EP1372872B1 - Coated reshaped aluminium semi-finished products and/or components and method for the production thereof - Google Patents

Coated reshaped aluminium semi-finished products and/or components and method for the production thereof Download PDF

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Publication number
EP1372872B1
EP1372872B1 EP02719679A EP02719679A EP1372872B1 EP 1372872 B1 EP1372872 B1 EP 1372872B1 EP 02719679 A EP02719679 A EP 02719679A EP 02719679 A EP02719679 A EP 02719679A EP 1372872 B1 EP1372872 B1 EP 1372872B1
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Prior art keywords
aluminium
coated
finished products
components
semi
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German (de)
French (fr)
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EP1372872A2 (en
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Dieter Lehmann
Michaela Gedan-Smolka
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Leibniz Institut fuer Polymerforschung Dresden eV
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Leibniz Institut fuer Polymerforschung Dresden eV
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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
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
    • B05D3/0209—Multistage baking
    • 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
    • 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
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/12—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by mechanical means
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
    • Y10T428/256—Heavy metal or aluminum or compound thereof

Definitions

  • the invention relates to the fields of chemistry, mechanical engineering and materials science and relates to coated formed aluminum semi-finished products and / or components which are coated with a two-stage curable / crosslinkable coating composition for a form-stable coating and a process for their preparation.
  • curable uretdione group-containing compositions which can be cured in two-stage reactions.
  • the first stage preferably proceeds via an allophanate formation of less than 160.degree. From temperatures greater than 170 ° C arise under Urethanitatien to form the crosslinked final state.
  • curable compositions preferably used for the production of powder coatings and their processes for the preparation and processing are described, which are used specifically for multi-stage reactions and preferably for two-stage reactions. These compounds cure in multi-step reactions, with the first step catalyzed at low temperatures.
  • a disadvantage of the known coatings is that substantially no deformation-stable coating can be achieved.
  • the object of the invention is to provide and produce coated shaped aluminum semi-finished products and / or components that are still reshapeable as semi-finished products while maintaining a closed coating and cured at higher temperatures, so that at the end also a closed coating is obtained.
  • the coated convertible aluminum semi-finished products and / or components according to the invention are coated with at least two-stage curable / crosslinkable coating compositions in the form of a melt coating composition or as a powder coating or as a paint dispersion or as a solvent system and at most partially cured / partially crosslinked.
  • the formed coating film is elastic and is present during subsequent forming processes substantially as a closed coating film.
  • the coated aluminum semi-finished products and / or components according to the invention are provided with at least one, in at least a second reaction stage after a forming process, substantially cured / crosslinked coating film, wherein the curing / crosslinking has occurred under the conditions of the Nachkristallisation the aluminum (alloy).
  • the coated formable aluminum semi-finished products and / or components are coated completely or partially or on one side or inside or outside with the coating film.
  • the coated convertible aluminum semi-finished products and / or components are provided with at least one further layer. It is also advantageous if adhesion is achieved by adhesive interactions and / or by chemical, preferably covalent bonds in the case of the coated formable aluminum semi-finished products and / or components.
  • At least one coating agent consists of a binder system consisting of one or more resin and hardener component (s) with or without additives and / or catalysts (n) is composed.
  • a binder system consisting of one or more resin and hardener component (s) with or without additives and / or catalysts (n) is composed.
  • the first stage for filming and partial curing / partial crosslinking at temperatures ⁇ 150 ° C is performed.
  • a temperature / time regime is set to maintain the formability of the aluminum semi-finished products and / or components after the first stage for filming and partial curing / partial crosslinking of the layer.
  • the partial curing / partial crosslinking is carried out thermally and / or photochemically and / or radiation-chemically. It is also advantageous if the second stage for curing / crosslinking is carried out at temperatures> 130 ° C.
  • the second stage for curing / crosslinking during and / or after at least one forming process under the conditions of the recrystallization of the aluminum (alloy) is performed. It is also advantageous that the coated formed aluminum semi-finished products and / or components are coated with at least one further layer and filmed in the at least second stage and cured / crosslinked together with the first (paint) layer.
  • the essence of the invention consists in the production of coated shaped aluminum semi-finished products and components, according to the Aluminum semi-finished products are coated and filmed in a thermal process and teilgehärtei / partially crosslinked.
  • the partial hardening / partial crosslinking of the layer for example thermally and radiation-chemically or only thermally, has such a mechanical stability that these semi-finished products can be easily stored and further processed at a later time.
  • a corresponding temperature / time regime must be maintained in the first stage of filming and partial curing / partial crosslinking. The rule here is that shorter reaction times should be selected at higher temperatures.
  • the partial curing / partial crosslinking can be carried out by radiation chemistry.
  • the elasticity of the partially cured (partially) (paint) layer can be adjusted by criteria - firstly by the composition of the binder system and secondly by the degree of partial cure / partial crosslinking, which can be determined by DSC measurements.
  • the composition of the binder system in particular elastic structural elements can be integrated in the resin component.
  • the formed (paint) film is thereby during or after the forming process as a closed (paint) film before, which in particular additional process steps can be omitted.
  • further layers for example topcoats, cover or color layers or overlays, can be applied, which can also be cured / crosslinked in the second stage at temperatures greater than 130.degree.
  • the rigidity of the component is achieved.
  • the adhesion between the formable aluminum semi-finished products and components and the layer and between the layers is advantageously achieved in addition to the adhesive interaction by chemical bonds.
  • a further improved adhesion is achieved by forming covalent bonds. Partial curing / partial crosslinking of a layer leaves functional and / or reactive groups on the surface which form a covalent bond with the functional and / or reactive groups of a further layer.
  • the compounds (A) and (B) are homogenized at a melt temperature of 90 ° C. To this mass are successively added the compounds (E), (D) and (C).
  • the compositions of the example mixtures are given in Table 1.
  • the homogenized masses are quenched by introduction into liquid nitrogen. These masses are further processed in a (laboratory) grinding plant with sifter to a coating powder.
  • the coating powder is applied to an aluminum sheet by means of powder coating and filmed in a convection oven at 140 ° C, 15 minutes and partially cured / partially crosslinked. It has been determined by DSC measurements that no further reactions from uretdione to allophanate are detectable under isothermal measurement conditions. By deep drawing, the coated aluminum sheet is formed into a cup as a model component at room temperature. There were no cracks or layer damage and there was a closed coating film.
  • Example 1 in the tables is the comparative example analogous to commercial coating compositions, in which after the coating and partial curing / partial crosslinking, the semi-finished aluminum product is no longer reshapeable.

Abstract

The invention relates to the field of chemistry and concerns coated reshaped aluminum semi-finished products and/or components which are coated with a two-step hardening/cross-linking coating agent and a method for the production thereof. The aim of the invention is to disclose and to produce coated reshaped aluminum semi-finished products and/or components which as semi-finished products can still be re-shaped and hardened at high temperatures. The object is attained through coated reshaped aluminum semi-finished products and/or components which are coated with an at least two-step hardening/cross-linking coating agent and at most partially hardened/cross linked, and the formed coating film is elastic. The object is also attained through a method in which aluminum semi-finished products and/or components are coated with at least one coating agent and the layer(s) in a first step are covered with film and partially hardened/partially cross-linked and substantially hardened/cross-linked in an at least second step during and/or after at least one reshaping process.

Description

Die Erfindung bezieht sich auf die Gebiete der Chemie, des Maschinenbaus und der Werkstofftechnik und betrifft beschichtete umgeformte Aluminiumhalbzeuge und/oder -bauteile, die mit einem zweistufig härtbaren/vernetzbaren Beschichtungsmittel für eine umformstabile Beschichtung beschichtet sind und ein Verfahren zu ihrer Herstellung.The invention relates to the fields of chemistry, mechanical engineering and materials science and relates to coated formed aluminum semi-finished products and / or components which are coated with a two-stage curable / crosslinkable coating composition for a form-stable coating and a process for their preparation.

Um Lackschichtsysteme auf Aluminium-Halbzeugen (Blechen) applizieren und mit den heute geforderten Eigenschaften, wie hohe Kratzfestigkeit, hoher Glanzgrad, Umweltverträglichkeit und hoher Ausnutzungsgrad realisieren zu können, werden die kommerziell eingesetzten Pulverlacksysteme bei Temperaturen zwischen 160 bis 220°C industriell eingebrannt. Dies hat zur Folge, dass sich der Grundwerkstoff Aluminium bei diesen Temperaturbereichen über Nachkristallisation verfestigt bzw. stark versprödet und für eine weitere umformtechnische Bearbeitung nicht mehr geeignet ist.In order to apply lacquer coating systems to aluminum semi-finished products (sheets) and to be able to realize the properties required today, such as high scratch resistance, high gloss, environmental compatibility and high utilization, the commercially used powder coating systems are baked at temperatures of 160 to 220 ° C industrial. This has the consequence that the base material aluminum solidifies at these temperature ranges on Nachkristallisation or strongly embrittled and no longer suitable for further forming technology.

In DE 198 56 878 / WO 00/34355 werden härtbare uretdiongruppenhaltige Massen beschrieben, die in Zweistufenreaktionen gehärtet werden können. Die erste Stufe läuft vorzugsweise über eine Allophanatbildung kleiner 160°C ab. Ab Temperaturen größer 170°C entstehen unter Urethanbindungen unter Ausbildung des vernetzten Endzustandes.
In DE 198 56 877 / WO 00/34391 werden "härtbare Massen", vorzugsweise eingesetzt zur Herstellung von Pulverlacken und deren Verfahren zur Herstellung und Verarbeitung beschrieben, die gezielt für Mehrstufenreaktionen und vorzugsweise für Zweistufenreaktionen eingesetzt werden. Diese Massen härten in Mehrstufenreaktionen aus, wobei die erste Stufe bei niedrigen Temperaturen katalysiert abläuft.
Nachteilig bei den bekannten Beschichtungen ist, dass im wesentlichen keine umformstabile Beschichtung erreicht werden kann.In DE 198 56 878 / WO 00/34355 describes curable uretdione group-containing compositions which can be cured in two-stage reactions. The first stage preferably proceeds via an allophanate formation of less than 160.degree. From temperatures greater than 170 ° C arise under Urethanbindungen to form the crosslinked final state.
In DE 198 56 877 / WO 00/34391 "curable compositions", preferably used for the production of powder coatings and their processes for the preparation and processing are described, which are used specifically for multi-stage reactions and preferably for two-stage reactions. These compounds cure in multi-step reactions, with the first step catalyzed at low temperatures.
A disadvantage of the known coatings is that substantially no deformation-stable coating can be achieved.

Die Aufgabe der Erfindung besteht darin, beschichtete umgeformte Aluminiumhalbzeuge und/oder -bauteile anzugeben und herzustellen, die als Halbzeuge noch umformbar sind und dabei eine geschlossene Beschichtung erhalten bleibt und bei höheren Temperaturen ausgehärtet werden, so dass am Ende ebenfalls eine geschlossene Beschichtung erhalten wird.The object of the invention is to provide and produce coated shaped aluminum semi-finished products and / or components that are still reshapeable as semi-finished products while maintaining a closed coating and cured at higher temperatures, so that at the end also a closed coating is obtained.

Die Aufgabe wird durch die in den Ansprüchen angegebene Erfindung gelöst. Weiterbildungen sind Gegenstand der Unteransprüche.The object is achieved by the invention specified in the claims. Further developments are the subject of the dependent claims.

Die erfindungsgemäßen beschichteten umformbaren Aluminiumhalbzeuge und/oder -bauteile sind mit einem mindestens zweistufig härtbaren/vernetzbaren Beschichtungsmittel in Form einer Schmelzebeschichtungsmasse oder als Pulverlack oder als Lackdispersion oder als Lösemittelsystem beschichtet und höchstens teilgehärtet/teilvernetzt. Dabei ist der ausgebildete Beschichtungsfilm elastisch und liegt während nachfolgender Umformprozesse im wesentlichen als geschlossener Beschichtungsfilm vor.
Die weiterhin erfindungsgemäßen beschichteten Aluminiumhalbzeuge und/oder - bauteile sind mit mindestens einem, in mindestens einer zweiten Reaktionsstufe nach einem Umformprozess, im wesentlichen ausgehärteten/vernetzten Beschichtungsfilm versehen, wobei die Aushärtung/Vernetzung unter den Bedingungen der Nachkristallisation der Aluminium(legierung) erfolgt ist.
Vorteilhafterweise liegen die beschichteten umformbaren Aluminiumhalbzeuge und/oder -bauteile in Form von Aluminiumfeinblech(en) oder Aluminiumrohr(en) oder Aluminiumsandwichhalbzeug(en) in Blech- oder Rohrform aus umformbaren Aluminium(legierungen) vor, die bei Temperaturen kleiner 150°C umformbar sind.
Weiterhin vorteilhafterweise sind die beschichteten umformbaren Aluminiumhalbzeuge und/oder -bauteile vollständig oder teilweise oder einseitig oder innen oder außen mit dem Beschichtungsfilm beschichtet.
Es ist auch vorteilhaft, dass die beschichteten umformbaren Aluminiumhalbzeuge und/oder -bauteile mit mindestens einer weiteren Schicht versehen sind.
Ebenfalls vorteilhaft ist es, wenn bei den beschichteten umformbaren Aluminiumhalbzeugen und/oder -bauteilen die Haftung durch adhäsive Wechselwirkungen und/oder durch chemische, vorzugsweise kovalente Bindungen erreicht ist.The coated convertible aluminum semi-finished products and / or components according to the invention are coated with at least two-stage curable / crosslinkable coating compositions in the form of a melt coating composition or as a powder coating or as a paint dispersion or as a solvent system and at most partially cured / partially crosslinked. In this case, the formed coating film is elastic and is present during subsequent forming processes substantially as a closed coating film.
The coated aluminum semi-finished products and / or components according to the invention are provided with at least one, in at least a second reaction stage after a forming process, substantially cured / crosslinked coating film, wherein the curing / crosslinking has occurred under the conditions of the Nachkristallisation the aluminum (alloy).
Advantageously, the coated formable aluminum semi-finished products and / or components in the form of aluminum sheet (s) or aluminum (s) or Aluminiumandandwichhalbzeugen (s) in sheet or tube form of deformable aluminum (alloys), which are deformable at temperatures below 150 ° C. ,
Further advantageously, the coated formable aluminum semi-finished products and / or components are coated completely or partially or on one side or inside or outside with the coating film.
It is also advantageous that the coated convertible aluminum semi-finished products and / or components are provided with at least one further layer.
It is also advantageous if adhesion is achieved by adhesive interactions and / or by chemical, preferably covalent bonds in the case of the coated formable aluminum semi-finished products and / or components.

Ferner ist vorteilhaft, wenn bei den beschichteten umformbaren Aluminiumhalbzeugen und/oder -bauteilen mindestens das eine Beschichtungsmittel aus einem Bindemittelsystem besteht, welches aus einer oder mehreren Harz- und Härterkomponente(n) mit oder ohne Additive(n) und/oder Katalysatore(n) zusammengesetzt ist.
Bei dem erfindungsgemäßen Verfahren zur Herstellung von beschichteten umformbaren Aluminiumhalbzeugen und/oder -bauteilen werden Aluminiumhalbzeuge in Form von Aluminiumfeinblech oder Aluminiumsandwichbauteilen oder Aluminiumrohr aus umformbarem Aluminium(legierung) und/oder Aluminiumbauteile mit mindestens einem Beschichtungsmittel in Form von Schmelzebeschichtungsmasse oder Pulverlack oder Lackdispersion oder Lösemittelsystem beschichtet. Die Schicht(en) werden in einer ersten Stufe verfilmt und teilgehärtet/teilvernetzt und in einer mindestens zweiten Stufe während und/oder nach mindestens einem Umformprozess im wesentlichen ausgehärtet/vernetzt.
Vorteilhafterweise wird die erste Stufe zur Verfilmung und Teilhärtung/Teilvernetzung bei Temperaturen ≤ 150°C durchgeführt.
Ebenfalls vorteilhafterweise wird zur Erhaltung der Umformbarkeit der Aluminiumhalbzeuge und/oder -bauteile nach der ersten Stufe zur Verfilmung und Teilhärtung/Teilvernetzung der Schicht ein Temperatur/Zeit-Regime eingestellt.
Ferner ist vorteilhaft, dass die Teilhärtung/Teilvernetzung thermisch und/oder photochemisch und/oder strahlenchemisch durchgeführt wird.
Es ist auch vorteilhaft, wenn die zweite Stufe zur Aushärtung/Vernetzung bei Temperaturen > 130°C durchgeführt wird.
Weiterhin vorteilhaft ist, dass die zweite Stufe zur Aushärtung/Vernetzung während und/oder nach mindestens einem Umformprozess unter den Bedingungen der Nachkristallisation der Aluminium(legierung) durchgeführt wird.
Es ist auch von Vorteil, dass die beschichteten umgeformten Aluminiumhalbzeuge und/oder -bauteile mit mindestens einer weiteren Schicht beschichtet werden und in der mindestens zweiten Stufe verfilmt und gemeinsam mit der ersten (Lack-)Schicht ausgehärtet/vernetzt werden.It is furthermore advantageous if at least one coating agent consists of a binder system consisting of one or more resin and hardener component (s) with or without additives and / or catalysts (n) is composed.
In the process according to the invention for the production of coated convertible aluminum semi-finished products and / or components, aluminum semi-finished products in the form of aluminum sheet or aluminum sandwich components or aluminum tube of deformable aluminum (alloy) and / or aluminum components are coated with at least one coating composition in the form of melt coating composition or powder coating or paint dispersion or solvent system , The layer (s) are filmed in a first stage and partially cured / partially crosslinked and substantially cured / crosslinked in at least a second stage during and / or after at least one forming process.
Advantageously, the first stage for filming and partial curing / partial crosslinking at temperatures ≤ 150 ° C is performed.
Also advantageously, a temperature / time regime is set to maintain the formability of the aluminum semi-finished products and / or components after the first stage for filming and partial curing / partial crosslinking of the layer.
Furthermore, it is advantageous that the partial curing / partial crosslinking is carried out thermally and / or photochemically and / or radiation-chemically.
It is also advantageous if the second stage for curing / crosslinking is carried out at temperatures> 130 ° C.
It is also advantageous that the second stage for curing / crosslinking during and / or after at least one forming process under the conditions of the recrystallization of the aluminum (alloy) is performed.
It is also advantageous that the coated formed aluminum semi-finished products and / or components are coated with at least one further layer and filmed in the at least second stage and cured / crosslinked together with the first (paint) layer.

Das Wesen der Erfindung besteht in der Herstellung von beschichteten umgeformten Aluminiumhalbzeugen und -bauteilen, die nach der Aluminiumhalbzeugherstellung beschichtet werden und in einem thermischen Prozess verfilmt und teilgehärtei/teilvernetzt werden. Die Teilhärtung/Teilvernetzung der Schicht beispielsweise thermisch und strahlenchemisch oder nur thermisch weist eine solche mechanische Stabilität auf, dass diese Halbzeuge problemlos zwischengelagert und zu einem späteren Zeitpunkt weiterverarbeitet werden können. Zur Erhaltung der Umformbarkeit der Aluminiumhalbzeuge und -bauteile muss ein entsprechendes Temperatur/Zeit-Regime in der ersten Stufe der Verfilmung und Teilhärtung/Teilvernetzung eingehalten werden. Dabei gilt, dass bei höheren Temperaturen kürzere Reaktionszeiten zu wählen sind. Bei niedrigen Temperaturen kann beispielsweise die Teilhärtung/Teilvernetzung strahlenchemisch durchgeführt werden.
Die Elastizität der teilgehärteten/teilvernetzten (Lack-)Schicht wird durch Kriterien einstellbar - erstens durch die Zusammensetzung des Bindemittelsystems und zweitens durch den Grad der Teilhärtung/Teilvernetzung, der über DSC-Messungen bestimmt werden kann. Bezüglich der Zusammensetzung des Bindemittelsystems können insbesondere elastische Strukturelemente in der Harzkomponente integriert sein. Der ausgebildete (Lack-)Film liegt dadurch während oder nach dem Umformprozess als geschlossener (Lack-)Film vor, wodurch insbesondere zusätzliche Verfahrensschritte entfallen können.
Nach dem Umformprozess können weitere Schichten, beispielsweise Top-Coats, Deck- oder Farbschichten oder Gleitschichten aufgebracht werden, die auch in der zweiten Stufe bei Temperaturen größer 130°C ausgehärtet/vernetzt werden können. Mit der Aushärtung/Vernetzung der Schicht(en) unter den Bedingungen der Nachkristallisation der Aluminium(legierung) wird die Steifigkeit des Bauteils erreicht.
Die Haftung zwischen den umformbaren Aluminiumhalbzeugen und -bauteilen und der Schicht und zwischen den Schichten wird vorteilhafterweise neben der adhäsiven Wechselwirkung durch chemische Bindungen erreicht. Eine weiter verbesserte Haftung wird durch Ausbildung kovalenter Bindungen erreicht. Durch die Teilhärtung/Teilvernetzung einer Schicht bleiben an der Oberfläche funktionelle und/oder reaktive Gruppen erhalten, die mit den funktionelle und/oder reaktiven Gruppen einer weiteren Schicht eine kovalente Bindung eingehen.The essence of the invention consists in the production of coated shaped aluminum semi-finished products and components, according to the Aluminum semi-finished products are coated and filmed in a thermal process and teilgehärtei / partially crosslinked. The partial hardening / partial crosslinking of the layer, for example thermally and radiation-chemically or only thermally, has such a mechanical stability that these semi-finished products can be easily stored and further processed at a later time. In order to maintain the formability of the aluminum semi-finished products and components, a corresponding temperature / time regime must be maintained in the first stage of filming and partial curing / partial crosslinking. The rule here is that shorter reaction times should be selected at higher temperatures. At low temperatures, for example, the partial curing / partial crosslinking can be carried out by radiation chemistry.
The elasticity of the partially cured (partially) (paint) layer can be adjusted by criteria - firstly by the composition of the binder system and secondly by the degree of partial cure / partial crosslinking, which can be determined by DSC measurements. With regard to the composition of the binder system, in particular elastic structural elements can be integrated in the resin component. The formed (paint) film is thereby during or after the forming process as a closed (paint) film before, which in particular additional process steps can be omitted.
After the forming process, further layers, for example topcoats, cover or color layers or overlays, can be applied, which can also be cured / crosslinked in the second stage at temperatures greater than 130.degree. With the hardening / crosslinking of the layer (s) under the conditions of the recrystallization of the aluminum (alloy), the rigidity of the component is achieved.
The adhesion between the formable aluminum semi-finished products and components and the layer and between the layers is advantageously achieved in addition to the adhesive interaction by chemical bonds. A further improved adhesion is achieved by forming covalent bonds. Partial curing / partial crosslinking of a layer leaves functional and / or reactive groups on the surface which form a covalent bond with the functional and / or reactive groups of a further layer.

Im nachfolgenden wird die Erfindung an mehreren Ausführungsbeispielen näher erläutert.In the following, the invention will be explained in more detail in several embodiments.

BeispieleExamples

In einem Laborkneter werden die Verbindungen (A) und (B) bei einer Massetemperatur von 90°C homogenisiert. Zu dieser Masse werden nacheinander die Verbindungen (E), (D) und (C) zugegeben.
Die Zusammensetzungen der Beispielmischungen sind in Tabelle 1 angegeben. Die homogenisierten Massen werden durch Einbringen in flüssigen Stickstoff abgeschreckt. Diese Massen werden in einer (Labor-)Mahlanlage mit Sichtereinrichtung zu einem Beschichtungspulver weiterverarbeitet. Tabelle 1: Zusammensetzung der Beispielmischungen* Komponenten/Beispiel 1 (Vergleich) 2 3 4 (A) 75,7 74,7 74,7 74,1 Hydroxylterminierter Polyester (B) 24,3 24,3 24,3 24,3 Uretdiongruppen enthaltende Polyadditionsverbindung (C) - 1,0 - - Dibutylzinndibutylat (D) - - 1,0 1,0 Zinkacetylacetonat (E) - 0,6 Acronal 4F * alle Angaben sind in Gew.-% In a laboratory kneader, the compounds (A) and (B) are homogenized at a melt temperature of 90 ° C. To this mass are successively added the compounds (E), (D) and (C).
The compositions of the example mixtures are given in Table 1. The homogenized masses are quenched by introduction into liquid nitrogen. These masses are further processed in a (laboratory) grinding plant with sifter to a coating powder. <b> Table 1: Composition of the example mixtures * </ b> Components / Example 1 (comparison) 2 3 4 (A) 75.7 74.7 74.7 74.1 Hydroxyl terminated polyester (B) 24.3 24.3 24.3 24.3 Uretdione group-containing polyaddition compound (C) - 1.0 - - Dibutylzinndibutylat (D) - - 1.0 1.0 zinc acetylacetonate (E) - 0.6 Acronal 4F * all data are in% by weight

Das Beschichtungspulver wird auf ein Aluminiumfeinblech mittels Pulverlackierung aufgebracht und in einem Umluftofen bei 140°C, 15 Minuten verfilmt und teilgehärtet/teilvernetzt. Es wurde über DSC-Messungen festgestellt, dass unter isothermen Messbedingungen keine weiteren Reaktionen vom Uretdion zum Allophanat nachweisbar sind.
Über Tiefziehen wird das beschichtete Aluminiumfeinblech zu einem Becher als Modellbauteil bei Raumtemperatur umgeformt. Dabei traten keine Rissbildungen bzw. Schichtschädigungen auf und es lag ein geschlossener Beschichtungsfilm vor.The coating powder is applied to an aluminum sheet by means of powder coating and filmed in a convection oven at 140 ° C, 15 minutes and partially cured / partially crosslinked. It has been determined by DSC measurements that no further reactions from uretdione to allophanate are detectable under isothermal measurement conditions.
By deep drawing, the coated aluminum sheet is formed into a cup as a model component at room temperature. There were no cracks or layer damage and there was a closed coating film.

Nach Aufbringen eines Pulverklarlackes als Top-Coat wird dieses Modellbauteil im Umluftofen bei 170°C in 20 Minuten ausgehärtet/vernetzt. Gleichzeitig erhöhte sich die Steifigkeit des Bauteils durch Nachkristallisation.
Die Charakterisierung des Vernetzungsgrades der Lackschichten erfolgt mittels Differential Scanning Calorimetrie (DSC). Im dynamischen DSC-Scan von 40 bis 220°C bei einer Aufheizgeschwindigkeit von 10 K/min wurde kein Reaktionspeak mehr festgestellt. Die Ergebnisse sind in Tabelle 2 angegeben. Tabelle 2: Ergebnisse der thermischen Untersuchungen Beispiel 1 (Vergleich) 2 3 4 Beginn der Reaktion 184 132 130 125 Tonset(°C) Reaktionsmaximum 212 161 143 141 Tmax(°C) After application of a powder clear coat as a topcoat, this model component is cured in a circulating air oven at 170 ° C in 20 minutes / crosslinked. At the same time, the rigidity of the component increased by recrystallization.
The characterization of the degree of crosslinking of the paint layers takes place by means of differential scanning calorimetry (DSC). In the dynamic DSC scan from 40 to 220 ° C at a heating rate of 10 K / min no reaction peak was detected. The results are shown in Table 2. <b> Table 2: Results of Thermal Studies </ b> example 1 (comparison) 2 3 4 Beginning of the reaction 184 132 130 125 T onset (° C) maximum reaction 212 161 143 141 Tmax (° C)

Beispiel 1 in den Tabellen ist das Vergleichsbeispiel analog zu kommerziellen Beschichtungsmitteln, in dem nach der Beschichtung und Teilhärtung/Teilvernetzung das Aluminiumhalbzeug nicht mehr umformbar ist.Example 1 in the tables is the comparative example analogous to commercial coating compositions, in which after the coating and partial curing / partial crosslinking, the semi-finished aluminum product is no longer reshapeable.

Claims (11)

  1. Coated reshapable aluminium semi-finished products and/or components coated with an at least two-stagedly curable/crosslinkable coating in the form of a melt coating mass or as a powder coating or as a lacquer dispersion or as a solvent system and at most partially cured/crosslinked at temperatures < 150°C, and the coating film formed is elastic and is present essentially as an uninterrupted coating film during subsequent reshaping operations and essentially as a fully cured/crosslinked coating film in a second reaction stage after a reshaping operation, the curing/crosslinking having taken place under the conditions of the post-crystallization of the aluminium (alloy).
  2. Coated reshapable aluminium semi-finished products and/or components according to Claim 1 in the form of thin aluminium sheet(s) or aluminium pipe(s) or aluminium sandwich semi-finished product(s) in sheet or pipe form made of reshapable aluminium (alloys), which are reshapable at temperatures less than 150°C.
  3. Coated reshapable aluminium semi-finished products and/or components according to Claim 1, coated with the coating film completely or partially or on one side or on the inside or on the outside.
  4. Coated reshapable aluminium semi-finished products and/or components according to Claim 1 wherein the coated aluminium semi-finished products and/or components are provided with at least one further layer.
  5. Coated reshapable aluminium semi-finished products and/or components according to Claim 1 wherein the adhesion is obtained through adhesive interactions and/or through chemical, preferably covalent, bonds.
  6. Coated reshapable aluminium semi-finished products and/or components according to Claim 1 wherein at least the one coating consists of a binder system composed of one or more resin and curative components with or without additive(s) and/or catalyst(s).
  7. Method for the production of coated reshapable aluminium semi-finished products and/or components according to Claim 1 wherein aluminium semi-finished products in the form of thin aluminium sheet or aluminium sandwich components or aluminium pipe made of reshapable aluminium (alloy) and/or aluminium components are coated with at least one at least two-stagedly curable/crosslinkable coating in the form of melt coating mass or powder coating or lacquer dispersion or solvent system and the layer(s) are filmed and partially cured/crosslinked in a first stage at temperatures < 150°C and fully cured/crosslinked in an at least second stage during and/or after at least one reshaping operation essentially under the conditions of the post-crystallization of the aluminium (alloy).
  8. Method according to Claim 7, wherein to maintain the reshapability of the aluminium semi-finished products and/or components after the first stage of filming and partial curing/crosslinking of the layer a temperature/time regime is set.
  9. Method according to Claim 7 wherein the partial curing/crosslinking is carried out thermally and/or photochemically and/or radiation chemically.
  10. Method according to Claim 7 wherein the second stage of full curing/crosslinking is carried out at temperatures > 130°C.
  11. Method according to Claim 7 wherein the coated reshaped aluminium semi-finished products and/or components are coated with at least one further layer and in the at least second stage are filmed and fully cured/crosslinked conjointly with the first (lacquer) layer.
EP02719679A 2001-03-13 2002-03-12 Coated reshaped aluminium semi-finished products and/or components and method for the production thereof Expired - Lifetime EP1372872B1 (en)

Applications Claiming Priority (3)

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DE10112991 2001-03-13
DE10112991 2001-03-13
PCT/DE2002/000924 WO2002072285A2 (en) 2001-03-13 2002-03-12 Coated aluminium semi-finished products and/or components and method for the production thereof

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EP1372872B1 true EP1372872B1 (en) 2008-07-02

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EP (1) EP1372872B1 (en)
AT (1) ATE399602T1 (en)
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CA (1) CA2440998A1 (en)
DE (2) DE10211512B4 (en)
DK (1) DK1372872T3 (en)
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DE102008040967A1 (en) * 2008-08-04 2010-02-11 Leibniz-Institut Für Polymerforschung Dresden E.V. Material-plastic composites and process for their preparation

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JPS5229349B2 (en) * 1971-10-11 1977-08-01
US4032678A (en) * 1974-09-12 1977-06-28 Bethlehem Steel Corporation Coated sheet metal and method of forming products therefrom
US3942672A (en) * 1974-12-20 1976-03-09 The Goodyear Tire & Rubber Company Polyurethane composition and method of preparation
US4125670A (en) * 1975-08-11 1978-11-14 Bethlehem Steel Corporation Thermosetting organic coated metallic sheet
US4444975A (en) * 1983-08-03 1984-04-24 Minnesota Mining And Manufacturing Company Wire coating composition for restoration of polyethylene insulation
JPH0780984B2 (en) * 1987-05-29 1995-08-30 武田薬品工業株式会社 One-component thermosetting resin composition for precoat metal
JP2788131B2 (en) * 1991-01-29 1998-08-20 日本パーカライジング株式会社 Method for forming composite film on aluminum or aluminum alloy surface
US5380792A (en) * 1993-04-19 1995-01-10 Miles Inc. Two-component aqueous polyurethane dispersions having improved pot life and coatings prepared therefrom
JPH07166125A (en) * 1993-12-13 1995-06-27 Kobe Steel Ltd Resin-coated aluminium or aluminium alloy material excellent in press forming properties and corrosion resistance and its production
JPH09131568A (en) * 1995-09-06 1997-05-20 Honda Motor Co Ltd Surface treated aluminum alloy plate excellent in formability and coating, baking and curing property and its production
DE19610465A1 (en) * 1996-03-16 1997-09-18 Huels Chemische Werke Ag New polyaddition compounds
US5789519A (en) * 1996-04-12 1998-08-04 Bayer Corporation High viscosity, high equivalent weight polyisocyanate mixtures containing allophanate and isocyanurate groups and their use in coating compositions
US5814137A (en) * 1996-11-04 1998-09-29 The Boeing Company Sol for coating metals
US5783652A (en) * 1997-11-04 1998-07-21 Bayer Corporation Reactivity improvement of urethane prepolymers of allophanate-modified diphenylmethane diisocyanates
DE19856877A1 (en) * 1998-12-10 2000-06-15 Inst Polymerforschung Dresden Curable composition and process for its manufacture and processing
DE19856878A1 (en) * 1998-12-10 2000-06-15 Inst Polymerforschung Dresden Curable compositions containing uretdione groups and a process for their preparation and processing and their use
JP2001017915A (en) * 1999-07-09 2001-01-23 Honda Motor Co Ltd Method for coating body of automobile
DE10027265A1 (en) * 2000-06-02 2001-12-13 Basf Coatings Ag Aluminum coils, useful for the production of automobile bodies, are coated with a multi-layer coating comprising a pigmented powder slurry, a powder slurry clear lacquer and a sol-gel coating agent .

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DE10211512B4 (en) 2007-05-31
WO2002072285A2 (en) 2002-09-19
AU2002250819A1 (en) 2002-09-24
DE10211512A1 (en) 2003-01-02
DE50212437D1 (en) 2008-08-14
US20040105972A1 (en) 2004-06-03
EP1372872A2 (en) 2004-01-02
ATE399602T1 (en) 2008-07-15
WO2002072285A3 (en) 2003-06-26
ES2309160T3 (en) 2008-12-16
DK1372872T3 (en) 2008-11-03
CA2440998A1 (en) 2002-09-19

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