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EP0061165B1 - Motor vehicle with multi-layer varnish coating, and process for multi-layer varnish coating - Google Patents

Motor vehicle with multi-layer varnish coating, and process for multi-layer varnish coating Download PDF

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Publication number
EP0061165B1
EP0061165B1 EP82102250A EP82102250A EP0061165B1 EP 0061165 B1 EP0061165 B1 EP 0061165B1 EP 82102250 A EP82102250 A EP 82102250A EP 82102250 A EP82102250 A EP 82102250A EP 0061165 B1 EP0061165 B1 EP 0061165B1
Authority
EP
European Patent Office
Prior art keywords
layer
lacquer
binder
esters
lacquer layer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP82102250A
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German (de)
French (fr)
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EP0061165A1 (en
Inventor
Hans-Joachim Dr. Dipl.-Chem. Graetz
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.)
Axalta Coating Systems Germany GmbH and Co KG
Original Assignee
Herberts GmbH
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/50—Multilayers
    • B05D7/56—Three layers or more
    • B05D7/57—Three layers or more the last layer being a clear coat
    • B05D7/572—Three layers or more the last layer being a clear coat all layers being cured or baked together
    • 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

Definitions

  • the invention relates to a motor vehicle with a multi-layer coating comprising a colored lacquer layer containing polyester / amine resins as a binder, a transparent effect lacquer layer thereon containing polyester / amine resins and cellulose ethers and / or esters or semi-semesters as binders, and containing a clear lacquer layer thereon thermosetting acrylic / melamine resin combinations or air-drying acrylic / isocyanate resin combinations as binders.
  • the invention also relates to a method for multi-layer painting of motor vehicles. It is known to provide motor vehicles with a multilayer coating on one or more corrosion protection layers, in particular when the coating is to have a so-called metallic effect.
  • Corrosion protection layers in the sense of the present invention are understood to mean all protective layers or lacquer layers which are applied to the metal parts before the final lacquer is applied. This also includes the filler layers that are usually applied before the final coating. If a final coating with a metallic effect is carried out, this usually includes a two-layer coating. The lower layer contains metal platelets, generally aluminum platelets, to produce the so-called metallic effect. If not only the silver metallic effect of the aluminum platelets is desired, but a colored metallic coating, this layer also contains appropriate color pigments.
  • a clear lacquer is then applied to this lacquer layer containing the metal flakes.
  • the metallic coating can contain cellulose esters, in particular cellulose acetobutyrate (cf. US Pat. No. 3639147). According to this prior art, it is also possible to apply the metallic lacquer layer and the clear lacquer layer by the so-called wet-on-wet method, i.e. the metallic paint layer is not cured before the clear coat is applied, and both layers are then cured together.
  • DE-OS No. 3035917 describes a method for applying a multi-layer coating on a motor vehicle, according to which an effect lacquer layer is applied to a colored lacquer layer, which contains titanium dioxide-coated mica flakes as an interference pigment, and a clear lacquer layer is optionally applied thereon.
  • an effect lacquer layer is applied to a colored lacquer layer, which contains titanium dioxide-coated mica flakes as an interference pigment, and a clear lacquer layer is optionally applied thereon.
  • at least the effect lacquer layer is applied by an electrostatic application method.
  • a prerequisite for carrying out this process is that the colored lacquer layer is stoved before the effect lacquer layer can be applied.
  • the method described above has the disadvantage that the stoving process has to be carried out twice.
  • the parts of the motor vehicle which are not to be painted have to be taped twice.
  • the colored lacquer layer is applied and baked, whereby the parts that are not to be painted must be protected by masking before applying a paint.
  • the masking tape has to be removed and the lacquer layer is sanded wet in order to achieve a better bond with the lacquer layer applied afterwards.
  • the parts that are not to be painted must then be taped again before the effect lacquer layer and, if appropriate, the clear lacquer layer are applied and baked. This process is technically very complicated.
  • the present invention is based on the object of creating motor vehicles with an effect lacquer layer which, as in DE-OS No. 3035917, has a more iridescent effect or different effects at different angles of view than the known metallic lacquer, but which are applied in a simpler manner can. It has surprisingly been found that this problem can be solved in that the three layers of colored lacquer layer, effect lacquer layer and clear lacquer layer are applied wet-on-wet and cured in one operation if the colored lacquer layer has a certain composition defined below.
  • the invention accordingly relates to a motor vehicle with a multilayer coating comprising a colored lacquer layer containing polyester / amine resins as a binder, a transparent effect lacquer layer thereon containing polyester / amine resins and cellulose ethers and / or esters or semesters as a binder, and one thereon located clear coat containing thermosetting acrylic / melamine resin combinations or air-drying acrylic / isocyanate resin combinations as a binder, which is characterized in that the colored coat 15 to 60 wt .-%, based on the binder content of this layer, of cellulose ethers and / or esters or semesters.
  • the invention furthermore relates to a process for the multilayer coating of motor vehicles, comprising a colored lacquer layer containing polyester / amine resins as a binder, a transparent effect lacquer layer thereon containing polyester / amine resins and cellulose ethers and / or esters or half-esters as binders, and a clear lacquer layer thereon containing a thermosetting acrylic / melamine resin combination or air-drying acrylic / isocyanate resin combination as a binder, which is characterized in that the colored lacquer layer comprises 15 to 60% by weight, based on the binder content of this layer Contains cellulose ethers and / or esters or half-esters, and that all three layers mentioned are applied wet-on-wet and cured together in one operation, the effect lacquer layer being applied by an electrostatic application process.
  • the colored lacquer layer preferably has a dry film thickness of 10 to 30 ⁇ m.
  • the colored lacquer layer contains, as a binder, the polyester / amine resin systems known according to the prior art for motor vehicle coatings. Oil-containing or oil-free polyesters can be used, in particular alkyd resins. The polyesters are present in a mixture with amine resins, with melamine resins being preferred.
  • the colored lacquer layer contains pigments commonly used in automotive painting. If a white layer is desired, white pigments are used, otherwise colored pigments.
  • the essential feature according to the invention is that the colored lacquer layer contains the above-mentioned cellulose ethers etc. According to the prior art, such cellulose ethers were added to the metallic lacquers in order to quickly fix the metallic flakes.
  • Another essential feature of the method for multi-layer painting according to the invention is that the effect lacquer layer is applied by an electrostatic application process.
  • cellulose ethers, etc. those compounds are used for the colored lacquer layer which are used according to the prior art for the metallic lacquers. As in the prior art, cellulose acetobutyrate is preferred.
  • the amount for the colored lacquer layer according to the invention is preferably at least 30% by weight, and preferably at most 50% by weight, based on the binder content of this layer.
  • an essential feature according to the invention is that the effect lacquer layer applied to the color lacquer layer is transparent. This is understood to mean an at least partial transparency, as is obtained when mica flakes coated with titanium dioxide are used as interference pigments as pigments. These pigments are known (see e.g. DE-OS No. 1959998 and DE-AS No. 1467468).
  • the effect lacquer layer according to the invention preferably contains the same binders as the color lacquer layer, and as already described above, as binders.
  • the effect lacquer layer also contains the cellulose ethers, etc. described above, expediently in an amount of 15 to 60% by weight.
  • the lower limit is preferably about 20% by weight.
  • the upper limit is preferably 40% by weight.
  • the amount of cellulose ethers etc. in the colored lacquer layer according to the invention is relatively high compared to the prior art.
  • the dry film thickness of the effect lacquer layer is expediently in the range from about 5 to 25 J.Lm.
  • the lower limit is preferably around 10 ⁇ m, while the upper limit is preferably around 15 ⁇ m.
  • the electrostatic application methods known per se can be used.
  • the paint in a stationary system, the paint can be sprayed over a rotating bell or disc in an electrostatic field, so-called @ Randsburg systems. It can also be sprayed with known electrostatic spray guns.
  • a clear lacquer layer is applied to the effect lacquer layer, which has either thermosetting acrylic / melamine-resin combinations or air-drying acrylic / isocyanate-resin combinations as binders. Both paint systems are known in the field of painting motor vehicles. If the heat-curable combinations are used, all layers of paint must be cured together in one operation by heating to elevated temperatures.
  • the usual curing temperatures according to the prior art are applied, e.g. B. from about 70 ° C to 170 ° C for periods of about 10 to 40 min, the duration of the baking process is usually inversely proportional to the temperature used.
  • the known air-drying systems are used according to the invention, which is mainly the case in motor vehicle refinishing
  • the motor vehicle provided with the three layers of lacquer according to the invention is dried under environmental conditions or to moderate temperatures of not more than about 80 ° C. warmed up. All three layers of paint are cured.
  • the dry film thickness of the clear lacquer layer is expediently 15 to 50 ⁇ m, 20 ⁇ m being preferred for the lower limit and 40 ⁇ m for the upper limit.
  • acrylic also means methacrylic resin systems, as are also used in this field according to the prior art (cf., inter alia, US Pat. No. 3639147, GB Pat. No. 1284755, DE-OS No. 2812397).
  • the proportion of coated with titanium dioxide Mica flakes in the effect lacquer layer are expediently 0.5 to 8% by weight, preferably at least about 1% by weight and at most about 6% by weight, calculated on the total weight of the lacquer. (Calculated on solids about 3 to 40 wt .-%, preferably 4 to 30 wt .-%, depending on the color of the substrate.)
  • those of the resin systems described above are preferably used which physically dry in 1 to 15, preferably 2 to 12, particularly preferably 3 to 8 minutes.
  • the effect lacquer layer it is expedient to apply the effect lacquer layer to the colored lacquer layer after 1 to 15, preferably 2 to 12, particularly preferably 3 to 8 minutes.
  • the layers applied in front of it must, as explained above, physically dry within the stated time to such an extent that substantial mixing or greater swelling of the lacquer layers applied to them is avoided during application.
  • the above-mentioned drying times for the effect varnish also have the effect that the binder solidifies very quickly and that therefore the mica platelets coated with titanium dioxide can no longer move in the layer.
  • the mica flakes Shortly after the application of the effect lacquer layer, the mica flakes predominantly assume an arrangement approximately parallel to the substrate. This arrangement leads to the special effect.
  • the mica platelets move, in particular can rotate, for a longer period of time in the applied layer, there is a risk that they will adopt a different orientation to a considerable extent, as a result of which the iridescent effect would be reduced or avoided.
  • the interference effect is particularly pronounced and is strongly obtained when the layers, in particular the effect lacquer layer and the colored lacquer layer, have the strengths specified above.
  • lacquers used according to the invention naturally contain the usual lacquer additives and solvents.
  • a color coat of paint with a dry film thickness of 20 ⁇ m which contains an oil-free polyester and melamine resin and a content of 40% by weight cellulose acetobutyrate, based on the binder content of this layer, is applied to the body parts, which are provided with corrosion protection layers in the usual way.
  • an effect lacquer layer with a dry film thickness of 10 ⁇ m is applied, using an oil-free polyester and melamine resin as a binder, using a stationary system for electrostatic painting using a rotating bell in an electrostatic field.
  • the clear lacquer layer is applied thereon, which contains an acrylic / melamine resin combination which is customary in motor vehicle painting in a customary solvent mixture.
  • the dry film thickness of this layer is approximately 30 ⁇ m. Then baked at about 140 ° C for 20 min.
  • a motor vehicle with a conventional filler coating is sanded. Then a colored lacquer layer is applied using the usual spraying method with a dry film thickness of 25 ⁇ m, which contains an oil-free polyester and melamine resin, has a content of 35% cellulose acetobutyrate, based on the binder content of this layer, and 55% rutile titanium dioxide, calculated on the total solid content , as well as usual paint additives and solvents.
  • the effect varnish is applied in a dry film thickness of 15 ⁇ m using an electrostatic hand spray gun.
  • a binder it contains an oil-free polyester, melamine resin and 30% by weight of cellulose acetobutyrate, based on the binder, and 5% by weight, based on the lacquer of the interference pigment described in Example 1.
  • a clear lacquer containing an acrylic / isocyanate-resin combination as a binder is applied in a dry film thickness of 30 ⁇ m. The mixture is then heated to 80 ° C. for 10 minutes or 50 ° C. for 1 hour, or else is dried under environmental conditions.
  • the vehicles painted in this way have an impressive iridescent effect. If the viewing direction is essentially vertical, the hue essentially corresponds to the hue of the interference pigment used. When the viewing angle changes, the background color appears more clearly.

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Paints Or Removers (AREA)
  • Laminated Bodies (AREA)

Description

Die Erfindung betrifft ein Kraftfahrzeug mit mehrschichtiger Lackierung umfassend eine Farblackschicht enthaltend Polyester/Amin-Harze als Bindemittel, eine darauf befindliche transparente Effektlackschicht enthaltend Polyester/Amin-Harze sowie Celluloseäther und/oder -ester bzw. -halbesterals Bindemittel, und eine darauf befindliche Klarlackschicht enthaltend hitzehärtbare Acryl/Melamin-Harz-Kombinationen oder lufttrocknende Acryl/Isocyanat-Harz-Kombinationen als Bindemittel.The invention relates to a motor vehicle with a multi-layer coating comprising a colored lacquer layer containing polyester / amine resins as a binder, a transparent effect lacquer layer thereon containing polyester / amine resins and cellulose ethers and / or esters or semi-semesters as binders, and containing a clear lacquer layer thereon thermosetting acrylic / melamine resin combinations or air-drying acrylic / isocyanate resin combinations as binders.

Ausserdem betrifft die Erfindung ein Verfahren zum mehrschichtigen Lackieren von Kraftfahrzeugen. Es ist bekannt, Kraftfahrzeuge mit einer mehrschichtigen Lackierung auf einer oder mehreren Korrosionsschutzschichten insbesondere dann zu versehen, wenn die Lackierung einen sogenannten Metalleffekt aufweisen soll. Unter Korrosionsschutzschichten im Sinne der vorliegenden Erfindung werden alle Schutzschichten bzw. Lackschichten verstanden, die auf die Metallteile vor dem Aufbringen der Endlackierung aufgebracht werden. Dazu gehören auch die in der Regel vor der Endlackierung aufgetragenen Füllerschichten. Wenn eine Endlackierung mit Metalleffekt durchgeführt wird, umfasst diese in der Regel eine zweischichtige Lackierung. Die untere Schicht enthält zur Erzeugung des sogenannten Metalleffektes Metallplättchen, im allgemeinen Aluminiumplättchen. Wenn nicht nur der Silbermetallic- Effekt der Aluminiumplättchen gewünscht wird, sondern eine farbige Metallic-Lackierung, enthält diese Schicht zusätzlich entsprechende Farbpigmente. Auf diese die Metallplättchen enthaltende Lackschicht wird dann ein Klarlack aufgebracht. Die Metallic-Lackierung kann neben dem Bindemittel Celluloseester, insbesondere Celluloseacetobutyratenthalten (vgl. US-PS Nr.3639147). Es ist nach diesem Stand der Technik auch möglich, die Metallic-Lackschicht und die Klarlackschicht nach dem sogenannten Nass-in-Nass-Verfahren aufzubringen, d.h. die Metallic-Lackschicht wird nicht ausgehärtet, bevor die Klarlackschicht aufgetragen wird, und beide Schichten werden dann gemeinsam gehärtet.The invention also relates to a method for multi-layer painting of motor vehicles. It is known to provide motor vehicles with a multilayer coating on one or more corrosion protection layers, in particular when the coating is to have a so-called metallic effect. Corrosion protection layers in the sense of the present invention are understood to mean all protective layers or lacquer layers which are applied to the metal parts before the final lacquer is applied. This also includes the filler layers that are usually applied before the final coating. If a final coating with a metallic effect is carried out, this usually includes a two-layer coating. The lower layer contains metal platelets, generally aluminum platelets, to produce the so-called metallic effect. If not only the silver metallic effect of the aluminum platelets is desired, but a colored metallic coating, this layer also contains appropriate color pigments. A clear lacquer is then applied to this lacquer layer containing the metal flakes. In addition to the binder, the metallic coating can contain cellulose esters, in particular cellulose acetobutyrate (cf. US Pat. No. 3639147). According to this prior art, it is also possible to apply the metallic lacquer layer and the clear lacquer layer by the so-called wet-on-wet method, i.e. the metallic paint layer is not cured before the clear coat is applied, and both layers are then cured together.

Die DE-OS Nr. 3035917 beschreibt ein Verfahren zum Aufbringen einer mehrschichtigen Lakierung auf ein Kraftfahrzeug, gemäss dem auf eine Farblackschicht eine Effektlackschicht aufgebracht wird, die mit Titandioxid beschichtete Glimmerplättchen als Interferenzpigment enthält, und gegebenenfalls hierauf eine Klarlackschicht aufgebracht wird. Nach diesem Verfahren wird zumindest die Effektlackschicht durch ein elektrostatischesAuftragsverfahren aufgebracht. Voraussetzung für die Durchführung dieses Verfahrens ist, dass die Farblackschicht eingebrannt wird, bevor die Effektlackschicht aufgebracht werden kann.DE-OS No. 3035917 describes a method for applying a multi-layer coating on a motor vehicle, according to which an effect lacquer layer is applied to a colored lacquer layer, which contains titanium dioxide-coated mica flakes as an interference pigment, and a clear lacquer layer is optionally applied thereon. According to this method, at least the effect lacquer layer is applied by an electrostatic application method. A prerequisite for carrying out this process is that the colored lacquer layer is stoved before the effect lacquer layer can be applied.

Das vorstehend beschriebene Verfahren hat den Nachteil, dass der Einbrennvorgang zweimal durchgeführt werden muss. Bei Reparaturlackierungen ist damit der zusätzliche Umstand verbunden, dass die nicht zu lackierenden Teile des Kraftfahrzeuges zweimal abgeklebt werden müssen. Zunächst wird die Farblackschicht aufgetragen und eingebrannt, wobei die nicht zu lackierenden Teile durch Abkleben vor einem Lackauftrag geschützt werden müssen. Nach dem Einbrennvorgang muss die Abklebung entfernt werden, und die Lackschicht wird nass geschliffen, um einen besseren Verbund zur danach aufgebrachten Lackschicht zu erreichen. Anschliessend müssen die nicht zu lackierenden Teile wiederum abgeklebt werden, bevor die Effektlackschicht und gegebenenfalls die Klarlackschicht aufgebracht und eingebrannt werden. Dieses Verfahren ist technisch sehr umständlich.The method described above has the disadvantage that the stoving process has to be carried out twice. In the case of refinishing, there is the additional circumstance that the parts of the motor vehicle which are not to be painted have to be taped twice. First, the colored lacquer layer is applied and baked, whereby the parts that are not to be painted must be protected by masking before applying a paint. After the baking process, the masking tape has to be removed and the lacquer layer is sanded wet in order to achieve a better bond with the lacquer layer applied afterwards. The parts that are not to be painted must then be taped again before the effect lacquer layer and, if appropriate, the clear lacquer layer are applied and baked. This process is technically very complicated.

Der vorliegenden Erfindung liegt die Aufgabenstellung zugrunde, Kraftfahrzeuge mit einer Effektlackschicht zu schaffen, die wie gemäss DE-OS Nr. 3035917 einen stärker changierenden Effekt bzw. unterschiedlichere Effekte bei verschiedenen Blickwinkeln aufweist als die bekannte Metallic-Lackierung, die aber in einfacherer Weise aufgebracht werden kann. Es wurde überraschenderweise gefunden, dass diese Aufgabenstellung dadurch gelöst werden kann, dass die drei Schichten Farblackschicht, Effektlackschicht und Klarlackschicht nass-in-nass aufgetragen und in einem Arbeitsgang gehärtet werden, wenn die Farblackschicht eine bestimmte nachfolgend definierte Zusammensetzung aufweist.The present invention is based on the object of creating motor vehicles with an effect lacquer layer which, as in DE-OS No. 3035917, has a more iridescent effect or different effects at different angles of view than the known metallic lacquer, but which are applied in a simpler manner can. It has surprisingly been found that this problem can be solved in that the three layers of colored lacquer layer, effect lacquer layer and clear lacquer layer are applied wet-on-wet and cured in one operation if the colored lacquer layer has a certain composition defined below.

Gegenstand der Erfindung ist demgemäss ein Kraftfahrzeug mit mehrschichtiger Lackierung umfassend eine Farblackschicht enthaltend Polyester/Amin-Harze als Bindemittel, eine darauf befindliche transparente Effektlackschicht enthaltend Polyester/Amin-Harze sowie Celluloseäther und/oder -ester bzw. -halbester als Bindemittel, und eine darauf befindliche Klarlackschicht enthaltend hitzehärtbare Acryl/Melamin-Harz-Kombinationen oder lufttrocknende Acryl/Isocyanat-Harz-Kombinationen als Bindemittel, das dadurch gekennzeichnet ist, dass die Farblackschicht 15 bis 60 Gew.-%, bezogen auf den Bindemittelanteil dieser Schicht, an Celluloseäthern und/oder -estern bzw. -halbestern enthält.The invention accordingly relates to a motor vehicle with a multilayer coating comprising a colored lacquer layer containing polyester / amine resins as a binder, a transparent effect lacquer layer thereon containing polyester / amine resins and cellulose ethers and / or esters or semesters as a binder, and one thereon located clear coat containing thermosetting acrylic / melamine resin combinations or air-drying acrylic / isocyanate resin combinations as a binder, which is characterized in that the colored coat 15 to 60 wt .-%, based on the binder content of this layer, of cellulose ethers and / or esters or semesters.

Weiterhin ist Gegenstand der Erfindung ein Verfahren zum mehrschichtigen Lackieren von Kraftfahrzeugen, umfassend eine Farblackschicht enthaltend Polyester/Amin-Harze als Bindemittel, eine darauf befindliche transparente Effektlackschicht enthaltend Polyester/Amin-Harze sowie Celluloseäther und/oder -ester bzw. -halbester als Bindemittel, und eine darauf befindliche Klarlackschicht enthaltend hitzehärtbare Acryl/Melamin-Harz-Kombination oder lufttrocknende Acryl/Isocyanat-Harz-Kombination als Bindemittel, das dadurch gekennzeichnet ist, dass die Farblackschicht 15 bis 60 Gew.-%, bezogen auf den Bindemittelanteil dieser Schicht, an Celluloseäthern und/oder -estern bzw. -halbestern enthält, und dass alle genannten drei Schichten nass-in-nass aufgetragen und gemeinsam in einem Arbeitsgang gehärtet werden, wobei die Effektlackschicht durch ein elektrostatisches Auftragsverfahren aufgebracht wird.The invention furthermore relates to a process for the multilayer coating of motor vehicles, comprising a colored lacquer layer containing polyester / amine resins as a binder, a transparent effect lacquer layer thereon containing polyester / amine resins and cellulose ethers and / or esters or half-esters as binders, and a clear lacquer layer thereon containing a thermosetting acrylic / melamine resin combination or air-drying acrylic / isocyanate resin combination as a binder, which is characterized in that the colored lacquer layer comprises 15 to 60% by weight, based on the binder content of this layer Contains cellulose ethers and / or esters or half-esters, and that all three layers mentioned are applied wet-on-wet and cured together in one operation, the effect lacquer layer being applied by an electrostatic application process.

Bevorzugt hat die Farblackschicht eine Trokkenfilmdicke von 10 bis 30 µm.The colored lacquer layer preferably has a dry film thickness of 10 to 30 μm.

Die Farblackschicht enthält als Bindemittel die gemäss dem Stand der Technik für Kraftfahrzeuglackierungen bekannten Polyester/Amin-Harz- Systeme. Es können ölhaltige oder ölfreie Polyester eingesetzt werden, insbesondere Alkydharze. Die Polyester liegen im Gemisch mit Aminharzen vor, wobei Melaminharze bevorzugt sind. Die Farblackschichtenthält in der Kraftfahrzeuglackierung üblicherweise eingesetzte Pigmente. Wenn eine weisse Schicht gewünscht wird, werden weisse Pigmente eingesetzt, anderenfalls farbige Pigmente. Das wesentliche Merkmal gemäss der Erfindung liegt darin, dass die Farblackschicht die oben genannten Celluloseäther usw. enthält. Nach dem Stand der Technik wurden solche Celluloseäther den Metallic-Lacken zugesetzt, um eine schnelle Fixierung der Metallic-Plättchen zu bewirken. Da dieses Problem bei Farblackschichten nicht auftreten kann, hat es nicht nahegelegen, die Celluloseäther usw. irgendwelchen Farblackschichten zuzusetzen, und in der Praxis ist dies bisher auch nicht erfolgt. Ein weiteres wesentliches Merkmal des Verfahrens zum mehrschichtigen Lackieren gemäss der Erfindung besteht darin, dass die Effektlackschicht durch ein elektrostatisches Auftragsverfahren aufgebracht wird. Durch Anwendung dieser Merkmale ist es überraschenderweise möglich, dass alle genannten drei Schichten nass-in-nass aufgetragen und gemeinsam in einem Arbeitsgang gehärtet werden. Es wird nicht geschliffen und dennoch ein einwandfreier Verbund der Lackschichten mit guter Oberfläche erhalten. Durch das Nichtanschleifen der Farblackschichtwird der zusätzliche Vorteil erzielt, dass ein gleichmässigerer Changiereffekt auftritt.The colored lacquer layer contains, as a binder, the polyester / amine resin systems known according to the prior art for motor vehicle coatings. Oil-containing or oil-free polyesters can be used, in particular alkyd resins. The polyesters are present in a mixture with amine resins, with melamine resins being preferred. The colored lacquer layer contains pigments commonly used in automotive painting. If a white layer is desired, white pigments are used, otherwise colored pigments. The essential feature according to the invention is that the colored lacquer layer contains the above-mentioned cellulose ethers etc. According to the prior art, such cellulose ethers were added to the metallic lacquers in order to quickly fix the metallic flakes. Since this problem cannot occur with colored lacquer layers, it has not been obvious to add the cellulose ethers etc. to any colored lacquer layers, and in practice this has not yet occurred. Another essential feature of the method for multi-layer painting according to the invention is that the effect lacquer layer is applied by an electrostatic application process. By using these features, it is surprisingly possible that all three layers mentioned are applied wet-on-wet and cured together in one operation. It is not sanded and yet a perfect bond of the lacquer layers with a good surface is obtained. By not sanding the colored lacquer layer, the additional advantage is achieved that a more even traversing effect occurs.

Als Celluloseäther usw. werden diejenigen Verbindungen für die Farblackschicht eingesetzt, die nach dem Stand der Technik für die Metallic-Lacke verwendet werden. Bevorzugt ist wie gemäss dem Stand der Technik Celluloseacetobutyrat. Die Menge beträgt für die Farblackschicht gemäss der Erfindung vorzugsweise mindestens 30 Gew.-%, und vorzugsweise höchstens 50 Gew.-%, bezogen auf den Bindemittelanteil dieser Schicht.As cellulose ethers, etc., those compounds are used for the colored lacquer layer which are used according to the prior art for the metallic lacquers. As in the prior art, cellulose acetobutyrate is preferred. The amount for the colored lacquer layer according to the invention is preferably at least 30% by weight, and preferably at most 50% by weight, based on the binder content of this layer.

Wesentliches Merkmal gemäss der Erfindung ist, dass die auf die Farblackschicht aufgetragene Effektlackschicht transparent ist. Es wird hierunter eine mindestens teilweise Transparenz verstanden, wie sie erhalten wird, wenn man als Pigmente mitTitandioxid beschichtete Glimmerplättchen als Interferenzpigmente verwendet. Diese Pigmente sind bekannt (vgl. z.B. DE-OS Nr. 1959998 und DE-AS Nr. 1467468). Die Effektlackschicht gemäss der Erfindung enthält als Bindemittel vorzugsweise die gleichen Bindemittel wie die Farblackschicht, und wie sie oben bereits beschrieben wurden. Die Effektlackschicht enthält ebenfalls die oben beschriebenen Celluloseäther usw., und zwar zweckmässig in einer Menge von 15 bis 60 Gew.-%. Vorzugsweise liegt die untere Grenze bei etwa 20 Gew.-%. Die obere Grenze liegt vorzugsweise bei 40 Gew.-%. In diesem Zusammenhang ist noch zu erwähnen, dass die Menge der Celluloseäther usw. in der Farblackschicht gemäss der Erfindung im Vergleich zum Stand der Technik relativ hoch liegt. Die Trockenfilmstärke der Effektlackschicht liegt zweckmässig im Bereich von etwa 5 bis 25 J.Lm. Die untere Grenze liegt vorzugsweise bei etwa 10 µm, während die obere Grenze vorzugsweise bei etwa 15 µm liegt. Überraschenderweise lassen sich einwandfreie und zufriedenstellende Effektlackierungen auf Kraftfahrzeugen unter Verwendung von Effektlackschichten mit diesen Pigmenten nur dann erzielen, wenn die Effektlackschicht durch ein elektrostatisches Auftragsverfahren aufgebracht wird. Dies ist besonders deshalb überraschend, weil Metallic-Lacke sich nicht oder nur unbefriedigend elektrostatisch auftragen lassen. Es hat deshalb nicht nahegelegen, an Stelle der Metallic-Lackschicht die Effektlackschicht gemäss der vorliegenden Erfindung durch ein elektrostatisches Auftragsverfahren aufzubringen.An essential feature according to the invention is that the effect lacquer layer applied to the color lacquer layer is transparent. This is understood to mean an at least partial transparency, as is obtained when mica flakes coated with titanium dioxide are used as interference pigments as pigments. These pigments are known (see e.g. DE-OS No. 1959998 and DE-AS No. 1467468). The effect lacquer layer according to the invention preferably contains the same binders as the color lacquer layer, and as already described above, as binders. The effect lacquer layer also contains the cellulose ethers, etc. described above, expediently in an amount of 15 to 60% by weight. The lower limit is preferably about 20% by weight. The upper limit is preferably 40% by weight. In this connection it should also be mentioned that the amount of cellulose ethers etc. in the colored lacquer layer according to the invention is relatively high compared to the prior art. The dry film thickness of the effect lacquer layer is expediently in the range from about 5 to 25 J.Lm. The lower limit is preferably around 10 µm, while the upper limit is preferably around 15 µm. Surprisingly, flawless and satisfactory effect coatings on motor vehicles can be achieved using effect coatings with these pigments only if the effect coating is applied by an electrostatic application process. This is particularly surprising because metallic lacquers cannot be applied or can only be unsatisfactorily applied electrostatically. It was therefore not obvious to apply the effect lacquer layer according to the present invention by an electrostatic application method instead of the metallic lacquer layer.

Es können die an sich bekannten elektrostatischen Auftragsverfahren angewandt werden. Beispielsweise kann in einer stationären Anlage der Lack über eine rotierende Glocke oder Scheibe in einem elektrostatischen Feld, sogenannten @Randsburg-Anlagen versprüht werden. Es kann auch mit bekannten elektrostatischen Handspritzpistolen gespritzt werden. Auf die Effektlackschicht wird eine Klarlackschicht aufgebracht, die als Bindemittel entweder hitzehärtbare Acryl/Melamin-Harz-Kombinationen oder lufttrocknende Acryl/Isocyanat-Harz-Kombinationen aufweist. Beide Lacksysteme sind auf dem Gebiet der Lakierung von Kraftfahrzeugen bekannt. Wenn die hitzehärtbaren Kombinationen eingesetzt werden, müssen nach Auftrag aller Lackschichten diese gemeinsam in einem Arbeitsgang durch Erhitzen auf erhöhte Temperaturen gehärtet werden. Es werden die nach dem Stand der Technik für die Endlackierung üblichen Härtetemperaturen angewandt, z. B. von etwa 70° C bis 170° Cfür Zeiträume von etwa 10 bis 40 min, wobei in der Regel die Dauer des Einbrennvorganges umgekehrt proportional zur angewandten Temperatur ist.The electrostatic application methods known per se can be used. For example, in a stationary system, the paint can be sprayed over a rotating bell or disc in an electrostatic field, so-called @ Randsburg systems. It can also be sprayed with known electrostatic spray guns. A clear lacquer layer is applied to the effect lacquer layer, which has either thermosetting acrylic / melamine-resin combinations or air-drying acrylic / isocyanate-resin combinations as binders. Both paint systems are known in the field of painting motor vehicles. If the heat-curable combinations are used, all layers of paint must be cured together in one operation by heating to elevated temperatures. The usual curing temperatures according to the prior art are applied, e.g. B. from about 70 ° C to 170 ° C for periods of about 10 to 40 min, the duration of the baking process is usually inversely proportional to the temperature used.

Wenn dagegen gemäss der Erfindung die bekannten lufttrocknenden Systeme eingesetzt werden, was hauptsächlich bei der Kraftfahrzeug-Reparaturlackierung der Fall ist, wird das mit den drei Lackschichten gemäss der Erfindung versehene Kraftfahrzeug bei Umwelt-Bedingungen getrocknet oder auf mässige Temperaturen von nicht über etwa 80° C erwärmt. Es erfolgt dabei eine Härtung aller drei Lackschichten.If, on the other hand, the known air-drying systems are used according to the invention, which is mainly the case in motor vehicle refinishing, the motor vehicle provided with the three layers of lacquer according to the invention is dried under environmental conditions or to moderate temperatures of not more than about 80 ° C. warmed up. All three layers of paint are cured.

Die Trockenfilmstärke der Klarlackschicht beträgt zweckmässig 15 bis 50 µm, wobei für die untere Grenze 20 µm und für die obere Grenze 40 µm bevorzugt sind.The dry film thickness of the clear lacquer layer is expediently 15 to 50 μm, 20 μm being preferred for the lower limit and 40 μm for the upper limit.

Unter dem Begriff Acryl werden gemäss der Erfindung auch Methacryl-Harz-Systeme verstanden, wie diese auch gemäss dem Stand der Technik auf diesem Gebiet eingesetzt werden (vgl. u.a. US-PS Nr. 3639147, GB-PS Nr. 1284755, DE-OS Nr. 2812397).According to the invention, the term acrylic also means methacrylic resin systems, as are also used in this field according to the prior art (cf., inter alia, US Pat. No. 3639147, GB Pat. No. 1284755, DE-OS No. 2812397).

Der Anteil an mit Titandioxid beschichteten Glimmerplättchen in der Effektlackschicht beträgt zweckmässig 0,5 bis 8 Gew.-%, vorzugsweise mindestens etwa 1 Gew.-% und höchstens etwa 6 Gew.-%, berechnet auf Gesamtgewicht des Lakkes. (Berechnet auf Festkörper etwa 3 bis 40 Gew.-%, vorzugsweise 4 bis 30 Gew.-%, je nach Farbe des Untergrunds.)The proportion of coated with titanium dioxide Mica flakes in the effect lacquer layer are expediently 0.5 to 8% by weight, preferably at least about 1% by weight and at most about 6% by weight, calculated on the total weight of the lacquer. (Calculated on solids about 3 to 40 wt .-%, preferably 4 to 30 wt .-%, depending on the color of the substrate.)

Für die Farblackschicht und die Effektlackschicht werden bevorzugt solche der oben beschriebenen Harzsysteme eingesetzt, die in 1 bis 15, vorzugsweise 2 bis 12, besonders bevorzugt 3 bis 8 min, physikalisch trocknen.For the colored lacquer layer and the effect lacquer layer, those of the resin systems described above are preferably used which physically dry in 1 to 15, preferably 2 to 12, particularly preferably 3 to 8 minutes.

Es ist zweckmässig, auf die Farblackschicht die Effektlackschicht nach 1 bis 15, vorzugsweise 2 bis 12, besonders bevorzugt 3 bis 8 min, aufzubringen. Das gleiche gilt sinngemäss für den Auftrag der Klarlackschicht auf die Effektlackschicht. Die jeweils davor aufgebrachten Schichten müssen also, wie oben dargelegt, innerhalb der genannten Zeit so weit physikalisch angetrocknet sein, dass ein wesentliches Durchmischen oder stärkeres Anquellen der darauf aufgebrachten Lackschichten beim Auftrag vermieden wird. Die oben genannten Trocknungszeiten für den Effektlack haben ausserdem die Wirkung, dass sehr schnell eine Verfestigung des Bindemittels eintritt, und dass deshalb die mit Titandioxid beschichteten Glimmerplättchen sich nicht mehr in der Schicht bewegen können. Kurz nach dem Auftrag der Effektlackschicht nehmen die Glimmerplättchen überwiegend eine Anordnung etwa parallel zum Untergrund an. Diese Anordnung führt zu dem besonderen Effekt. Wenn sich aber die Glimmerplättchen längere Zeit in der aufgetragenen Schicht bewegen, insbesondere drehen können, besteht die Gefahr, dass sie zu einem erheblichen Anteil eine andere Orientierung einnehmen, wodurch der changierende Effekt vermindert oder vermieden würde.It is expedient to apply the effect lacquer layer to the colored lacquer layer after 1 to 15, preferably 2 to 12, particularly preferably 3 to 8 minutes. The same applies analogously to the application of the clear coat on the effect coat. The layers applied in front of it must, as explained above, physically dry within the stated time to such an extent that substantial mixing or greater swelling of the lacquer layers applied to them is avoided during application. The above-mentioned drying times for the effect varnish also have the effect that the binder solidifies very quickly and that therefore the mica platelets coated with titanium dioxide can no longer move in the layer. Shortly after the application of the effect lacquer layer, the mica flakes predominantly assume an arrangement approximately parallel to the substrate. This arrangement leads to the special effect. However, if the mica platelets move, in particular can rotate, for a longer period of time in the applied layer, there is a risk that they will adopt a different orientation to a considerable extent, as a result of which the iridescent effect would be reduced or avoided.

Überraschenderweise wird der Interferenzeffekt besonders ausgeprägt und stark dann erhalten, wenn die Schichten, insbesondere die Effektlackschicht und die Farblackschicht, die oben angegebenen Stärken aufweisen.Surprisingly, the interference effect is particularly pronounced and is strongly obtained when the layers, in particular the effect lacquer layer and the colored lacquer layer, have the strengths specified above.

Die gemäss der Erfindung verwendeten Lacke enthalten naturgemäss die üblichen lacktechnischen Zusatzstoffe und Lösungsmittel.The lacquers used according to the invention naturally contain the usual lacquer additives and solvents.

Beispie/1 :Example / 1:

Bei der Serienlackierung von Kraftfahrzeugen wird auf die in üblicher Weise mit Korrosionsschutzschichten versehenen Karosserieteile eine Farblackschicht in einer Trockenfilmstärke von 20 µm aufgebracht, die einen ölfreien Polyester und Melaminharz enthält, einen Gehalt von 40 Gew.-% Celluloseacetobutyrat, bezogen auf den Bindemittelgehalt dieser Schicht, aufweist und 35% 'wBayferrox 3920 FF (anorganisches Braunpigment), berechnet auf Gesamtfestanteil, sowie übliche Lackzusätze und Lösemittel enthält.In the series painting of motor vehicles, a color coat of paint with a dry film thickness of 20 µm, which contains an oil-free polyester and melamine resin and a content of 40% by weight cellulose acetobutyrate, based on the binder content of this layer, is applied to the body parts, which are provided with corrosion protection layers in the usual way. has and 35% 'wBayferrox 3920 FF (inorganic brown pigment), calculated on total solid content, as well as conventional paint additives and solvents.

Nach 5 min Ablüftzeit wird, ohne anzuschleifen, nass-in-nass mit Hilfe einer stationären Anlage zum elektrostatischen Lackieren unter Verwendung einer rotierenden Glocke im elektrostatischen Feld eine Effektlackschicht in einer Trokkenfilmstärke von 10 µm aufgebracht, die einen ölfreien Polyester und Melaminharz als Bindemittel enthält, einen Gehalt von etwa 32 Gew.-% Celluloseacetobutyrat, bezogen auf den Bindemittelgehalt dieser Schicht, aufweist und 2 Gew.-% mit Titandioxid in Rutil-Form beschichtete Glimmerplättchen, bezogen auf den Lack, und übliche Lackzusätze und Lösungsmittel enthält. Möglichst schnell danach, in der Praxis nach etwa 3 bis 5 min, wird hierauf die Klarlackschicht aufgebracht, die eine in der Kraftfahrzeuglackierung übliche Acryl/ Melamin-Harz-Kombination in einem üblichen Lösungsmittelgemisch enthält. Die Trockenfilmstärke dieser Schicht beträgt etwa 30 µm. Danach wird 20 min bei etwa 140°C eingebrannt.After a flash-off time of 5 minutes, without grinding, an effect lacquer layer with a dry film thickness of 10 µm is applied, using an oil-free polyester and melamine resin as a binder, using a stationary system for electrostatic painting using a rotating bell in an electrostatic field. has a content of about 32% by weight of cellulose acetobutyrate, based on the binder content of this layer, and 2% by weight of mica platelets coated with titanium dioxide in rutile form, based on the lacquer, and conventional lacquer additives and solvents. As quickly as possible thereafter, in practice after about 3 to 5 minutes, the clear lacquer layer is applied thereon, which contains an acrylic / melamine resin combination which is customary in motor vehicle painting in a customary solvent mixture. The dry film thickness of this layer is approximately 30 µm. Then baked at about 140 ° C for 20 min.

Beispiel 2:Example 2:

Ein Kraftfahrzeug mit einer üblichen Füllerlakierung wird angeschliffen. Hierauf wird eine Farblackschicht nach den üblichen Spritzverfahren mit einer Trockenfilmstärke von 25 µm aufgebracht, die einen ölfreien Polyester und Melaminharz enthält, einen Gehalt von 35% Celluloseacetobutyrat, bezogen auf den Bindemittelgehalt dieser Schicht, aufweist und 55% Rutil-Titandioxid, berechnet auf den Gesamtfestanteil, sowie übliche Lackzusätze und Lösemittel enthält.A motor vehicle with a conventional filler coating is sanded. Then a colored lacquer layer is applied using the usual spraying method with a dry film thickness of 25 µm, which contains an oil-free polyester and melamine resin, has a content of 35% cellulose acetobutyrate, based on the binder content of this layer, and 55% rutile titanium dioxide, calculated on the total solid content , as well as usual paint additives and solvents.

Nach einer Ablüftzeit von 8 min wird mittels einer elektrostatischen Handspritzpistole der Effektlack in einer Trockenfilmstärke von 15 µm aufgebracht. Er enthält als Bindemittel einen ölfreien Polyester, Melaminharz und 30 Gew.-% Celluloseacetobutyrat, bezogen auf das Bindemittel, und 5 Gew.-%, bezogen auf den Lack des im Beispiel 1 beschriebenen Interferenzpigments. Nach 5 min wird mit einem Klarlack, enthaltend eine Acryl/ Isocyanat-Harz-Kombination als Bindemittel, in einer Trockenfilmstärke von 30 µm beschichtet. Danach wird 10 min auf 80°C oder 1 h lang auf 50°C erwärmt oder auch unter Umweltbedingungen getrocknet.After a flash-off time of 8 minutes, the effect varnish is applied in a dry film thickness of 15 µm using an electrostatic hand spray gun. As a binder, it contains an oil-free polyester, melamine resin and 30% by weight of cellulose acetobutyrate, based on the binder, and 5% by weight, based on the lacquer of the interference pigment described in Example 1. After 5 minutes, a clear lacquer containing an acrylic / isocyanate-resin combination as a binder is applied in a dry film thickness of 30 μm. The mixture is then heated to 80 ° C. for 10 minutes or 50 ° C. for 1 hour, or else is dried under environmental conditions.

Die so lackierten Kraftfahrzeuge haben einen eindrucksvollen changierenden Effekt. Bei im wesentlichen senkrechter Blickrichtung entspricht der Farbton im wesentlichen dem Farbton des verwendeten Interferenzpigments. Bei Veränderung des Blickwinkels tritt die Untergrundfarbe stärker in Erscheinung.The vehicles painted in this way have an impressive iridescent effect. If the viewing direction is essentially vertical, the hue essentially corresponds to the hue of the interference pigment used. When the viewing angle changes, the background color appears more clearly.

Claims (4)

1. A motor vehicle having a multilayered lacquering, comprising a layer of coloured lacquer containing polyester amine resins as binder, a transparent layer of effect lacquer which is applied thereto and which contains polyester amine resins and cellulose-ethers and/or -esters or -semi-esters as binder and a layer of clear lacquer which is applied thereto containing thermosetting acrylo/melamine-resin combinations or air-drying acrylo/isocyanate-resin combinations as binder, characterised in that the coloured layer of lacquer contains from 15 to 60%, by weight, of cellulose-ethers and/or -esters or -semi-esters based on the proportion of binder of this layer.
2. A motor vehicle according to Claim 1, characterised in that the layer of coloured lacquer has a thickness of film when dry of from 10 to 30 [im.
3. A process for the multilayered lacquering of motor vehicles, comprising a layer of coloured lacquer containing polyester amine resins as binder, a transparent layer of effect lacquer which is applied thereto and which contains polyester amine resins and cellulose-ethers and/or -esters or -semi-esters as binder, and a layer of clear lacquer which is applied thereto and which contains a thermosetting acrylo/melamine-resin combination or an air-drying acrylo/isocyanate-resin combination as binder, characterised in that the layer of coloured lacquer contains from 15 to 60%, by weight, of cellulose-ethers and/or -esters or -semi-esters, based on the binder proportion of this layer, and all the above-mentioned three layers are applied wet-in-wet and are hardened together in one stage, the layer of effect lacquer being applied by an electrostatic process of application.
4. A process according to Claim 3, characterised in that the layer of coloured lacquer is applied in a quantity such that the thickness of the film when dry is from 10 to 30 µm.
EP82102250A 1981-03-24 1982-03-19 Motor vehicle with multi-layer varnish coating, and process for multi-layer varnish coating Expired EP0061165B1 (en)

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DE19813111478 DE3111478A1 (en) 1981-03-24 1981-03-24 MOTOR VEHICLE WITH MULTI-LAYER PAINTING AND METHOD FOR MULTI-LAYER PAINTING
DE3111478 1981-03-24

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DE3709978A1 (en) * 1987-03-26 1988-10-06 Herberts Gmbh METHOD FOR THE PRODUCTION OF PIGMENTED, AIR-DRYING METALLIC BASE VARNISHES, AND THE USE THEREOF
DE3721703A1 (en) * 1987-07-01 1989-01-12 Herberts Gmbh METHOD AND DEVICE FOR LACQUERING WORKPIECES WITH ELECTRICALLY INSULATING SURFACE BY ELECTROSTATIC APPLICATION OR. SPRAY ORDER
DE3727081A1 (en) * 1987-08-14 1989-02-23 Merck Patent Gmbh Coatings
US5425969A (en) * 1992-06-26 1995-06-20 Toyota Jidosha Kabushiki Kaisha Method of coating articles made of polypropylene with an electrically conductive primer and electrostatically applied overcoat
EP0688840A3 (en) * 1994-06-20 1996-08-07 Herberts & Co Gmbh Coating composition and its use for preparing multi-layer coatings
JP4507535B2 (en) * 2003-09-02 2010-07-21 東亞合成株式会社 Paint composition
JP6955313B2 (en) * 2017-10-30 2021-10-27 関西ペイント株式会社 Multi-color finish painting method and manufacturing method of painted products

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US3370025A (en) * 1967-03-24 1968-02-20 Eastman Kodak Co Ethanolic lacquers based on cellulose butyrate
DE1644769B2 (en) * 1968-02-06 1975-11-06 Chemische Werke Huels Ag, 4370 Marl Coating agents
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