EP1257368B1 - Method for producing color and/or effect-producing multilayer paints on car bodies - Google Patents

Method for producing color and/or effect-producing multilayer paints on car bodies Download PDF

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Publication number
EP1257368B1
EP1257368B1 EP01905723A EP01905723A EP1257368B1 EP 1257368 B1 EP1257368 B1 EP 1257368B1 EP 01905723 A EP01905723 A EP 01905723A EP 01905723 A EP01905723 A EP 01905723A EP 1257368 B1 EP1257368 B1 EP 1257368B1
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EP
European Patent Office
Prior art keywords
process according
surfacer
aqueous
electrostatic
cured
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
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EP01905723A
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German (de)
French (fr)
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EP1257368A2 (en
Inventor
Joachim Woltering
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BASF Coatings GmbH
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BASF Coatings 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
    • B05D7/52—Two layers
    • B05D7/53—Base coat plus clear coat type
    • B05D7/534—Base coat plus clear coat type the first layer being let to dry at least partially before applying the second layer
    • 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
    • B05D7/53—Base coat plus clear coat type
    • B05D7/536—Base coat plus clear coat type 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
    • 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
    • B05D7/574—Three layers or more the last layer being a clear coat at least some layers being let to dry at least partially before applying the next layer
    • 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
    • B05D7/576—Three layers or more the last layer being a clear coat each layer being cured, at least partially, separately

Definitions

  • the present invention relates to a novel process for producing multicoat color and / or effect paint systems on automobile bodies in which a powder slurry clearcoat is used.
  • the inner parts of the automobile bodies are usually first painted by pneumatic spraying or compressed air spraying.
  • the pneumatic spraying is chosen because the cavities and depressions due to the formation of Faraday cages are difficult to electrostatically coat.
  • the object of the present invention is to find a new process for the production of multicoat color and / or effect paint systems on automobile bodies that no longer has the disadvantages of the prior art but, even when using powder slurry clearcoats, provides coatings which do not have visible elevations or flow defects more.
  • the new process for producing multicoat color and / or effect paint systems on automobile bodies is referred to below as the "process according to the invention”.
  • the new process causes that located on the outer skin of the car body, applied by electrostatic painting, wet powder slurry clearcoat layers can easily absorb the spray mist droplets from the interior painting, whereby a much better flow is achieved.
  • the automobile bodies used in the method according to the invention usually have a cathodically deposited and thermally cured electrodeposition coating. However, they may also have a cathodically deposited electrodeposition coating which is not thermally cured, but merely dried or partially cured.
  • the electrodeposition coating or the electrodeposition coating layer can be overcoated with a filler which is cured either alone or together with the electrodeposition coating layer (wet-in-wet process).
  • the coating with a filler takes place in particular in the areas which are exposed to a strong mechanical stress, such as by stone chipping.
  • suitable fillers in particular aqueous fillers, which are also referred to as antistonechip primers or functional layers, for example from the patents US 4,537,926 A1 . EP 0 529 335 A1 . EP 0 595 186 A1 . EP 0 639 660 A1 . DE 44 38 504 A1 . DE 43 37 961 A1 . WO 89/10387 . US 4,450,200 A1 . US 4,614,683 A1 or WO 490/26827 described.
  • these fillers can also be applied to the baked electrodeposition coatings and then pre-dried or partially thermally cured. In this variant of the method according to the invention, they are then cured together with the aqueous basecoat films and powder slurry clearcoat films applied to the surfacer layers (extended wet-on-wet process).
  • the surfacer coatings are coated with water-based paints.
  • suitable aqueous basecoats in particular waterborne basecoats based on polyurethane, are from the patents EP 0 089 497 A1 .
  • EP 0 708 788 A1 are from the patents EP 0 089 497 A1 .
  • the resulting aqueous basecoat films are not cured, but pre-dried or partially cured.
  • the aqueous powder clearcoat materials are applied to the aqueous basecoat films, resulting in powder slurry clearcoat films.
  • suitable powder slurry clearcoats are known from U.S. Patent US-A-4,268,542 and the patent applications DE 195 40 977 A1 . DE 195 18 392 A1 . DE 196 17 086 A1 . DE-A-196 13 547 . EP 0 652 264 A1 . DE 196 18 657 A1 . DE 196 52 813 A1 . DE 196 17 086 A1 or DE-A-198 14 471 A1 known.
  • the aqueous powder clearcoats are applied by electrostatic painting the body exterior parts, followed by pneumatic spraying (compressed air spraying) of the body interior parts.
  • the electrostatic coating can be carried out by means of an electrostatic spray gap, an electrostatic spray bell or an electrostatic spray disc.
  • the electrostatic coating can be done by electrostatic assisted mechanical atomization. Preferably, this is performed by means of electrostatic high rotation disks or high rotation bells.
  • pneumatic spraying or air pressure painting has no special features, but can be done by hand or with the help of conventional and known paint sprayers or robots.
  • the application is carried out when illuminated with visible light of a wavelength of about 550 microns or in the absence of light, when the aqueous basecoat materials and / or the powder slurry clearcoats are curable thermally and with actinic radiation.
  • visible light a wavelength of about 550 microns or in the absence of light
  • the aqueous basecoat materials and / or the powder slurry clearcoats are curable thermally and with actinic radiation.
  • the coating materials to be used according to the invention are applied in a wet layer thickness such that, after their curing, coatings result with the layer thicknesses necessary and advantageous for their functions.
  • a basecoat they are from 5 to 50, preferably from 5 to 40, particularly preferably from 5 to 30 and in particular from 10 to 25 ⁇ m, and in the case of a clearcoat they are from 10 to 100, preferably from 15 to 80, particularly preferably from 20 to 75 and in particular 25 to 70 microns.
  • the aqueous basecoat films are cured thermally or thermally and with actinic radiation together with the powder slurry clearcoat films and, if appropriate, the underlying non or fully cured coating films. Curing with heat and with actinic radiation is also referred to in the art as dual cure.
  • actinic radiation means electromagnetic radiation such as near infrared (NIR), visible light, UV light or X-radiation, but in particular UV light, or corpuscular radiation such as electron radiation.
  • the curing can take place after a certain rest period or ventilation time. It may have a duration of 30 seconds to 2 hours, preferably 1 minute to 1 hour, and especially 1 minute to 45 minutes.
  • the rest period serves, for example, for the course and degassing of the layers and for evaporation of volatile constituents, such as any remaining solvent and / or water.
  • this cure can be supplemented with actinic radiation from other sources.
  • electron beams it is preferable to operate under an inert gas atmosphere. This can be ensured, for example, by supplying carbon dioxide and / or nitrogen directly to the surface of the clearcoat film. Even in the case of curing with UV radiation, to avoid the formation of ozone, under inert gas can be used.
  • the usual and known radiation sources and optical aids are used.
  • suitable radiation sources are flash lamps from the company VISIT, mercury high- or low-pressure vapor lamps, optionally doped with lead, to open a beam window up to 405 nm, or electron beam sources.
  • Their arrangement is known in principle and can be adapted to the conditions of the workpiece and the process parameters.
  • the non-direct radiation accessible areas such as cavities, folds and other design undercuts with point, small area or omnidirectional, associated with an automatic moving device for the irradiation of cavities or Edges, (partially) cured.
  • the curing can be done in stages, d. H. by multiple exposure or irradiation with actinic radiation. This can also be done alternately, d. h., That is cured alternately with UV radiation and electron radiation.
  • the thermal curing has no special features, but takes place by the usual and known methods such as heating in a convection oven or irradiation with IR and / or NIR lamps. As in the case of curing with actinic radiation, the thermal curing can also take place in stages. Advantageously, the thermal curing takes place at temperatures of 90 ° C to 180 ° C.
  • thermal curing and curing with actinic radiation can be used simultaneously or sequentially. Be the two Hardening methods used sequentially, for example, can be started with the thermal curing and terminated with the curing with actinic radiation. In other cases, it may be advantageous to begin and terminate curing with actinic radiation.
  • multi-layer color and / or effect coating can still be coated with a layer of an organically modified ceramic material, such as is commercially available, for example, under the brand Ormocer®.
  • the color and / or effect multicoat paint systems produced in accordance with the method of the invention have a particularly high gloss.
  • they In comparison with the multicoat paint systems produced in the usual and known manner, they have significantly less haze and hardly any disturbing surface structures, such as orange peel structures. They are therefore of particularly high optical quality. Since the other advantages of aqueous basecoats and powder slurry clearcoats are fully retained, they are of particularly high technical and economic value to users and their customers.
  • spray mist of a customary and known powder slurry clearcoat was applied to the surface of test panels coated with a black basecoat and flashed off for two minutes at room temperature. Subsequently, the powder slurry clearcoat was in Wedge shape applied over the spray mist droplets and flashed off for two minutes at room temperature. Subsequently, spray mist droplets and powder slurry clearcoats wedge were pre-dried at 40 ° C for 10 minutes and then baked at 150 ° C for 30 minutes.
  • the waviness of the powder slurry clearcoats of the example and the comparative experiment was measured by means of the wavescan method.
  • a laser beam was directed onto the surface at an angle of 60 °, and the fluctuations of the reflected light in a so-called long wave range (0.6 to 10 mm, observation distance: 2.5 m) and in the so-called short wave range (0.1 to 0.6 mm, observation distance: 45 cm) registered with the aid of a measuring device.

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  • 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)

Abstract

A process for producing colour and/or effect producing multi-layer paints on car bodies comprises applying a water based paint onto the body and drying or partially curing the resulting paint layer. An aqueous powder slurry clear coat is applied to the layer, and the layers are then cured by heat and actinic radiation. The clear coat is applied electrostatically to the body exterior and then pneumatically spraying the interior components.

Description

Die vorliegende Erfindung betrifft ein neues Verfahren zur Herstellung farb- und/oder effektgebender Mehrschichtlackierungen auf Automobilkarosserien, bei dem ein Pulverslurry-Klarlack verwendet wird.The present invention relates to a novel process for producing multicoat color and / or effect paint systems on automobile bodies in which a powder slurry clearcoat is used.

Bei der Automobilserienlackierung werden üblicherweise zuerst die Innenteile der Automobilkarosserien durch pneumatisches Spritzen oder Druckluftspritzen lackiert. Das pneumatische Spritzen wird deshalb gewählt, weil sich die Hohlräume und Vertiefungen aufgrund der Ausbildung von Faraday-Käfigen nur schlecht elektrostatisch beschichten lassen.In automotive OEM finishing, the inner parts of the automobile bodies are usually first painted by pneumatic spraying or compressed air spraying. The pneumatic spraying is chosen because the cavities and depressions due to the formation of Faraday cages are difficult to electrostatically coat.

Bei der Innenlackierung werden die Türen geöffnet, und es werden von Hand oder mit Hilfe eines Lackierautomaten die Fälze und die Innenseiten der Türen lackiert. Dabei entsteht aber Spritznebel, der auf die Außenhaut der Karosserie fällt. Hiervon sind insbesondere der Bereich um die Türen und die Motorhaube betroffen. Dieser Spritznebel trocknet bei Verwendung von Pulverklarlack-Slurries besonders rasch an und wird bei der nachfolgenden elektrostatischen Beschichtung der Karosserieaußenteile von der dabei angewandten Pulverklarlack-Slurry nur überdeckt, aber nicht wiederaufgenommen. Nach dem Einbrennen liegen daher an den Stellen, an denen der Spritznebel aufgetroffen ist, Erhebungen oder Verlaufsstörungen vor, die bei einer Größe von mehr als 0,5 µm sichtbar werden. Da diese Erhebungen oder Verlaufsstörungen außerdem noch an besonders leicht sichtbaren Bereichen der Karosserie vorliegen, sind sie optisch besonders auffallend und erwecken den Eindruck nicht ausreichender Qualität des Gesamtprodukts.In interior painting, the doors are opened, and by hand or with the help of an automatic varnishing machine, the rabbets and the insides of the doors are painted. But this creates spray mist that falls on the outer skin of the body. This particularly affects the area around the doors and the bonnet. This spray mist dries particularly quickly when using powder clearcoat slurries and is only covered in the subsequent electrostatic coating of the body exterior parts of the applied powder clearcoat slurry, but not resumed. After firing are therefore at the points where the spray mist has hit, surveys or flow disturbances, which are visible at a size of more than 0.5 microns. Since these elevations or flow disturbances are still present in particularly easily visible areas of the body, they are visually particularly striking and give the impression of insufficient quality of the overall product.

Diese Effekte sind bei lösemittelhaltigen Klarlacken nicht so ausgeprägt, da diese höhere Festkörpergehalte aufweisen, so daß die Differenz zwischen dem Festkörpergehalt des Naßlacks und dem Festkörpergehalt des Spritznebels geringer ist als im Falle der Pulverslurry-Klarlacke. Außerdem haben die lösemittelhaltigen Klarlacke eine geringere Viskosität, weswegen sie sich besser ausspreiten. Dadurch wird auch der Spritznebel flächiger. Nicht zuletzt trocknen sie wegen ihres Gehalts an hochsiedenden organischen Lösemitteln ("langen Lösemittel") nicht so schnell ein und können daher von hierauf applizierten Klarlacken wesentlich besser aufgenommen werden.These effects are not so pronounced with solventborne clearcoats, as they have higher solids contents, so that the difference between the Solid content of the wet paint and the solids content of the spray mist is lower than in the case of powder slurry clearcoats. In addition, the solvent-containing clearcoats have a lower viscosity, which is why they spread better. This also makes the spray mist more flat. Last but not least, because of their content of high-boiling organic solvents ("long solvents"), they do not dry so quickly and can therefore be much better absorbed by clearcoats applied thereon.

Aufgabe der vorliegenden Erfindungen ist es, ein neues Verfahren zur Herstellung von farb- und/oder effektgebenden Mehrschichtlackierungen auf Automobilkarosserien zu finden, daß die Nachteile des Standes der Technik nicht mehr länger aufweist, sondern auch bei Verwendung von Pulverslurry-Klarlacken Lackierungen liefert, die keine sichtbaren Erhebungen oder Verlaufsstörungen mehr aufweisen.The object of the present invention is to find a new process for the production of multicoat color and / or effect paint systems on automobile bodies that no longer has the disadvantages of the prior art but, even when using powder slurry clearcoats, provides coatings which do not have visible elevations or flow defects more.

Demgemäß wurde das neue Verfahren zur Herstellung farb- und/oder effektgebender Mehrschichtlackierungen auf Automobilkarosserien durch

  1. (I) Applikation eines Wasserbasislacks auf die Karosserie und Trocknung oder partielle Härtung der resultierenden Wasserbasislackschicht
  2. (II) Applikation eines wäßrigen Pulverslurry-Klarlacks auf die getrocknete oder partiell gehärtete Wasserbasislackschicht (II) und
  3. (III) Härtung der Schichten (I) und (II) durch Hitze oder Hitze und aktinische Strahlung (Dual Cure),
gefunden, bei dem die Applikation des wäßrigen Pulverslurry-Klarlacks (II) durch (IIa) elektrostatische Lackierung der Karosserieaußenteile, gefolgt von (II b) pneumatischem Spritzen (Druckluftspritzen) der Karosserieinnenteile,
erfolgt.Accordingly, the new process for producing multicoat color and / or effect paint systems on automobile bodies has been accomplished
  1. (I) Application of a water-based paint to the body and drying or partial curing of the resulting aqueous basecoat film
  2. (II) application of an aqueous powder slurry clearcoat to the dried or partially cured aqueous basecoat film (II) and
  3. (III) curing of layers (I) and (II) by heat or heat and actinic radiation (dual cure),
in which the application of the aqueous powder slurry clearcoat (II) by (IIa) electrostatic painting of the body exterior parts, followed by (II b) pneumatic spraying (compressed air spraying) of the interior body parts,
he follows.

Im folgenden wird das neue Verfahren zur Herstellung farb- und/oder effektgebender Mehrschichtlackierungen auf Automobilkarosserien als "erfindungsgemäßes Verfahren" bezeichnet.The new process for producing multicoat color and / or effect paint systems on automobile bodies is referred to below as the "process according to the invention".

Überraschenderweise bewirkt das neue Verfahren, daß die auf der Außenhaut der Automobilkarosserie befindliche, durch elektrostatische Lackierung applizierte, nasse Pulverslurry-Klarlackschichten problemlos die Spritznebeltropfen aus der Innenlackierung aufnehmen können, wodurch ein wesentlich besserer Verlauf erzielt wird.Surprisingly, the new process causes that located on the outer skin of the car body, applied by electrostatic painting, wet powder slurry clearcoat layers can easily absorb the spray mist droplets from the interior painting, whereby a much better flow is achieved.

Die bei dem erfindungsgemäßen Verfahren eingesetzten Automobilkarosserien weisen üblicherweise eine kathodisch abgeschiedene und thermisch gehärtete Elektrotauchlackierung auf. Sie können aber auch eine kathodisch abgeschiedene Elektrotauchlackschicht aufweisen, die nicht thermisch gehärtet, sondern lediglich getrocknet oder partiell gehärtet ist. Die Elektrotauchlackierung oder die Elektrotauchlackschicht wird kann mit einem Füller überschichtet, der entweder für sich alleine oder gemeinsam mit der Elektrotauchlackschicht gehärtet wird (Naß-in-naß-Verfahren). Die Überschichtung mit einem Füller erfolgt insbesondere in den Bereichen, die einer starken mechanischen Beanspruchung, wie beispielsweise durch Steinschlag, ausgesetzt sind.The automobile bodies used in the method according to the invention usually have a cathodically deposited and thermally cured electrodeposition coating. However, they may also have a cathodically deposited electrodeposition coating which is not thermally cured, but merely dried or partially cured. The electrodeposition coating or the electrodeposition coating layer can be overcoated with a filler which is cured either alone or together with the electrodeposition coating layer (wet-in-wet process). The coating with a filler takes place in particular in the areas which are exposed to a strong mechanical stress, such as by stone chipping.

Beispiele geeigneter kathodischer Elektrotauchlacke sowie ggf. von Naß-in-naß-Verfahren werden in der japanischen Patentanmeldung 1975-142501 (japanische Offenlegungsschrift JP 52-065534 A2 , Chemical Abstracts Referat Nr. 87: 137427 ) oder den Patentschriften US 4,375,498 A1 , US 4,537,926 A1 , US 4,761,212 A1 , EP 0 529 335 A1 , DE 41 25 459 A1 , EP 0 595 186 A1 , EP 0 074 634 A1 , EP 0 505 445 A1 , DE 42 35 778 A1 , EP 0 646 420 A1 , EP 0 639 660 A1 , EP 0 817 648 A1 , DE 195 12 017 C1 , EP 0 192 113 A2 , DE 41 26 476 A1 oder WO 98/07794 beschrieben.Examples of suitable cathodic electrodeposition paints and, if necessary, wet-on-wet processes are described in US Pat Japanese Patent Application 1975-142501 (Japanese Laid-Open Publication JP 52-065534 A2 . Chemical Abstracts Unit No. 87: 137427 ) or the patents US 4,375,498 A1 . US 4,537,926 A1 . US 4,761,212 A1 . EP 0 529 335 A1 . DE 41 25 459 A1 . EP 0 595 186 A1 . EP 0 074 634 A1 . EP 0 505 445 A1 . DE 42 35 778 A1 . EP 0 646 420 A1 . EP 0 639 660 A1 . EP 0 817 648 A1 . DE 195 12 017 C1 . EP 0 192 113 A2 . DE 41 26 476 A1 or WO 98/07794 described.

Desgleichen sind geeignete Füller, insbesondere wäßrige Füller, die auch als Steinschlagschutzgrundierungen oder Funktionsschichten bezeichnet werden, beispielsweise aus den Patentschriften US 4,537,926 A1 , EP 0 529 335 A1 , EP 0 595 186 A1 , EP 0 639 660 A1 , DE 44 38 504 A1 , DE 43 37 961 A1 , WO 89,/10387 , US 4,450,200 A1 , US 4,614,683 A1 oder WO 490/26827 beschrieben.Likewise suitable fillers, in particular aqueous fillers, which are also referred to as antistonechip primers or functional layers, for example from the patents US 4,537,926 A1 . EP 0 529 335 A1 . EP 0 595 186 A1 . EP 0 639 660 A1 . DE 44 38 504 A1 . DE 43 37 961 A1 . WO 89/10387 . US 4,450,200 A1 . US 4,614,683 A1 or WO 490/26827 described.

Diese Füller können indes auch auf die eingebrannten Elektrotauchlackierungen appliziert werden und anschließend vorgetrocknet bzw. partiell thermisch gehärtet werden. Bei dieser Variante des erfindungsgemäßen Verfahrens werden sie dann gemeinsam mit den auf die Füllerschichten applizierten Wasserbasislackschichten und Pulverslurry-Klarlackschichten gemeinsam gehärtet (erweitertes Naß-in-naß-Verfahren).However, these fillers can also be applied to the baked electrodeposition coatings and then pre-dried or partially thermally cured. In this variant of the method according to the invention, they are then cured together with the aqueous basecoat films and powder slurry clearcoat films applied to the surfacer layers (extended wet-on-wet process).

Im Innenbereich der Automobilkarosserie kann auch auf die Füllerlackierung oder Steinschlagschutzgrundierung verzichtet werden, weil hier i. a. keine Gefahr einer mechanischen Beanspruchung besteht.In the interior of the car body can be dispensed with the primer coat or Steinschlagschutzgrundierung, because here i. a. there is no risk of mechanical stress.

Im weiteren Verlauf des erfindungsgemäßen Verfahrens werden die Füllerlackierungen mit Wasserbasislacken beschichtet. Beispiele geeigneter Wasserbasislacke, insbesondere Wasserbasislacke auf Polyurethanbasis, sind aus den Patentschriften EP 0 089 497 A1 , EP 0 256 540 A1 , EP 0 260 447 A1 , EP 0 297 576 A1 , WO 96/12747 , EP 0 523 610 A1 , EP 0 228 003 A1 , EP 0 397 806 A1 , EP 0 574 417 A1 , EP 0 531 510 A1 , EP 0 581 211 A1 , EP 0 708 788 A1 , EP 0 593 454 A1 , DE-A-43 28 092 A1 , EP 0 299 148 A1 , EP 0 394 737 A1 , EP 0 590 484 A1 , EP 0 234 362 A1 , EP 0 234 361 A1 , EP 0 543 817 A1 , WO 95/14721 , EP 0 521 928 A1 , EP 0 522 420 A1 , EP 0 522 419 A1 , EP 0 649 865 A1 , EP 0 536 712 A1 , EP 0 596 460 A1 , EP 0 596 461 A1 , EP 0 584 818 A1 , EP 0 669 356 A1 , EP 0 634 431 A1 , EP 0 678 536 A1 , EP 0 354 261 A1 , EP 0 424 705 A1 , WO 97/49745 , WO 97/49747 , EP 0 401 565 A1 oder EP 0 817 684 , Spalte 5, Zeilen 31 bis 45, bekannt.In the further course of the process according to the invention, the surfacer coatings are coated with water-based paints. Examples of suitable aqueous basecoats, in particular waterborne basecoats based on polyurethane, are from the patents EP 0 089 497 A1 . EP 0 256 540 A1 . EP 0 260 447 A1 . EP 0 297 576 A1 . WO 96/12747 . EP 0 523 610 A1 . EP 0 228 003 A1 . EP 0 397 806 A1 . EP 0 574 417 A1 . EP 0 531 510 A1 . EP 0 581 211 A1 . EP 0 708 788 A1 . EP 0 593 454 A1 . DE-A-43 28 092 A1 . EP 0 299 148 A1 . EP 0 394 737 A1 . EP 0 590 484 A1 . EP 0 234 362 A1 . EP 0 234 361 A1 . EP 0 543 817 A1 . WO 95/14721 . EP 0 521 928 A1 . EP 0 522 420 A1 . EP 0 522 419 A1 . EP 0 649 865 A1 . EP 0 536 712 A1 . EP 0 596 460 A1 . EP 0 596 461 A1 . EP 0 584 818 A1 . EP 0 669 356 A1 . EP 0 634 431 A1 . EP 0 678 536 A1 . EP 0 354 261 A1 . EP 0 424 705 A1 . WO 97/49745 . WO 97/49747 . EP 0 401 565 A1 or EP 0 817 684 , Column 5, lines 31 to 45, known.

Üblicherweise werden die resultierenden Wasserbasislackschichten nicht gehärtet, sondern vorgetrocknet bzw. partiell gehärtet.Usually, the resulting aqueous basecoat films are not cured, but pre-dried or partially cured.

Auf die Wasserbasislackschichten werden die wäßrigen Pulverslurry-Klarlacke appliziert, so daß Pulverslurry-Klarlackschichten resultieren. Beispiele geeigneter Pulverslurry-Klarlacke sind aus der US-Patentschrift US-A-4,268,542 und den Patentanmeldungen DE 195 40 977 A1 , DE 195 18 392 A1 , DE 196 17 086 A1 , DE-A-196 13 547 , EP 0 652 264 A1 , DE 196 18 657 A1 , DE 196 52 813 A1 , DE 196 17 086 A1 oder DE-A-198 14 471 A1 bekannt.The aqueous powder clearcoat materials are applied to the aqueous basecoat films, resulting in powder slurry clearcoat films. Examples of suitable powder slurry clearcoats are known from U.S. Patent US-A-4,268,542 and the patent applications DE 195 40 977 A1 . DE 195 18 392 A1 . DE 196 17 086 A1 . DE-A-196 13 547 . EP 0 652 264 A1 . DE 196 18 657 A1 . DE 196 52 813 A1 . DE 196 17 086 A1 or DE-A-198 14 471 A1 known.

In erfindungsgemäßer Verfahrensweise werden die wäßrigen Pulverslurry-Klarlacke durch elektrostatische Lackierung der Karosserieaußenteile, gefolgt von pneumatischem Spritzen (Druckluftspritzen) der Karosserieinnenteile appliziert.In the inventive method, the aqueous powder clearcoats are applied by electrostatic painting the body exterior parts, followed by pneumatic spraying (compressed air spraying) of the body interior parts.

Dabei kann die elektrostatische Lackierung mittels eines elektrostatischen Sprühspalts, einer elektrostatischen Sprühglocke oder einer elektrostatischen Sprühscheibe erfolgen.In this case, the electrostatic coating can be carried out by means of an electrostatic spray gap, an electrostatic spray bell or an electrostatic spray disc.

Des weiteren kann die elektrostatische Lackierung durch Elektrostatik-unterstützte mechanische Zerstäubung erfolgen. Vorzugsweise wird diese mit Hilfe von elektrostatischen Hochrotationsscheiben oder Hochrotationsglocken durchgeführt.Furthermore, the electrostatic coating can be done by electrostatic assisted mechanical atomization. Preferably, this is performed by means of electrostatic high rotation disks or high rotation bells.

Auch das pneumatische Spritzen oder Druckluftlackieren weist keine methodischen Besonderheiten auf, sondern kann per Hand oder mit Hilfe von üblichen und bekannten Lackierautomaten oder -robotern durchgeführt werden.Also, the pneumatic spraying or air pressure painting has no special features, but can be done by hand or with the help of conventional and known paint sprayers or robots.

Ergänzend wird hierzu auf Römpp Lexikon Lacke und Druckfarben, Georg Thieme Verlag, Stuttgart, New York, 1998 , Seite 186: »Elektrostatische Lackierung«, Seite 187: »Elektrostatische Sprühpistolen«, »Elektrostatisches Sprühen«, sowie Seite 165: »Druckluftspritzen«, verwiesen.In addition to this is on Rompp Lexikon Lacke und Druckfarben, Georg Thieme Verlag, Stuttgart, New York, 1998 , Page 186: "Electrostatic coating", page 187: "Electrostatic spray guns", "Electrostatic spraying", and page 165: "Compressed air spraying", referenced.

Selbstverständlich können diese Applikationsmethoden im Rahmen des erfindungsgemäßen Verfahrens auch für die Herstellung der übrigen Lackschichten, ausgenommen der kathodisch abscheidbaren Elektrotauchlackschicht, angewandt werden.Of course, in the context of the process according to the invention, these application methods can also be used for the production of the other lacquer layers, with the exception of the cathodically depositable electrodeposition lacquer layer.

Bevorzugt wird die Applikation bei Beleuchtung mit sichtbarem Licht einer Wellenlänge von über 550 µm oder unter Lichtausschluß durchgeführt, wenn die Wasserbasislacke und/oder die Pulverslurry-Klarlacke thermisch und mit aktinischer Strahlung härtbar sind. Hierdurch werden eine stoffliche Änderung oder Schädigung des erfindungsgemäß zu verwendenden Beschichtungsstoffs und des Overspray vermieden.Preferably, the application is carried out when illuminated with visible light of a wavelength of about 550 microns or in the absence of light, when the aqueous basecoat materials and / or the powder slurry clearcoats are curable thermally and with actinic radiation. As a result, a material change or damage to be avoided according to the invention to be used coating material and overspray.

Im allgmeinen werden die erfindungsgemäß zu verwendenden Beschichtungsstoffe in einer Naßschichtdicke appliziert, daß nach ihrer Aushärtung Beschichtungen mit der für ihre Funktionen notwendigen und vorteilhaften Schichtdicken resultieren. Im Falle einer Basislackierung liegen sie bei 5 bis 50, vorzugsweise 5 bis 40, besonders bevorzugt 5 bis 30 und insbesondere 10 bis 25 µm, und im Falle einer Klarlackierung liegen sie bei 10 bis 100, vorzugsweise 15 bis 80, besonders bevorzugt 20 bis 75 und insbesondere 25 bis 70 µm.In general, the coating materials to be used according to the invention are applied in a wet layer thickness such that, after their curing, coatings result with the layer thicknesses necessary and advantageous for their functions. In the case of a basecoat, they are from 5 to 50, preferably from 5 to 40, particularly preferably from 5 to 30 and in particular from 10 to 25 μm, and in the case of a clearcoat they are from 10 to 100, preferably from 15 to 80, particularly preferably from 20 to 75 and in particular 25 to 70 microns.

Nach der Applikation werden die Wasserbasislackschichten gemeinsam mit den Pulverslurry-Klarlackschichten sowie gegebenenfalls den darunter liegenden nicht oder nicht vollständig gehärteten Lackschichten thermisch oder thermisch und mit aktinischer Strahlung gehärtet. Die Härtung mit Hitze und mit aktinischer Strahlung wird von der Fachwelt auch als Dual Cure bezeichnet. Im Rahmen der vorliegenden Erfindung ist unter aktinischer Strahlung elektromagnetische Strahlung wie nahes Infrarot (NIR), sichtbares Licht, UV-Licht oder Röntgenstrahlung, insbesondere aber UV-Licht, oder Korpuskularstrahlung wie Elektronenstrahlung zu verstehen.After application, the aqueous basecoat films are cured thermally or thermally and with actinic radiation together with the powder slurry clearcoat films and, if appropriate, the underlying non or fully cured coating films. Curing with heat and with actinic radiation is also referred to in the art as dual cure. In the context of the present invention, actinic radiation means electromagnetic radiation such as near infrared (NIR), visible light, UV light or X-radiation, but in particular UV light, or corpuscular radiation such as electron radiation.

Die Aushärtung kann nach einer gewissen Ruhezeit oder Ablüftzeit erfolgen. Sie kann eine Dauer von 30 s bis 2 h, vorzugsweise 1 min bis 1 h und insbesondere 1 min bis 45 min haben. Die Ruhezeit dient beispielsweise zum Verlauf und zur Entgasung der Schichten und zum Verdunsten von flüchtigen Bestandteilen wie gegebenenfalls noch vorhandenem Lösemittel und/oder Wasser.The curing can take place after a certain rest period or ventilation time. It may have a duration of 30 seconds to 2 hours, preferably 1 minute to 1 hour, and especially 1 minute to 45 minutes. The rest period serves, for example, for the course and degassing of the layers and for evaporation of volatile constituents, such as any remaining solvent and / or water.

Vorzugsweise wird bei der Härtung mit aktinischer Strahlung eine Dosis von 1.000 bis 2.000, bevorzugt 1.100 bis 1.900, besonders bevorzugt 1.200 bis 1.800, ganz besonders bevorzugt 1.300 bis 1.700 und insbesondere 1.400 bis 1.600 mJ/cm2 angewandt. Gegebenenfalls kann diese Härtung mit aktinischer Strahlung von anderen Strahlenquellen ergänzt werden. Im Falle von Elektronenstrahlen wird vorzugsweise unter Inertgasatmosphäre gearbeitet. Dies kann beispielsweise durch Zuführen von Kohlendioxid und/oder Stickstoff direkt an die Oberfläche der Klarlackschicht gewährleistet werden. Auch im Falle der Härtung mit UV-Strahlung kann, um die Bildung von Ozon zu vermeiden, unter Inertgas gearbeitet werden.In the case of curing with actinic radiation, it is preferable to use a dose of from 1,000 to 2,000, preferably from 1,100 to 1,900, particularly preferably from 1,200 to 1,800, very particularly preferably from 1,300 to 1,700 and in particular from 1,400 to 1,600 mJ / cm 2 . Optionally, this cure can be supplemented with actinic radiation from other sources. In the case of electron beams, it is preferable to operate under an inert gas atmosphere. This can be ensured, for example, by supplying carbon dioxide and / or nitrogen directly to the surface of the clearcoat film. Even in the case of curing with UV radiation, to avoid the formation of ozone, under inert gas can be used.

Für die Härtung mit aktinischer Strahlung werden die üblichen und bekannten Strahlenquellen und optischen Hilfsmaßnahmen angewandt. Beispiele geeigneter Strahlenquellen sind Blitzlampen der Firma VISIT, Quecksilberhoch- oder - niederdruckdampflampen, welche gegebenenfalls mit Blei dotiert sind, um ein Strahlenfenster bis zu 405 nm zu öffnen, oder Elektronenstrahlquellen. Deren Anordnung ist im Prinzip bekannt und kann den Gegebenheiten des Werkstücks und der Verfahrensparameter angepaßt werden. Bei kompliziert geformten Werkstücken, wie sie für Automobilkarosserien vorgesehen sind, können die nicht direkter Strahlung zugänglichen Bereiche (Schattenbereiche) wie Hohlräume, Falzen und anderen konstruktionsbedingte Hinterschneidungen mit Punkt-, Kleinflächen- oder Rundumstrahlern, verbunden mit einer automatischen Bewegungseinrichtung für das Bestrahlen von Hohlräumen oder Kanten, (partiell) ausgehärtet werden.For curing with actinic radiation, the usual and known radiation sources and optical aids are used. Examples of suitable radiation sources are flash lamps from the company VISIT, mercury high- or low-pressure vapor lamps, optionally doped with lead, to open a beam window up to 405 nm, or electron beam sources. Their arrangement is known in principle and can be adapted to the conditions of the workpiece and the process parameters. In complicated shaped workpieces, such as are provided for automobile bodies, the non-direct radiation accessible areas (shadow areas) such as cavities, folds and other design undercuts with point, small area or omnidirectional, associated with an automatic moving device for the irradiation of cavities or Edges, (partially) cured.

Die Anlagen und Bedingungen dieser Härtungsmethoden werden beispielsweise in R. Holmes, U.V. and E.B. Curing Formulations for Printing Inks, Coatings and Paints, SITA Technology, Academic Press, London, United Kindom 1984 , beschrieben.The facilities and conditions of these curing methods are used, for example, in R. Holmes, UV and EB Curing Formulations for Printing Inks, Coatings and Paints, SITA Technology, Academic Press, London, United Kindom 1984 , described.

Hierbei kann die Aushärtung stufenweise erfolgen, d. h. durch mehrfache Belichtung oder Bestrahlung mit aktinischer Strahlung. Dies kann auch alternierend erfolgen, d. h., daß abwechselnd mit UV-Strahlung und Elektronenstrahlung gehärtet wird.Here, the curing can be done in stages, d. H. by multiple exposure or irradiation with actinic radiation. This can also be done alternately, d. h., That is cured alternately with UV radiation and electron radiation.

Auch die thermische Härtung weist keine methodischen Besonderheiten auf, sondern erfolgt nach den üblichen und bekannten Methoden wie Erhitzen in einem Umluftofen oder Bestrahlen mit IR- und/oder NIR-Lampen. Wie bei der Härtung mit aktinischer Strahlung kann auch die thermische Härtung stufenweise erfolgen. Vorteilhafterweise erfolgt die thermische Härtung bei Temperaturen von 90 °C bis 180 °C.The thermal curing has no special features, but takes place by the usual and known methods such as heating in a convection oven or irradiation with IR and / or NIR lamps. As in the case of curing with actinic radiation, the thermal curing can also take place in stages. Advantageously, the thermal curing takes place at temperatures of 90 ° C to 180 ° C.

Bei Dual Cure können thermische Härtung und Härtung mit aktinischer Strahlung gleichzeitig oder nacheinander angewandt werden. Werden die beiden Härtungsmethoden nacheinander verwendet, kann beispielsweise mit der thermischen Härtung begonnen und mit der Härtung mit aktinischer Strahlung geendet werden. In anderen Fällen kann es sich als vorteilhaft erweisen, mit der Härtung mit aktinischer Strahlung zu beginnen und hiermit zu enden.With Dual Cure, thermal curing and curing with actinic radiation can be used simultaneously or sequentially. Be the two Hardening methods used sequentially, for example, can be started with the thermal curing and terminated with the curing with actinic radiation. In other cases, it may be advantageous to begin and terminate curing with actinic radiation.

Selbstverständlich können die vorstehend beschriebenen Härtungsmethoden im Rahmen des erfindungsgemäßen Verfahrens auch zur Härtung der übrigen Lackschichten angewandt werden.Of course, the curing methods described above in the context of the method according to the invention can also be used for curing the other lacquer layers.

Die durch das erfindungsgemäße Verfahren resultierende mehrschichtige farb- und/oder effektgebende Lackierung kann noch mit einer Schicht aus einem organisch modifizierten Keramikmaterial, wie es beispielsweise unter der Marke Ormocer® im Handel erhältlich ist, beschichtet werden.The resulting by the process according to the invention multi-layer color and / or effect coating can still be coated with a layer of an organically modified ceramic material, such as is commercially available, for example, under the brand Ormocer®.

Die in erfindungsgemäßer Verfahrensweise hergestellten farb- und/oder effektgebenden Mehrschichtlackierungen weisen eine besonders hohen Glanz auf. Im Vergleich zu den in üblicher und bekannter Weise hergestellten Mehrschichtlackierungen haben sie signifikant weniger Schleier und kaum bis gar keine störenden Oberflächenstrukturen wie Orangenhautstrukturen. Sie sind daher von besonders hoher optischer Qualität. Da die sonstigen Vorteile von Wasserbasislackierungen und Pulverslurry-Klarlackierungen in vollem Umfang erhalten bleiben, sind sie für die Anwender und deren Kunden von einem besonders hohen technischen und wirtschaftlichen Wert.The color and / or effect multicoat paint systems produced in accordance with the method of the invention have a particularly high gloss. In comparison with the multicoat paint systems produced in the usual and known manner, they have significantly less haze and hardly any disturbing surface structures, such as orange peel structures. They are therefore of particularly high optical quality. Since the other advantages of aqueous basecoats and powder slurry clearcoats are fully retained, they are of particularly high technical and economic value to users and their customers.

Beispiel und VergleichsversuchExample and comparative experiment

Für den Vergleichsversuch wurde Spritznebel eines üblichen und bekannten Pulverslurry-Klarlacks auf die Oberfläche von Prüftafeln, die mit einer schwarzen Basislackierung beschichtet waren appliziert und während zwei Minuten bei Raumtemperatur abgelüftet. Anschließend wurde der Pulverslurry-Klarlack in Keilform über die Spritznebel-Tröpfchen appliziert und während zwei Minuten bei Raumtemperatur abgelüftet. Anschließend wurden Spritznebel-Tröpfchen und Pulverslurry-Klarlacke-Keil bei 40°C während 10 Minuten vorgetrocknet und dann während 30 Minuten bei 150 °C eingebrannt.For the comparative experiment, spray mist of a customary and known powder slurry clearcoat was applied to the surface of test panels coated with a black basecoat and flashed off for two minutes at room temperature. Subsequently, the powder slurry clearcoat was in Wedge shape applied over the spray mist droplets and flashed off for two minutes at room temperature. Subsequently, spray mist droplets and powder slurry clearcoats wedge were pre-dried at 40 ° C for 10 minutes and then baked at 150 ° C for 30 minutes.

Für das Beispiel wurde der Vergleichsversuch wiederholt, nur daß zunächst der Pulverslurry-Klarlack in Keilform und anschließend die Spritznebel appliziert wurden.For the example of the comparative experiment was repeated, except that first the powder slurry clearcoat in wedge shape and then the spray mist were applied.

Die Welligkeit der Pulverslurry-Klarlackierungen des Beispiels und des Vergleichsversuchs wurde mit Hilfe der Wavescan-Methode gemessen. Zu diesem Zweck wurde ein Laserstrahl unter einem Winkel von 60° auf die Oberfläche gerichtet, und es wurden auf einer Meßstrecke von 10 cm die Schwankungen des reflektierten Lichts im sogenannten long wave-Bereich (0,6 bis 10 mm; Beobachtungabstand: 2,5 m) und im sogenannten short wave-Bereich (0,1 bis 0,6 mm; Beobachtungsabstand: 45 cm) mit Hilfe eines Meßgeräts registriert.The waviness of the powder slurry clearcoats of the example and the comparative experiment was measured by means of the wavescan method. For this purpose, a laser beam was directed onto the surface at an angle of 60 °, and the fluctuations of the reflected light in a so-called long wave range (0.6 to 10 mm, observation distance: 2.5 m) and in the so-called short wave range (0.1 to 0.6 mm, observation distance: 45 cm) registered with the aid of a measuring device.

Glanz und Haze wurden reflektometrisch unter einem Winkel von 20° mit einem Reflektometer der Firma BYK nach DIN 67530: 1982-01 oder ISO 2813: 1994 gemessen.Gloss and haze were measured reflectometrically at an angle of 20 ° with a reflectometer from BYK according to DIN 67530: 1982-01 or ISO 2813: 1994.

Die Ergebnisse finden sich in der Tabelle 1 (Vergleichsversuch) und in der Tabelle 2 (Beispiel). Der Vergleich der Ergebnisse zeigt, daß das erfindungsgemäße Verfahren Pulverslurry-Klarlackierungen mit signifikant besseren optischen Eigenschaften und Oberflächeneigenschaften lieferte. Tabelle 1: Glanz, Haze und Welligkeit von in üblicher und bekannter Weise hergestellten Pulverslurry-Klarlackierungen (Vergleichsversuch) Nebel/Keil (µm) Glanz Haze Welligkeit:
Long Wave Short Wave 30 76,0 50,4 46,0 54,3 40 77,0 33,6 35,2 34,3 50 77,1 28,3 16,3 17,5 Tabelle 2: Glanz, Haze und Welligkeit von in erfindungsgemäßer Weise hergestellten Pulverslurry-Klarlackierungen (Beispiel) Nebel/Keil (µm) Glanz Haze Welligkeit:
Long Wave Short Wave 30 77 4 32,6 22,5 33,1 40 78,0 27,1 9,9 15,1 50 77,7 27,6 6,9 15,3 The results can be found in Table 1 (comparative experiment) and in Table 2 (Example). Comparison of the results shows that the process according to the invention provided powder slurry clearcoats with significantly better optical properties and surface properties. <b> Table 1: Gloss, Haze and waviness of powder slurry clearcoats prepared in the usual and known manner (comparative experiment) </ b> Fog / wedge (μm) shine Haze ripple:
Long Wave Short Wave 30 76.0 50.4 46.0 54.3 40 77.0 33.6 35.2 34.3 50 77.1 28.3 16.3 17.5 Fog / wedge (μm) shine Haze ripple:
Long Wave Short Wave 30 77 4 32.6 22.5 33.1 40 78.0 27.1 9.9 15.1 50 77.7 27.6 6.9 15.3

Claims (8)

  1. A process for producing multicoat color and/or effect paint systems on automobile bodies by
    (I) applying an aqueous base coat material to the body and drying or partially curing the resultant aqueous basecoat film,
    (II) applying an aqueous powder slurry clearcoat material to the dried or partially cured aqueous basecoat film (II), and
    (III) curing the films (I) and (II) by heat or by heat and actinic radiation (dual cure),
    which comprises applying the aqueous powder slurry clearcoat material (II) by
    (IIa) electrostatic coating of the exterior body parts, followed by
    (IIb) pneumatic spraying (compressed air spraying) of the interior body parts.
  2. The process according to claim 1, wherein electrostatic coating (IIa) is carried out by means of an electrostatic spraying slot, an electrostatic spraying bell or an electrostatic spraying disk.
  3. The process according to claim 1, wherein electrostatic coating (IIa) is carried out by means of electrostatically assisted mechanical atomization.
  4. The process according to claim 3, wherein electrostatically assisted mechanical atomization is carried out by means of electrostatic high-speed rotating disks or high-speed rotating bells.
  5. The process according to any of claims 1 to 4, wherein prior to the application of the aqueous basecoat material a surfacer is applied to the body and the resulting surfacer film is cured or alternatively a surfacer is applied to the body and the resulting surfacer film is dried or partially cured.
  6. The process according to claim 5, wherein an aqueous surfacer is used.
  7. The process according to any of claims 1 to 6, wherein a polyurethane-based aqueous basecoat material is used.
  8. The process according to any of claims 1 to 7, wherein the body is coated with a cathodically depositable electrocoat material which is thermally cured or dried or partially thermally cured before the application of the surfacer and is then baked together with the surfacer film.
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DE50113194D1 (en) 2007-12-13
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US20030108681A1 (en) 2003-06-12
ATE376890T1 (en) 2007-11-15
EP1257368A2 (en) 2002-11-20
WO2001062401A2 (en) 2001-08-30
AU2001233731A1 (en) 2001-09-03
WO2001062401A3 (en) 2002-03-14
CA2400621C (en) 2008-01-15
BR0108686A (en) 2002-11-12
MXPA02006950A (en) 2003-03-27
CA2400621A1 (en) 2001-08-30

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