EP1457267A1 - Method for manufacturing of formed metal parts of aluminium sheet with a decorative surface - Google Patents

Method for manufacturing of formed metal parts of aluminium sheet with a decorative surface Download PDF

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Publication number
EP1457267A1
EP1457267A1 EP03405173A EP03405173A EP1457267A1 EP 1457267 A1 EP1457267 A1 EP 1457267A1 EP 03405173 A EP03405173 A EP 03405173A EP 03405173 A EP03405173 A EP 03405173A EP 1457267 A1 EP1457267 A1 EP 1457267A1
Authority
EP
European Patent Office
Prior art keywords
layer
sol
continuous
strip
aluminum
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.)
Withdrawn
Application number
EP03405173A
Other languages
German (de)
French (fr)
Inventor
Walter Hotz
Volkmar Gillich
Roman Fuchs
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.)
3A Composites International AG
Original Assignee
Alcan Technology and Management Ltd
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
Application filed by Alcan Technology and Management Ltd filed Critical Alcan Technology and Management Ltd
Priority to EP03405173A priority Critical patent/EP1457267A1/en
Priority to EP04405138A priority patent/EP1457266B1/en
Priority to DE502004000159T priority patent/DE502004000159D1/en
Priority to SI200430012T priority patent/SI1457266T1/en
Priority to ES04405138T priority patent/ES2252727T3/en
Priority to PL04405138T priority patent/PL1457266T3/en
Publication of EP1457267A1 publication Critical patent/EP1457267A1/en
Withdrawn legal-status Critical Current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
    • B05D7/52—Two layers
    • B05D7/54—No clear coat specified
    • B05D7/546—No clear coat specified each layer being cured, at least partially, separately
    • 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
    • B05D7/14—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 to metal, e.g. car bodies
    • 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
    • C23C22/05—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 using aqueous solutions
    • C23C22/06—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 using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/48—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 using aqueous solutions using aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
    • C23C22/56—Treatment of aluminium 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
    • B05D2202/20—Metallic substrate based on light metals
    • B05D2202/25—Metallic substrate based on light metals based on Al
    • 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
    • B05D2701/00—Coatings being able to withstand changes in the shape of the substrate or to withstand welding
    • B05D2701/10—Coatings being able to withstand changes in the shape of the substrate or to withstand welding withstanding draw and redraw process, punching
    • 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 invention relates to a method for producing weather and corrosion resistant Formed sheet metal parts made of aluminum or an aluminum alloy with a decorative surface.
  • the parts are first made from a conventional process Band punched out and formed. Pretreatment and application Further surface layers are carried out on the parts that have already been formed. This procedure is very complex and complex Handling connected because the sheet metal parts to be treated in different baths put on holder and often from one holder to another have to be repositioned.
  • the invention has for its object a method of the aforementioned To create kind that under the continuous production of formed parts Allows application of a coil coating process.
  • the sol-gel varnish is preferably an alcoholic silane solution, preferably an alkoxysilane solution, and an aqueous colloidal silica solution manufactured polysiloxane and consists in particular of cross-linked inorganic polysiloxanes with over carbon bonds with the Silicon-linked organic groups, especially alkyl groups.
  • polysiloxane is the term for polymers made from cross-linked siloxanes.
  • Aluminum with a purity of 98.3% and higher can be used depending on the requirements placed on the surface quality e.g. Aluminum with a purity of 99.0% and higher, sometimes also with a purity of 99.5%. In particularly stored cases, a purity of 99.8% and be displayed higher.
  • the purities mentioned can also Aluminum alloys are used. Preferred alloys are those of the series AA 1000, AA 3000 and AA 5000.
  • Alloys contain, for example, 0.25 to 5% by weight, in particular 0.5 to 4% by weight magnesium or 0.2 to 2% by weight manganese, or 0.5 to 5% by weight Magnesium and 0.2 to 2 wt .-% manganese, in particular 1 wt .-% magnesium and 0.5% by weight of manganese, or 0.1 to 12% by weight, preferably 0.1 to 5 %
  • copper or 0.5 to 6% by weight zinc and 0.5 to 5% by weight magnesium, or 0.5 to 6% by weight zinc, 0.5 to 5% by weight magnesium and 0.5 to 5% by weight Copper, 0.5 to 2% by weight iron and 0.2 to 2% by weight manganese, in particular 1.5% by weight iron and 0.4% by weight manganese, or AIMgSi or AIFeSi alloys.
  • Other examples are AIMgCu alloys such as AlMg0.8Cu or AIMg alloys such as AIMg1, or AIFeMn alloys such as AlFeMn1.5.
  • the sheet metal parts can for example be bent, deep drawn or cold extruded or roll forming, but also be formed using other forming processes.
  • the pretreatment layer can be made, for example, by chromating, Phosphating or layer produced by anodic oxidation.
  • the pre-treatment layer made of anodized aluminum.
  • the pretreatment layer can have a thickness of, for example, at least 10 nm, preferably of at least 20 nm, in particular of at least 50 nm and advantageously have at least 100 nm.
  • the maximum thickness of the pretreatment layer is, for example, 5000 nm, preferably 1500 nm and especially 300 nm.
  • the pretreatment layer is preferably an anodically produced oxide layer, built up in a non-redissolving or in a redissolving electrolyte has been.
  • the pretreatment layer is preferably a porous, anodic generated oxide layer.
  • the anodization preferably takes place in an acidic electrolyte from the Series of phosphoric, citric, tartaric, chromic acid electrolytes and especially from the series of sulfuric acid electrolytes.
  • the anodization takes place in the AC or DC method.
  • the pretreatment layer can also be a yellow chromating layer, a green chromating layer, a phosphate layer or a chrome-free pretreatment layer, those contained in at least one of the elements Ti, Zr, F, Mo or Mn Electrolyte has been formed included.
  • the aluminum surface can be pretreated in a chemical or electrochemical processes or an alkaline pickling process be subjected. Such glossy or pickling processes are before nodize performed.
  • the belt surface is expediently degreased and cleaned.
  • the pretreatment can only be degreased and cleaned of the belt surface.
  • the belt surface can be cleaned on known way, e.g. chemical and / or electrochemical and acidic or alkaline. Its purpose is to remove foreign substances and, if necessary the naturally created oxide layer on the aluminum surface.
  • Suitable cleaning agents are e.g. acidic, aqueous degreasing agents, alkaline Degreasing agent based on polyphosphate and borate.
  • a cleaning with moderate to heavy material removal forms pickling or etching by means of strongly alkaline or acidic pickling solutions, e.g. Caustic soda or a mixture of nitric acid and hydrofluoric acid.
  • the existing one Removed oxide layer and its impurities. With strongly attacking alkaline Pickling may require acidic after-treatment.
  • the aluminum strip runs through the various treatment baths continuously at a speed of, for example, 40 m / min.
  • the protective layer and if necessary, additional layers are applied.
  • the sol-gel lacquer applied to the pretreatment layer is preferably a from an alcoholic silane solution, in particular an alkoxysilane solution, and a colonial silica solution polysiloxane.
  • the polysiloxane is particularly hydrolyzed by a condensation reaction between and crosslinkable silanes, especially alkoxysilanes, and colloidal Silica produces.
  • the condensation reaction between hydrolyzed silanes, especially alkoxysilanes, with each other as well as hydrolyzed silanes, especially alkoxysilanes, and colloidal silica leads to the formation of an inorganic Network of polysiloxanes.
  • organic groups in particular Alkyl groups or simple alkyl groups via carbon bonds built into the inorganic network.
  • the organic groups or the alkyl groups do not take part directly in the polymerization or the Cross-linking of the siloxanes, i.e. they are not used to form an organic Polymer system but only for functionalization.
  • the function is that the organic groups, especially the alkyl groups, attached to the outside of the polysiloxanes during the sol-gel process and thereby form a layer that is water-repellent to the outside, which gives the sol-gel varnish a pronounced hydrophobic property gives.
  • sol-gel process described leads, as mentioned, by targeted hydrolysis and condensation of alkoxides of silicon and silica to form a sol-gel lacquer from an inorganic network with built-in alkyl groups.
  • the polysiloxanes thus obtained are therefore rather inorganic Classify polymers.
  • sol-gel lacquer as Protective layer is expediently based on two basic solutions A and B.
  • Solution A is an alcoholic solution of one or more different ones Alkoxysilanes, the alkoxysilanes not in an anhydrous medium hydrolyzed form.
  • An alcohol is expediently used as solvent, such as, for example, methyl, ethyl, propyl or butyl alcohol and preferably isopropyl alcohol, used.
  • alkoxysilanes are described by the general formula X n Si (OR) 4-n , in which "R” is simple alkyl, preferably from the group comprising methyl, ethyl, propyl and butyl. "X” is also expediently an alkyl, preferably from the group comprising methyl, ethyl, propyl and butyl.
  • Suitable alkoxysilanes are, for example, tetramethoxysilanes (TMOS) and preferably tetraethoxysilane (TEOS) and methyltrimethoxysilane (MTMOS) and other alkoxysilanes.
  • solution A is made from tetraethoxysilane (TEOS) and / or methyltrimethoxysilane (MTMOS) with a methyl, Ethyl or propyl alcohol and especially with an isopropyl alcohol as Prepared solvent.
  • TEOS tetraethoxysilane
  • MTMOS methyltrimethoxysilane
  • Solution A can e.g. 25-35% by weight, in particular 30% by weight, TEOS and 15-25% by weight, in particular 20% by weight, Contain MTMOS, both dissolved in 40-60% by weight, in particular 50% by weight, Isopropyl alcohol.
  • Solution B contains colloidal silica dissolved in water.
  • solution B is adjusted to a pH between 2.0-4, preferably between 2.5-3.0 and in particular 2.7, using acid, preferably nitric acid (HNO 3 ).
  • the silica used is expediently a silica stabilized in an acidic environment, the pH of the silica advantageously being 2-4.
  • the silica is advantageously low in alkali.
  • the alkali content (eg Na 2 O) of the silica is preferably below 0.04% by weight.
  • Solution B contains, for example, 70-80% by weight, in particular 75% by weight, water as solvent and 20-30% by weight, in particular 25% by weight, of colloidal silica.
  • Solution B is expediently adjusted to a pH between 2.0-3.5, preferably between 2.5-3.0, and in particular 2.7, using nitric acid (HNO 3 ).
  • HNO 3 nitric acid
  • a preferred silica solution is, for example, by the company Nissan Chemical Industries Ltd. with the product name "SNOWTEX® O".
  • the sol-gel lacquer is expediently applied in gel form to the surface of the Aluminum tape applied and then dried or hardened.
  • the continuous coating is done in the coil painting process, too Coil coating process called.
  • a typical coil coating process is a Roller application process with two or three rollers.
  • the layer thickness of the cured Sol-gel lacquer is preferably at least 1 ⁇ m and is preferably between 1 and 4.5 ⁇ m, in particular between 1 and 3 ⁇ m. contains If the sol-gel lacquer also contains color pigments, the layer thickness can be up to 10 ⁇ m.
  • the drying process consists of the water remaining in the sol-gel varnish and drive out alcohols, whereby the sol-gel varnish hardens and a weather-resistant and corrosion-resistant protective layer on the belt surface arises.
  • the tape coated with the sol-gel varnish is expediently used Radiation, such as UV radiation, electron radiation, laser radiation, or by means of Heat radiation, such as IR radiation, or by means of convection heating or a combination of the aforementioned drying or curing processes, dried respectively. hardened.
  • Radiation such as UV radiation, electron radiation, laser radiation, or by means of Heat radiation, such as IR radiation, or by means of convection heating or a combination of the aforementioned drying or curing processes, dried respectively. hardened.
  • the temperature measured on the belt surface for drying or hardening the sol-gel lacquer is expediently greater than 60 ° C., preferably greater than 150 ° C and especially greater than 200 ° C.
  • the elevated temperature is furthermore expediently less than 400 ° C., preferably less than 350 ° C. and in particular less than 300 °.
  • the temperature is particularly preferred between 250 ° C and 300 ° C.
  • the temperature specification is a so-called "Peak Metal Temperature” (PMT).
  • the elevated temperature can, for example, last for 5 seconds to 2 minutes act on the tape.
  • the sol-gel varnish is preferred for a period of time less than 90 seconds, especially less than 60 seconds, and preferably more than 10 seconds, especially more than Dried or hardened for 30 seconds.
  • the Drying times tend to be in the lower range of the specified stay times.
  • Convection heating can be carried out expediently by applying heated gases such as air, nitrogen, noble gases or mixtures thereof.
  • heated gases such as air, nitrogen, noble gases or mixtures thereof.
  • the sol-gel lacquer layer is dried in a continuous oven.
  • the formed parts are after the application and drying of the protective layer punched out of the band and formed.
  • the forming hardly leads to crack formation in the protective layer.
  • the formed parts produced by the process according to the invention have thanks to the hard protective layer with excellent adhesion good protection against weather, corrosion and mechanical Abrasion and are characterized by good UV resistance out.
  • the molded parts produced according to the invention have a sol-gel protective layer made of polysiloxanes with a high surface hardness.
  • the sol-gel protective layer expediently has a pencil method according to Wolf Wilburn "according to DIN 55350 part 18 hardness of greater than "f ', preferably greater than” h ", in particular greater than” 2h “and advantageous from larger "3h", whereby larger in the sense of harder to understand is.
  • the sol-gel layer is also characterized by excellent adhesion on the formed sheet metal parts.
  • the pH of solution B is adjusted to approximately 2.7 with the addition of an acid, in particular nitric acid (HNO 3 ).
  • sol-gel varnish and the coating of the aluminum strip is carried out in a preferred embodiment as follows:
  • the solutions A and B are under continuous Stirring transferred into a mixed solution, heat due to reaction is released.
  • the mixed solution is over a certain time, for example for 1 h to 10 h, preferably during 4 to 8 h, in particular stirred for around 6 h.
  • the mixture is then filtered.
  • the filter serves to hold back larger Particles such as Particles of colonial silica.
  • the pore diameter or the mesh size of the filter depends on the desired layer thickness, because particles with a larger diameter than the desired layer thickness affect the surface quality of the protective layer. Filtration can for example using a polypropylene filter with a porosity of 1 ⁇ m.
  • the mixed solution is expediently at a pH of 2-4, preferably from 2 to 3.5, in particular from 2.5 to 3, and particularly preferably from 2.7, held.
  • the pH is adjusted using acid, preferably using Nitric acid.
  • the sol-gel varnish can be removed using one of the the aforementioned method is applied to the belt surface and subsequently, can be dried or hardened as described above.
  • the sol-gel varnish after its manufacture and before application to the belt surface during a few minutes to several hours, preferably between 1 and 24 hours, especially between 12 and 22 h and particularly preferably for around 17 h immobilized.
  • the element analysis of the hardened sol-gel varnish using XPS has e.g. the elements oxygen, silicon and around 5 - 20 at.% (atomic percent) carbon after.

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Abstract

A coil-coating process for the production of weather- and corrosion-resistant, decorative formed parts from aluminum (or aluminum alloy) strip involves the application and hardening of a protective, polysiloxane-based sol-gel varnish before stamping out and forming the parts. A method for the production of weather- and corrosion-resistant formed parts with a decorative surface from aluminum or Al alloy sheet by a coil-coating process involves (1) preparation of a strip of Al or Al alloy (2) optional continuous degreasing (3) optional burnishing by an electrochemical, chemical or mechanical method (4) continuous pretreatment to form a primer layer (5) continuous application of polysiloxane-based sol-gel varnish to form a protective layer (6) continuous drying and hardening in a through-type oven (7) stamping out the parts (8) forming the stamped-out parts .

Description

Die Erfindung betrifft ein Verfahren zur Herstellung witterungs- und korrosionsbeständiger umgeformter Blechteile aus Aluminium oder aus einer Aluminiumlegierung mit dekorativer Oberfläche.The invention relates to a method for producing weather and corrosion resistant Formed sheet metal parts made of aluminum or an aluminum alloy with a decorative surface.

Bei der Herstellung von dekorativen Umformteilen aus Aluminiumblech, wie z.B. Zierleisten, werden die Teile in herkömmlichen Verfahren zunächst aus einem Band ausgestanzt und umgeformt. Die Vorbehandlung und das Aufbringen weiterer Oberflächenschichten wird an den bereits umgeformten Teilen durchgeführt. Diese Verfahrensweise ist sehr aufwendig und mit einem komplexen Handling verbunden, da die in verschiedenen Bädern zu behandelnden Blechteile auf Halter aufgesteckt und oft auch von einem Halter auf einen anderen umgesteckt werden müssen.In the production of decorative formed parts from aluminum sheet, such as Decorative strips, the parts are first made from a conventional process Band punched out and formed. Pretreatment and application Further surface layers are carried out on the parts that have already been formed. This procedure is very complex and complex Handling connected because the sheet metal parts to be treated in different baths put on holder and often from one holder to another have to be repositioned.

Der Erfindung liegt die Aufgabe zugrunde, ein Verfahren der eingangs genannten Art zu schaffen, das die kontinuierliche Herstellung von Umformteilen unter Anwendung eines Coil-Coating-Verfahrens ermöglicht.The invention has for its object a method of the aforementioned To create kind that under the continuous production of formed parts Allows application of a coil coating process.

Zur erfindungsgemässen Lösung der Aufgabe führt ein Verfahren, das nacheinander die folgenden Schritte umfasst:

  • Bereitstellen eines Bandes aus Aluminium oder aus einer Aluminiumlegierung,
  • gegebenenfalls kontinuierliches Entfetten des Bandes,
  • gegebenenfalls elektrochemisches, chemisches oder mechanisches Glänzen des gegebenenfalls entfetteten Bandes,
  • kontinuierliche Vorbehandlung des gegebenenfalls entfetteten und/oder geglänzten Bandes zur Erzeugung einer als Haftgrund für eine Lackschicht geeigneten Vorbehandlungsschicht,
  • kontinuierliches Lackieren des vorbehandelten Bandes mit einem Sol-Gel-Lack aus einem Polysiloxan zur Erzeugung einer Schutzschicht,
  • kontinuierliches Trocknen und Härten der Schutzschicht in einem Durchlaufofen,
  • Ausstanzen der mit der Schutzschicht versehenen Blechteile aus dem Band,
  • Umformen der ausgestanzten Blechteile.
A method which comprises the following steps in succession leads to the achievement of the object according to the invention:
  • Providing a strip made of aluminum or an aluminum alloy,
  • if necessary, continuous degreasing of the belt,
  • optionally electrochemical, chemical or mechanical glossing of the optionally degreased strip,
  • continuous pretreatment of the possibly degreased and / or polished tape to produce a pretreatment layer suitable as a primer for a lacquer layer,
  • continuous painting of the pre-treated tape with a sol-gel paint made of a polysiloxane to create a protective layer,
  • continuous drying and hardening of the protective layer in a continuous furnace,
  • Punching the sheet metal parts provided with the protective layer out of the strip,
  • Forming the punched sheet metal parts.

Der Sol-Gel-Lack ist bevorzugt ein aus einer alkoholischen Silan-Lösung, vorzugsweise einer Alkoxysilan-Lösung, und einer wässrigen kolloidalen Kieselsäure-Lösung hergestelltes Polysiloxan und besteht insbesondere aus vernetzten anorganischen Polysiloxanen mit über Kohlenstoffbindungen mit dem Silizium verbundenen organischen Gruppen, insbesondere Alkylgruppen. Polysiloxan ist dabei der Begriff für Polymere aus vernetzten Siloxanen.The sol-gel varnish is preferably an alcoholic silane solution, preferably an alkoxysilane solution, and an aqueous colloidal silica solution manufactured polysiloxane and consists in particular of cross-linked inorganic polysiloxanes with over carbon bonds with the Silicon-linked organic groups, especially alkyl groups. polysiloxane is the term for polymers made from cross-linked siloxanes.

Als Bandmaterial für die Herstellung der Umformteile kann handelsübliches Aluminium mit einer Reinheit von 98,3% und höher verwendet werden, je nach den an die Oberflächenqualität gestellten Anforderungen z.B. Aluminium mit einer Reinheit von 99,0% und höher, fallweise auch mit einer Reinheit von 99,5%. In besonders gelagerten Fällen kann auch eine Reinheit von 99,8% und höher angezeigt sein. Neben Aluminium der genannte Reinheiten können auch Aluminiumlegierungen eingesetzt werden. Bevorzugte Legierungen sind diejenigen der Reihen AA 1000, AA 3000 und AA 5000. Weitere in Frage kommende Legierungen enthalten beispielsweise 0,25 bis 5 Gew.-%, insbesondere 0,5 bis 4 Gew.-% Magnesium oder 0,2 bis 2 Gew.-% Mangan, oder 0,5 bis 5 Gew.-% Magnesium und 0,2 bis 2 Gew.-% Mangan, insbesondere 1 Gew.-% Magnesium und 0,5 Gew.-% Mangan, oder 0,1 bis 12 Gew.-%, vorzugsweise 0,1 bis 5 Gew.-% Kupfer, oder 0,5 bis 6 Gew.-% Zink und 0,5 bis 5 Gew.-% Magnesium, oder 0,5 bis 6 Gew.-% Zink, 0,5 bis 5 Gew.-% Magnesium und 0,5 bis 5 Gew.-% Kupfer, 0,5 bis 2 Gew.-% Eisen und 0,2 bis 2 Gew.-% Mangan, insbesondere 1,5 Gew.-% Eisen und 0,4 Gew.-% Mangan, oder AIMgSi- oder AIFeSi-Legierungen. Weitere Beispiele sind AIMgCu-Legierungen, wie AlMg0,8Cu oder AIMg-Legierungen, wie AIMg1, oder AIFeMn-Legierungen wie AlFeMn1,5.Commercial material can be used as the strip material for the production of the formed parts Aluminum with a purity of 98.3% and higher can be used depending on the requirements placed on the surface quality e.g. Aluminum with a purity of 99.0% and higher, sometimes also with a purity of 99.5%. In particularly stored cases, a purity of 99.8% and be displayed higher. In addition to aluminum, the purities mentioned can also Aluminum alloys are used. Preferred alloys are those of the series AA 1000, AA 3000 and AA 5000. Further possible ones Alloys contain, for example, 0.25 to 5% by weight, in particular 0.5 to 4% by weight magnesium or 0.2 to 2% by weight manganese, or 0.5 to 5% by weight Magnesium and 0.2 to 2 wt .-% manganese, in particular 1 wt .-% magnesium and 0.5% by weight of manganese, or 0.1 to 12% by weight, preferably 0.1 to 5 % By weight copper, or 0.5 to 6% by weight zinc and 0.5 to 5% by weight magnesium, or 0.5 to 6% by weight zinc, 0.5 to 5% by weight magnesium and 0.5 to 5% by weight Copper, 0.5 to 2% by weight iron and 0.2 to 2% by weight manganese, in particular 1.5% by weight iron and 0.4% by weight manganese, or AIMgSi or AIFeSi alloys. Other examples are AIMgCu alloys such as AlMg0.8Cu or AIMg alloys such as AIMg1, or AIFeMn alloys such as AlFeMn1.5.

Die Blechteile können beispielsweise durch Biegen, Tiefziehen, Kaltfliesspressen oder Rollumformen, aber auch über andere Umformverfahren geformt werden.The sheet metal parts can for example be bent, deep drawn or cold extruded or roll forming, but also be formed using other forming processes.

Die Vorbehandlungsschicht kann beispielsweise eine durch Chromatierung, Phosphatierung oder durch anodische Oxidation erzeugte Schicht sein. Vorzugsweise ist die Vorbehandlungsschicht aus anodisch oxidiertem Aluminium.The pretreatment layer can be made, for example, by chromating, Phosphating or layer produced by anodic oxidation. Preferably is the pre-treatment layer made of anodized aluminum.

Die Vorbehandlungsschicht kann eine Dicke von beispielsweise wenigstens 10 nm, vorzugsweise von wenigstens 20 nm, insbesondere von wenigstens 50 nm und vorteilhaft von wenigstens 100 nm aufweisen. Die maximale Dicke der Vorbehandlungsschicht beträgt beispielsweise 5000 nm, vorzugsweise 1500 nm und insbesondere 300 nm.The pretreatment layer can have a thickness of, for example, at least 10 nm, preferably of at least 20 nm, in particular of at least 50 nm and advantageously have at least 100 nm. The maximum thickness of the pretreatment layer is, for example, 5000 nm, preferably 1500 nm and especially 300 nm.

Die Vorbehandlungsschicht ist bevorzugt eine anodisch erzeugte Oxidschicht, die in einem nicht rücklösenden oder in einem rücklösenden Elektrolyten aufgebaut wurde. Die Vorbehandlungsschicht ist vorzugsweise eine poröse, anodisch erzeugte Oxidschicht.The pretreatment layer is preferably an anodically produced oxide layer, built up in a non-redissolving or in a redissolving electrolyte has been. The pretreatment layer is preferably a porous, anodic generated oxide layer.

Die Anodisation findet vorzugsweise in einem sauren Elektrolyten aus der Reihe der Phosphorsäure-, Zitronensäure-, Weinsäure-, Chromsäureelektrolyte und insbesondere aus der Reihe der Schwefelsäureelektrolyte statt. Die Anodisation erfolgt im Wechsel- oder im Gleichstromverfahren.The anodization preferably takes place in an acidic electrolyte from the Series of phosphoric, citric, tartaric, chromic acid electrolytes and especially from the series of sulfuric acid electrolytes. The anodization takes place in the AC or DC method.

Die Vorbehandlungsschicht kann auch eine Gelbchromatierschicht, eine Grünchromatierschicht, eine Phosphatschicht oder eine chromfreie Vorbehandlungsschicht, die in einem wenigstens eines der Elemente Ti, Zr, F, Mo oder Mn enthaltenden Elektrolyten ausgebildet worden ist, enthalten.The pretreatment layer can also be a yellow chromating layer, a green chromating layer, a phosphate layer or a chrome-free pretreatment layer, those contained in at least one of the elements Ti, Zr, F, Mo or Mn Electrolyte has been formed included.

Ferner kann die Aluminiumoberfläche zur Vorbehandlung in einem chemischen oder elektrochemischen Verfahren geglänzt oder einem alkalischen Beizprozess unterzogen werden. Solche Glänz- oder Beizverfahren werden vor dem nodisieren durchgeführt. Furthermore, the aluminum surface can be pretreated in a chemical or electrochemical processes or an alkaline pickling process be subjected. Such glossy or pickling processes are before nodize performed.

Vor dem Auftrag einer Vorbehandlungsschicht oder Durchführung erster Vorbehandlungsschritte wird die Bandoberfläche zweckmässigerweise entfettet und gereinigt. Die Vorbehandlung kann auch lediglich ein Entfetten und Reinigen der Bandoberfläche beinhalten. Die Reinigung der Bandoberfläche kann auf an sich bekannte Weise, z.B. chemisch und/oder elektrochemisch und sauer oder alkalisch, erfolgen. Sie bezweckt die Entfernung von Fremdsubstanzen und gegebenenfalls der natürlich entstanden Oxidschicht auf der Aluminiumoberfläche. Als Reinigungsmittel eignen sich z.B. saure, wässrige Entfettungsmittel, alkalische Entfettungsmittel auf der Basis von Polyphosphat und Borat. Eine Reinigung mit mässigem bis starkem Materialabtrag bildet das Beizen oder Ätzen mittels stark alkalischen oder sauren Beizlösungen, wie z.B. Natronlauge oder ein Gemisch aus Salpetersäure und Flusssäure. Dabei wird die vorhandene Oxidschicht samt ihren Verunreinigungen entfernt. Bei stark angreifenden alkalischen Beizen ist gegebenenfalls eine saure Nachbehandlung notwendig.Before applying a pre-treatment layer or performing the first pre-treatment steps the belt surface is expediently degreased and cleaned. The pretreatment can only be degreased and cleaned of the belt surface. The belt surface can be cleaned on known way, e.g. chemical and / or electrochemical and acidic or alkaline. Its purpose is to remove foreign substances and, if necessary the naturally created oxide layer on the aluminum surface. Suitable cleaning agents are e.g. acidic, aqueous degreasing agents, alkaline Degreasing agent based on polyphosphate and borate. A cleaning with moderate to heavy material removal forms pickling or etching by means of strongly alkaline or acidic pickling solutions, e.g. Caustic soda or a mixture of nitric acid and hydrofluoric acid. The existing one Removed oxide layer and its impurities. With strongly attacking alkaline Pickling may require acidic after-treatment.

Mit an sich bekannten elektrochemischen, chemischen oder mechanischen Glänzverfahren kann ebenfalls eine Reinigung der Bandoberfläche erzielt werden. Durch den Glänzvorgang kann zudem das optische Erscheinungsbild der Bandoberfläche am Endprodukt beeinflusst werden.With known electrochemical, chemical or mechanical Shine processes can also be used to clean the belt surface. Due to the glossy process, the visual appearance of the Belt surface on the end product can be influenced.

Im Rahmen des erfindungsgemässen Verfahrens kann bei einer bevorzugten Ausführung die Vorbehandlungsschicht beispielsweise unter Einhaltung der folgenden Verfahrensbedingung auf das Aluminiumband aufgebracht werden:

  • a) Entfetten bei pH 9 - 9,5 bei ca. 50°C,
  • b) Spülen mit Leitungswasser (Raumtemperatur),
  • c) Elektrochemisches Glänzen,
  • d) Spülen mit Leitungswasser (Raumtemperatur),
  • e) Anodisieren in 20% H2SO4 bei ca. 25°C und 20V Spannung,
  • f) Spülen in Leitungswasser bei ca. 50°C und
  • g) Spülen in entionisiertem Wasser bei ca. 85°C.
    • In the context of the method according to the invention, in a preferred embodiment, the pretreatment layer can be applied to the aluminum strip, for example, in compliance with the following process conditions:
  • a) degreasing at pH 9 - 9.5 at approx. 50 ° C,
  • b) rinsing with tap water (room temperature),
  • c) electrochemical shine,
  • d) rinsing with tap water (room temperature),
  • e) anodizing in 20% H 2 SO 4 at approx. 25 ° C and 20V voltage,
  • f) rinsing in tap water at approx. 50 ° C and
  • g) Rinse in deionized water at approx. 85 ° C.

    • Das Aluminiumband durchläuft die verschiedenen Behandlungsbäder kontinuierlich mit einer Geschwindigkeit von beispielsweise 40 m/min.The aluminum strip runs through the various treatment baths continuously at a speed of, for example, 40 m / min.

    Auf die Vorbehandlungsschicht können anschliessend die Schutzschicht und gegebenenfalls weitere Schichten aufgebracht werden.The protective layer and if necessary, additional layers are applied.

    Der auf die Vorbehandlungsschicht aufgetragene Sol-Gel-Lack ist bevorzugt ein aus einer alkoholischen Silan-Lösung, insbesondere einer Alkoxysilan-Lösung, und einer kolonialen Kieselsäure-Lösung hergestelltes Polysiloxan. Das Polysiloxan wird insbesondere durch eine Kondensationsreaktion zwischen hydrolisierten und vernetzbaren Silanen, insbesondere Alkoxysilanen, und kolloidaler Kieselsäure erzeugt.The sol-gel lacquer applied to the pretreatment layer is preferably a from an alcoholic silane solution, in particular an alkoxysilane solution, and a colonial silica solution polysiloxane. The polysiloxane is particularly hydrolyzed by a condensation reaction between and crosslinkable silanes, especially alkoxysilanes, and colloidal Silica produces.

    Die Kondensationsreaktion zwischen hydrolisierten Silanen, insbesondere Alkoxysilanen, untereinander sowie hydrolisierten Silanen, insbesondere Alkoxysilanen, und kolloidaler Kieselsäure führt zur Ausbildung eines anorganischen Netzwerkes von Polysiloxanen. Gleichzeitig werden organische Gruppen, insbesondere Alkylgruppen bzw. einfache Alkylgruppen über Kohlenstoffbindungen in das anorganische Netzwerk eingebaut. Die organischen Gruppen, bzw. die Alkyl-Gruppen, nehmen jedoch nicht direkt an der Polymerisation bzw. der Vernetzung der Siloxane teil, d.h. sie dienen nicht zur Ausbildung eines organischen Polymersystems sondern lediglich zur Funktionalisierung. Die Funktion liegt darin, dass die organischen Gruppen, insbesondere die Alkyl-Gruppen, während des Sol-Gel-Prozesses an den Aussenseiten der Polysiloxane angehängt werden und dadurch eine gegen aussen wasserabstossende Lage ausbilden, welche dem Sol-Gel-Lack eine ausgeprägte hydrophobe Eigenschaft verleiht.The condensation reaction between hydrolyzed silanes, especially alkoxysilanes, with each other as well as hydrolyzed silanes, especially alkoxysilanes, and colloidal silica leads to the formation of an inorganic Network of polysiloxanes. At the same time, organic groups, in particular Alkyl groups or simple alkyl groups via carbon bonds built into the inorganic network. The organic groups or the alkyl groups, however, do not take part directly in the polymerization or the Cross-linking of the siloxanes, i.e. they are not used to form an organic Polymer system but only for functionalization. The function is that the organic groups, especially the alkyl groups, attached to the outside of the polysiloxanes during the sol-gel process and thereby form a layer that is water-repellent to the outside, which gives the sol-gel varnish a pronounced hydrophobic property gives.

    Der beschriebene Sol-Gel-Prozess führt, wie erwähnt, durch gezielte Hydrolyse und Kondensation von Alkoxiden des Siliziums und Kieselsäure zu einem Sol-Gel-Lack aus einem anorganischen Netzwerk mit eingebauten Alkylgruppen. Die dadurch erhaltenen Polysiloxane sind deshalb eher den anorganischen Polymeren einzuordnen.The sol-gel process described leads, as mentioned, by targeted hydrolysis and condensation of alkoxides of silicon and silica to form a sol-gel lacquer from an inorganic network with built-in alkyl groups. The polysiloxanes thus obtained are therefore rather inorganic Classify polymers.

    Bei der Herstellung einer bevorzugten Ausführung eines Sol-Gel-Lackes als Schutzschicht wird zweckmässigerweise von zwei Basislösungen A und B ausgegangen.In the production of a preferred embodiment of a sol-gel lacquer as Protective layer is expediently based on two basic solutions A and B.

    Die Lösung A ist eine alkoholische Lösung eines oder mehrerer verschiedener Alkoxysilane, wobei die Alkoxysilane in einem wasserfreien Medium in nicht hydrolisierter Form vorliegen. Als Lösungsmittel wird zweckmässig ein Alkohol, wie beispielsweise Methyl-, Ethyl-, Propyl- oder Butylalkohol und bevorzugt Isopropylalkohol, verwendet.Solution A is an alcoholic solution of one or more different ones Alkoxysilanes, the alkoxysilanes not in an anhydrous medium hydrolyzed form. An alcohol is expediently used as solvent, such as, for example, methyl, ethyl, propyl or butyl alcohol and preferably isopropyl alcohol, used.

    Die Alkoxysilane werden durch die allgemeine Formel XnSi(OR)4-n beschrieben, in welcher "R" ein einfaches Alkyl ist, vorzugsweise aus der Gruppe umfassend Methyl, Ethyl, Propyl und Buthyl. "X" ist zweckmässig ebenfalls ein Alkyl, vorzugsweise aus der Gruppe umfassend Methyl, Ethyl, Propyl und Buthyl. Zweckmässige Alkoxysilane sind beispielsweise Tetramethoxysilane (TMOS) und bevorzugt Tetraethoxysilan (TEOS) und Methyltrimethoxysilan (MTMOS) und weitere Alkoxysilane.The alkoxysilanes are described by the general formula X n Si (OR) 4-n , in which "R" is simple alkyl, preferably from the group comprising methyl, ethyl, propyl and butyl. "X" is also expediently an alkyl, preferably from the group comprising methyl, ethyl, propyl and butyl. Suitable alkoxysilanes are, for example, tetramethoxysilanes (TMOS) and preferably tetraethoxysilane (TEOS) and methyltrimethoxysilane (MTMOS) and other alkoxysilanes.

    In besonders bevorzugter Ausführungsform wird die Lösung A aus Tetraethoxysilan (TEOS) und/oder Methyltrimethoxysilan (MTMOS) mit einem Methyl-, Ethyl- oder Propyl-Alkohol und insbesondere mit einem Isopropylalkohol als Lösungsmittel zubereitet. Die Lösung A kann z.B. 25 - 35 Gew.-%, insbesondere 30 Gew.-%, TEOS und 15 - 25 Gew.-%, insbesondere 20 Gew.-%, MTMOS enthalten, beides gelöst in 40 - 60 Gew.-%, insbesondere 50 Gew.-%, Isopropylalkohol.In a particularly preferred embodiment, solution A is made from tetraethoxysilane (TEOS) and / or methyltrimethoxysilane (MTMOS) with a methyl, Ethyl or propyl alcohol and especially with an isopropyl alcohol as Prepared solvent. Solution A can e.g. 25-35% by weight, in particular 30% by weight, TEOS and 15-25% by weight, in particular 20% by weight, Contain MTMOS, both dissolved in 40-60% by weight, in particular 50% by weight, Isopropyl alcohol.

    Die Lösung B enthält in Wasser gelöste kolloidale Kieselsäure. In zweckmässiger Ausführung wird die Lösung B mittels Säure, vorzugsweise mittels Salpetersäure (HNO3), auf einen pH-Wert zwischen 2,0 - 4, vorzugsweise zwischen 2,5 - 3,0 und insbesondere von 2,7 eingestellt. Solution B contains colloidal silica dissolved in water. In an expedient embodiment, solution B is adjusted to a pH between 2.0-4, preferably between 2.5-3.0 and in particular 2.7, using acid, preferably nitric acid (HNO 3 ).

    Die verwendete Kieselsäure ist zweckmässig eine in saurem Milieu stabilisierte Kieselsäure, wobei der pH-Wert der Kieselsäure vorteilhaft bei 2 - 4 liegt. Die Kieselsäure ist vorteilhaft möglichst alkaliarm. Der Alkaligehalt (z.B. Na2O) der Kieselsäure liegt bevorzugt unter 0,04 Gew.-%.The silica used is expediently a silica stabilized in an acidic environment, the pH of the silica advantageously being 2-4. The silica is advantageously low in alkali. The alkali content (eg Na 2 O) of the silica is preferably below 0.04% by weight.

    Die Lösung B enthält beispielsweise 70 - 80 Gew.-%, insbesondere 75 Gew.-%, Wasser als Lösungsmittel und 20 - 30 Gew.-%, insbesondere 25 Gew.-%, kolloidale Kieselsäure. Die Lösung B ist zweckmässig mittels Salpetersäure (HNO3) auf einen pH-Wert zwischen 2,0 - 3,5, vorzugsweise zwischen 2,5 - 3,0, und insbesondere von 2,7 eingestellt. Eine bevorzugte Kieselsäure-Lösung wird beispielsweise durch die Firma Nissan Chemical Industries Ltd. mit dem Produktname "SNOWTEX® O" vertrieben.Solution B contains, for example, 70-80% by weight, in particular 75% by weight, water as solvent and 20-30% by weight, in particular 25% by weight, of colloidal silica. Solution B is expediently adjusted to a pH between 2.0-3.5, preferably between 2.5-3.0, and in particular 2.7, using nitric acid (HNO 3 ). A preferred silica solution is, for example, by the company Nissan Chemical Industries Ltd. with the product name "SNOWTEX® O".

    Das Zusammenführen und Mischen der beiden Basislösungen A und B führt in Gegenwart der Salpetersäure zu einer Hydrolysereaktion zwischen dem in Lösung B enthaltenen Wasser und den in Lösung A enthaltenen Alkoxysilanen. Hydrolysereaktion: Si(OR)n+nH2O → Si(OH)n +nR(OH) Gleichzeitig tritt eine Kondensationsreaktion ein, bei der unter Wasserabspaltung aus jeweils zwei Si-OH-Gruppen eine Siloxan-Bindung (Si-O-Si) aufgebaut wird. Durch fortschreitende Polymerisation entsteht dabei ein Netzwerk von Polysiloxanen, an welche Alkyl-Gruppen angegliedert sind. Die neue Mischlösung liegt in einem gelförmigen Zustand vor. Die beiden Lösungen A und B werden bevorzugt in einem Gewichtsverhältnis von 7 : 3 Teilen gemischt.The combination and mixing of the two basic solutions A and B in the presence of the nitric acid leads to a hydrolysis reaction between the water contained in solution B and the alkoxysilanes contained in solution A. Hydrolysis reaction: Si (OR) n + nH 2 O → Si (OH) n + nR (OH) At the same time, a condensation reaction occurs in which a siloxane bond (Si-O-Si) is built up from two Si-OH groups each with elimination of water. As the polymerization progresses, a network of polysiloxanes to which alkyl groups are attached is formed. The new mixed solution is in a gel state. The two solutions A and B are preferably mixed in a weight ratio of 7: 3 parts.

    Der Sol-Gel-Lack wird zweckmässigerweise in Gel-Form auf die Oberfläche des Aluminiumbandes aufgetragen und anschliessend getrocknet bzw. gehärtet.The sol-gel lacquer is expediently applied in gel form to the surface of the Aluminum tape applied and then dried or hardened.

    Die kontinuierliche Beschichtung erfolgt im Bandlackierungsverfahren, auch Coil-Coating-Verfahren genannt. Ein typisches Coil-Coating-Verfahren ist ein Walzenauftragverfahren mit zwei oder drei Walzen. Die Schichtdicke des ausgehärteten Sol-Gel-Lackes beträgt bevorzugt wenigstens 1 µm und liegt vorzugsweise zwischen 1 und 4,5 µm, insbesondere zwischen 1 und 3 µm. Enthält der Sol-Gel-Lack zusätzlich noch Farbpigmente, kann die Schichtdicke bis 10 µm betragen.The continuous coating is done in the coil painting process, too Coil coating process called. A typical coil coating process is a Roller application process with two or three rollers. The layer thickness of the cured Sol-gel lacquer is preferably at least 1 μm and is preferably between 1 and 4.5 µm, in particular between 1 and 3 µm. contains If the sol-gel lacquer also contains color pigments, the layer thickness can be up to 10 µm.

    Der Trocknungsprozess besteht darin, die im Sol-Gel-Lack verbleibenden Wasser und Alkohole auszutreiben, wodurch der Sol-Gel-Lack aushärtet und eine witterungsbeständige und korrosionsfeste Schutzschicht auf der Bandoberfläche entsteht.The drying process consists of the water remaining in the sol-gel varnish and drive out alcohols, whereby the sol-gel varnish hardens and a weather-resistant and corrosion-resistant protective layer on the belt surface arises.

    Das mit dem Sol-Gel-Lack beschichtete Band wird zweckmässigerweise mittels Strahlung, wie UV-Strahlung, Elektronenstrahlung, Laserstrahlung, oder mittels Wärmestrahlung, wie IR-Strahlung, oder mittels Konvektionserwärmung oder einer Kombination der vorgenannten Trockungs- bzw. Härtungsverfahren, getrocknet resp. gehärtet.The tape coated with the sol-gel varnish is expediently used Radiation, such as UV radiation, electron radiation, laser radiation, or by means of Heat radiation, such as IR radiation, or by means of convection heating or a combination of the aforementioned drying or curing processes, dried respectively. hardened.

    Die an der Bandoberfläche gemessene Temperatur zur Trockung bzw. Härtung des Sol-Gel-Lackes ist zweckmässig grösser als 60° C, vorzugsweise grösser als 150° C und insbesondere grösser als 200° C. Die erhöhte Temperatur ist ferner zweckmässigerweise kleiner als 400°C, vorzugsweise kleiner als 350°C und insbesondere kleiner als 300°. Die Temperatur liegt besonders bevorzugt zwischen 250°C und 300°C. Bei der Temperaturangabe handelt es sich um eine sogenannte "Peak Metal Temperature" (PMT).The temperature measured on the belt surface for drying or hardening the sol-gel lacquer is expediently greater than 60 ° C., preferably greater than 150 ° C and especially greater than 200 ° C. The elevated temperature is furthermore expediently less than 400 ° C., preferably less than 350 ° C. and in particular less than 300 °. The temperature is particularly preferred between 250 ° C and 300 ° C. The temperature specification is a so-called "Peak Metal Temperature" (PMT).

    Die erhöhte Temperatur kann beispielsweise während 5 Sekunden bis 2 Minuten auf das Band einwirken. Der Sol-Gel-Lack wird während einer Zeit von vorzugsweise weniger als 90 Sekunden, insbesondere von weniger als 60 Sekunden, und von vorzugsweise mehr als 10 Sekunden, insbesondere von mehr als 30 Sekunden getrocknet bzw. gehärtet. Bei Einsatz von IR-Strahlung liegen die Trockungszeiten eher im unteren Bereich der angegebenen Aufenthaltszeiten.The elevated temperature can, for example, last for 5 seconds to 2 minutes act on the tape. The sol-gel varnish is preferred for a period of time less than 90 seconds, especially less than 60 seconds, and preferably more than 10 seconds, especially more than Dried or hardened for 30 seconds. When using IR radiation, the Drying times tend to be in the lower range of the specified stay times.

    Die Konvektionserwärmung kann zweckmässig durch eine Beaufschlagung mit erwärmten Gasen, wie Luft, Stickstoff, Edelgase oder Gemischen daraus, erfolgen. Die Sol-Gel-Lackschicht wird in einem Durchlaufofen getrocknet.Convection heating can be carried out expediently by applying heated gases such as air, nitrogen, noble gases or mixtures thereof. The sol-gel lacquer layer is dried in a continuous oven.

    Die Umformteile werden nach dem Auftrag und Trocknung der Schutzschicht aus dem Band ausgestanzt und umgeformt. Die Umformung führt dabei kaum zu Rissbildung in der Schutzschicht.The formed parts are after the application and drying of the protective layer punched out of the band and formed. The forming hardly leads to crack formation in the protective layer.

    Die nach dem erfindungsgemässen Verfahren hergestellten Umformteile weisen dank der harten und eine ausgezeichnete Haftung aufweisenden Schutzschicht eine gute Schutzwirkung gegen Witterungseinflüsse, Korrosion und mechanischen Abrieb auf und zeichnen sich durch eine gute UV-Beständigkeit aus.The formed parts produced by the process according to the invention have thanks to the hard protective layer with excellent adhesion good protection against weather, corrosion and mechanical Abrasion and are characterized by good UV resistance out.

    Die erfindungsgemäss hergestellten Umformteile verfügen dank der Sol-Gel-Schutzschicht aus Polysiloxanen über eine hohe Oberflächenhärte. Die Sol-Gel-Schutzschicht weist zweckmässigerweise eine nach der Methode "Bleistiftverfahren nach Wolf Wilburn" nach DIN 55350 Teil 18 gemessene Härte von grösser "f', vorzugsweise von grösser "h", insbesondere von grösser "2h" und vorteilhaft von grösser "3h" auf, wobei grösser im Sinne von härter zu verstehen ist.The molded parts produced according to the invention have a sol-gel protective layer made of polysiloxanes with a high surface hardness. The sol-gel protective layer expediently has a pencil method according to Wolf Wilburn "according to DIN 55350 part 18 hardness of greater than "f ', preferably greater than" h ", in particular greater than" 2h "and advantageous from larger "3h", whereby larger in the sense of harder to understand is.

    Die Sol-Gel-Schicht zeichnet sich zudem durch eine ausgezeichnete Haftung auf den umgeformten Blechteilen aus.The sol-gel layer is also characterized by excellent adhesion on the formed sheet metal parts.

    Nachfolgend wird anhand eines Beispiels die Zubereitung und Herstellung einer besonders bevorzugten Ausführung eines Sol-Gel-Lackes beschrieben. Dazu werden eine Lösung A und eine Lösung B vorbereitet.The preparation and manufacture of a described particularly preferred embodiment of a sol-gel lacquer. To a solution A and a solution B are prepared.

    Lösung A enthält:

  • 50 Gew.-% Isopropylalkohol
  • 30 Gew.-% Tetraethoxysilan (TEOS)
  • 20 Gew.-% Methyltrimethoxysilan (MTMOS)
    • Solution A contains:
  • 50% by weight isopropyl alcohol
  • 30% by weight tetraethoxysilane (TEOS)
  • 20% by weight methyltrimethoxysilane (MTMOS)

    • Lösung B enthält:

  • 75 Gew.-% Wasser
  • 25 Gew.-% Kolloidale Kieselsäure
    • Solution B contains:
  • 75% by weight of water
  • 25% by weight colloidal silica

    • Der pH-Wert der Lösung B ist unter Zugabe einer Säure, insbesondere Salpetersäure (HNO3), auf ca. 2,7 eingestellt.The pH of solution B is adjusted to approximately 2.7 with the addition of an acid, in particular nitric acid (HNO 3 ).

    Die Herstellung des Sol-Gel-Lackes und die Beschichtung des Aluminiumbandes erfolgt in bevorzugter Ausführung wie folgt:The production of the sol-gel varnish and the coating of the aluminum strip is carried out in a preferred embodiment as follows:

    Einer Basislösung A, wie zuvor beschrieben, in einem Anteil von 70 Gew.-% der Mischlösung wird unter Rühren eine Lösung B in einem Anteil von 30 Gew.-% der Mischlösung zugegeben. Die Lösungen A und B werden unter kontinuierlichem Rühren in eine Mischlösung überführt, wobei reaktionsbedingt Wärme freigesetzt wird.A base solution A, as described above, in a proportion of 70% by weight of the Mixed solution becomes a solution B in a proportion of 30% by weight with stirring added to the mixed solution. The solutions A and B are under continuous Stirring transferred into a mixed solution, heat due to reaction is released.

    Die Mischlösung wird über eine bestimmte Zeit, beispielsweise während 1 h bis 10 h, vorzugsweise währen 4 bis 8 h, insbesondere während rund 6 h gerührt. Das Gemisch wird anschliessend filtriert. Der Filter dient dem Rückhalt grösserer Partikel, wie z.B. Partikel von kolonialer Kieselsäure. Der Porendurchmesser bzw. die Maschenweite des Filters richtet sich nach der angestrebten Schichtdicke, da Partikel mit grösserem Durchmesser als die angestrebte Schichtdicke die Oberflächenqualität der Schutzschicht beeinträchtigen. Die Filtration kann beispielsweise mittels Polypropylenfilter mit einer Porosität von 1 µm erfolgen.The mixed solution is over a certain time, for example for 1 h to 10 h, preferably during 4 to 8 h, in particular stirred for around 6 h. The mixture is then filtered. The filter serves to hold back larger Particles such as Particles of colonial silica. The pore diameter or the mesh size of the filter depends on the desired layer thickness, because particles with a larger diameter than the desired layer thickness affect the surface quality of the protective layer. Filtration can for example using a polypropylene filter with a porosity of 1 µm.

    Die Mischlösung wird zweckmässig auf einem pH-Wert von 2 - 4, vorzugsweise von 2 bis 3,5, insbesondere von 2,5 bis 3, und besonders bevorzugt von 2,7, gehalten. Die Angleichung des pH-Wertes erfolgt mittels Säure, bevorzugt mittels Salpetersäure.The mixed solution is expediently at a pH of 2-4, preferably from 2 to 3.5, in particular from 2.5 to 3, and particularly preferably from 2.7, held. The pH is adjusted using acid, preferably using Nitric acid.

    Nach Abschluss des Rührvorganges kann der Sol-Gel-Lack mittels eines der vorgenannten Verfahrens auf die Bandoberfläche aufgetragen und nachfolgend, wie vorgängig beschrieben, getrocknet bzw. gehärtet werden. After completion of the stirring process, the sol-gel varnish can be removed using one of the the aforementioned method is applied to the belt surface and subsequently, can be dried or hardened as described above.

    In vorteilhafter Ausführung des Herstellungsverfahrens wird der Sol-Gel-Lack nach seiner Herstellung und vor dem Auftrag auf die Bandoberfläche während weniger Minuten bis mehreren Stunden, vorzugsweise zwischen 1 und 24 h, insbesondere zwischen 12 und 22 h und besonders bevorzugt während rund 17 h ruhig gestellt.In an advantageous embodiment of the manufacturing process, the sol-gel varnish after its manufacture and before application to the belt surface during a few minutes to several hours, preferably between 1 and 24 hours, especially between 12 and 22 h and particularly preferably for around 17 h immobilized.

    Die Elementanalyse des ausgehärteten Sol-Gel-Lackes mittels XPS (X-Ray Photoelectron Spectroscopy) weist z.B. die Elemente Sauerstoff, Silizium und rund 5 - 20 at.% (Atomprozente) Kohlenstoff nach.The element analysis of the hardened sol-gel varnish using XPS (X-Ray Photoelectron Spectroscopy) has e.g. the elements oxygen, silicon and around 5 - 20 at.% (atomic percent) carbon after.

    Claims (11)

    Verfahren zur Herstellung witterungs- und korrosionsbeständiger umgeformter Blechteile aus Aluminium oder aus einer Aluminiumlegierung mit dekorativer Oberfläche unter Anwendung eines Coil-Coating-Verfahrens, umfassend nacheinander die Schritte: Bereitstellen eines Bandes aus Aluminium oder aus einer Aluminiumlegierung, gegebenenfalls kontinuierliches Entfetten des Bandes, gegebenenfalls elektrochemisches, chemisches oder mechanisches Glänzen des gegebenenfalls entfetteten Bandes, kontinuierliche Vorbehandlung des gegebenenfalls entfetteten und/oder geglänzten Bandes zur Erzeugung einer als Haftgrund für eine Lackschicht geeigneten Vorbehandlungsschicht, kontinuierliches Lackieren des vorbehandelten Bandes mit einem Sol-Gel-Lack aus einem Polysiloxan zur Erzeugung einer Schutzschicht, kontinuierliches Trocknen und Härten der Schutzschicht in einem Durchlaufofen, Ausstanzen der mit der Schutzschicht versehenen Blechteile aus dem Band, Umformen der ausgestanzten Blechteile. Process for producing weatherproof and corrosion-resistant formed sheet metal parts made of aluminum or of an aluminum alloy with a decorative surface using a coil coating process, comprising the steps in succession: Providing a strip made of aluminum or an aluminum alloy, if necessary, continuous degreasing of the belt, optionally electrochemical, chemical or mechanical glossing of the optionally degreased strip, continuous pretreatment of the possibly degreased and / or polished tape to produce a pretreatment layer suitable as a primer for a lacquer layer, continuous painting of the pre-treated tape with a sol-gel paint made of a polysiloxane to create a protective layer, continuous drying and hardening of the protective layer in a continuous furnace, Punching the sheet metal parts provided with the protective layer out of the strip, Forming the punched sheet metal parts. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass der Sol-Gel-Lack ein aus einer alkoholischen Silan-Lösung, vorzugsweise einer Alkoxysilan-Lösung, und einer wässrigen kolloidalen Kieselsäure-Lösung hergestelltes Polysiloxan ist.A method according to claim 1, characterized in that the sol-gel lacquer is a polysiloxane made from an alcoholic silane solution, preferably an alkoxysilane solution, and an aqueous colloidal silica solution. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass der Sol-Gel-Lack aus vernetzten anorganischen Polysiloxanen mit über Kohlenstoffbindungen mit dem Silizium verbundenen organischen Gruppen, insbesondere Alkylgruppen, besteht.Method according to Claim 1 or 2, characterized in that the sol-gel lacquer consists of crosslinked inorganic polysiloxanes with organic groups, in particular alkyl groups, which are bonded to the silicon via carbon bonds. Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass als Band ein Glänzwerkstoff oder ein Werkstoff mit einer matten dekorativen Oberfläche eingesetzt wird.Method according to one of claims 1 to 3, characterized in that a glossy material or a material with a matt decorative surface is used as the band. Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass als Vorbehandlungsschicht auf der Bandoberfläche eine anodische Oxidschicht erzeugt wird.Method according to one of claims 1 to 4, characterized in that an anodic oxide layer is produced as a pretreatment layer on the strip surface. Verfahren nach Anspruch 5, dadurch gekennzeichnet, dass die anodische Oxidschicht eingefärbt wird.A method according to claim 5, characterized in that the anodic oxide layer is colored. Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass als Vorbehandlungsschicht auf der Bandoberfläche eine Chromatschicht erzeugt wird.Method according to one of claims 1 to 4, characterized in that a chromate layer is produced as a pretreatment layer on the strip surface. Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass als Vorbehandlungsschicht auf der Bandoberfläche eine chromfreie Schicht erzeugt wird.Method according to one of claims 1 to 4, characterized in that a chromium-free layer is produced as a pretreatment layer on the belt surface. Verfahren nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, dass die Dicke der Schutzschicht wenigstes 1 µm beträgt und bevorzugt zwischen 1 und 10 µm, insbesondere zwischen 1 und 4,5 µm und besonders bevorzugt zwischen 1 und 3 µm liegt.Method according to one of claims 1 to 8, characterized in that the thickness of the protective layer is at least 1 µm and preferably between 1 and 10 µm, in particular between 1 and 4.5 µm and particularly preferably between 1 and 3 µm. Verfahren nach einem der Ansprüche 1 bis 10, dadurch gekennzeichnet, dass der Sol-Gel-Lack Farbpigmente enthält.Method according to one of claims 1 to 10, characterized in that the sol-gel lacquer contains color pigments. Verfahren nach einem der Ansprüche 1 bis 11, dadurch gekennzeichnet, dass die ausgestanzten und umgeformten Blechteile als dekorative Teile, insbesondere als Zierteile wie Zierleisten im Automobilbau verwendet werden.Method according to one of claims 1 to 11, characterized in that the punched and formed sheet metal parts are used as decorative parts, in particular as decorative parts such as trim strips in automobile construction.
    EP03405173A 2003-03-12 2003-03-12 Method for manufacturing of formed metal parts of aluminium sheet with a decorative surface Withdrawn EP1457267A1 (en)

    Priority Applications (6)

    Application Number Priority Date Filing Date Title
    EP03405173A EP1457267A1 (en) 2003-03-12 2003-03-12 Method for manufacturing of formed metal parts of aluminium sheet with a decorative surface
    EP04405138A EP1457266B1 (en) 2003-03-12 2004-03-09 Method for manufacturing of formed metal parts of aluminium sheet with a decorative surface
    DE502004000159T DE502004000159D1 (en) 2003-03-12 2004-03-09 Method for producing formed aluminum sheet metal parts with a decorative surface
    SI200430012T SI1457266T1 (en) 2003-03-12 2004-03-09 Method for manufacturing of formed metal parts of aluminium sheet with a decorative surface
    ES04405138T ES2252727T3 (en) 2003-03-12 2004-03-09 PROCEDURE FOR MANUFACTURING CONFORMED PARTS OF ALUMINUM SHEET WITH DECORATIVE SURFACE.
    PL04405138T PL1457266T3 (en) 2003-03-12 2004-03-09 Method for manufacturing of formed metal parts of aluminium sheet with a decorative surface

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    EP03405173A EP1457267A1 (en) 2003-03-12 2003-03-12 Method for manufacturing of formed metal parts of aluminium sheet with a decorative surface

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    EP1457267A1 true EP1457267A1 (en) 2004-09-15

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    WO2015092332A1 (en) * 2013-12-20 2015-06-25 Seb S.A. Method of manufacturing a heating article provided with a sol-gel coating
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    CN107881543A (en) * 2017-12-05 2018-04-06 马鞍山市东方仪表有限公司 A kind of preparation method of aluminium alloy automobile instrument panel surface enamel
    CN112144050A (en) * 2020-09-24 2020-12-29 蚌埠学院 Silicon-based chromium-free passivation solution for Bundy tube and preparation method thereof
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    Cited By (15)

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    EP1970256A3 (en) * 2007-03-16 2011-01-26 Süddeutsche Aluminium Manufaktur GmbH Motor vehicle component with sol-gel coating
    US8377561B2 (en) 2007-03-16 2013-02-19 Suddeutsche Aluminium Manufaktur Gmbh Motor vehicle component comprising sol-gel coating
    US8747641B2 (en) 2007-03-16 2014-06-10 Suddeutsche Aluminium Manufaktur Gmbh Partial pigmentation of a coating layer to prevent interference on aluminum components or components comprising aluminum
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    WO2017021387A1 (en) * 2015-08-05 2017-02-09 Poligrat Gmbh Abrasion- and peel-resistant sol-gel coating on aluminium and method for producing a coating of this type
    CN107881543A (en) * 2017-12-05 2018-04-06 马鞍山市东方仪表有限公司 A kind of preparation method of aluminium alloy automobile instrument panel surface enamel
    CN112144050A (en) * 2020-09-24 2020-12-29 蚌埠学院 Silicon-based chromium-free passivation solution for Bundy tube and preparation method thereof
    CN112144050B (en) * 2020-09-24 2022-12-23 蚌埠学院 Silicon-based chromium-free passivation solution for Bundy tube and preparation method thereof
    CN112323053A (en) * 2020-10-14 2021-02-05 蚌埠学院 Silicon-based chromium-free passivation solution for brass surface and preparation method thereof
    CN112323053B (en) * 2020-10-14 2021-12-28 蚌埠学院 Silicon-based chromium-free passivation solution for brass surface and preparation method thereof
    CN114045491A (en) * 2021-12-14 2022-02-15 无锡邦得机械有限公司 Surface processing method for aluminum alloy casting

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    ES2252727T3 (en) 2006-05-16

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