lackbeschichteten Materials mit einer Konversionsschicht auf einem insbesondere bandförmigen Aluminiumträger

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE729723C (de) * 1939-06-06 1942-12-22 Metallgesellschaft Ag Schwaerze zur Nachbehandlung von Phosphatoberflaechenschichten
DE800200C (de) * 1948-11-28 1950-10-14 Mahle Kg Verfahren zum Aufbringen farbiger Schutzschichten auf Gegenstaende aus Magnesium oder Magnesiumlegierungen
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
JPS6022067B2 (ja) * 1982-09-30 1985-05-30 日本パ−カライジング株式会社 金属表面の皮膜形成方法
DE3514387C2 (de) * 1984-04-27 2003-12-24 Clariant Finance Bvi Ltd 1:2-Metallkomplex-azoverbindungen, ihre Herstellung und Verwendung
JPH0730459B2 (ja) * 1987-08-03 1995-04-05 日本パ−カライジング株式会社 金属へのセラミックコ−ティング法
JPH0815584B2 (ja) * 1990-11-30 1996-02-21 日本鋼管株式会社 溶接可能な着色鋼板
JP2844953B2 (ja) * 1991-03-29 1999-01-13 日本鋼管株式会社 溶接可能な着色鋼板
DE4138218C2 (de) * 1991-11-21 1994-08-04 Doerken Ewald Ag Verwendung von Nachtauchmitteln für die Nachbehandlung von chromatierten oder passivierten Verzinkungsschichten
JP3171027B2 (ja) * 1994-10-25 2001-05-28 松下電器産業株式会社 アルミニウム酸化皮膜およびその製造法
EP0756755B1 (fr) * 1995-02-20 1998-11-11 Koninklijke Philips Electronics N.V. Dispositif de presentation d'information comprenant un ecran d'affichage muni d'un enduit absorbeur de lumiere
DE19620668C1 (de) * 1996-05-22 1997-09-11 Feinchemie Gmbh Sebnitz Thermisch härtbarer Mehrkomponenten-Lack

Also Published As

Publication number Publication date
CZ20023495A3 (cs) 2003-09-17
DE10014035A1 (de) 2001-10-04
AU2001256120A1 (en) 2001-10-03
EP1266048A2 (fr) 2002-12-18
DE50111587D1 (de) 2007-01-18
ATE347625T1 (de) 2006-12-15
WO2001071060A1 (fr) 2001-09-27
HUP0204415A2 (en) 2003-04-28
WO2001071060B1 (fr) 2001-12-13
DE10014035B4 (de) 2006-07-13

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