EP0061165A1 - 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 PDFInfo
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- EP0061165A1 EP0061165A1 EP82102250A EP82102250A EP0061165A1 EP 0061165 A1 EP0061165 A1 EP 0061165A1 EP 82102250 A EP82102250 A EP 82102250A EP 82102250 A EP82102250 A EP 82102250A EP 0061165 A1 EP0061165 A1 EP 0061165A1
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- layer
- lacquer layer
- binder
- esters
- effect
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- 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
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- 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 half-esters as a binder, and a clear lacquer layer thereon containing 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.
- 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 involves 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 plates 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 (see US Pat. No. 3,639,147). 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 lacquer layer is not cured before the clear lacquer layer is applied, and both layers are then cured together.
- DE-OS 30 35 917 describes a method for applying a multilayer coating to a motor vehicle, according to which an effect coating layer is applied to a color coating layer, which contains titanium dioxide-coated mica platelets as an interference pigment, and optionally a clear coating layer thereon is applied.
- a color coating layer which contains titanium dioxide-coated mica platelets as an interference pigment, and optionally a clear coating layer thereon is applied.
- 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 baking 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, the parts that are not to be painted must be protected by masking before applying a paint. After the stoving process, the masking must 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 paint layer and, if appropriate, the clear coat layer are applied and baked. This process is technically very complicated.
- the present invention is based on the task of creating motor vehicles with an effect lacquer layer which, as in DE-OS 30 35 917, has a more iridescent effect or different effects at different angles 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 de finished composition.
- 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 binders, and one thereon located clearcoat layer containing heat-curable acrylic-melamine-resin combinations or air-drying acrylic-isocyanate-resin combinations as a binder, which is characterized in that the colored lacquer layer is 15 to 60% by weight, 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 ether and / or ester or half-ester as binder, 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 proportion of binder in this layer Contains cellulose ethers and / or esters or half-esters, and that all three layers mentioned wet-on-wet applied and ge can be 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 usually 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 cellulose ethers, etc. According to the prior art, such cellulose ethers were added to the metallic lacquers in order to bring about a rapid fixation of 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 it is obtained when mica platelets coated with titanium dioxide are used as interference pigments. These pigments are known (see, for example, DE-OS 19 59 998 and DE-AS 14 67 468).
- 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, and advantageously 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 ⁇ m .
- the lower limit is preferably about 10 / ⁇ m, while the upper limit is preferably about 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 (registered trademark) 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.
- There are applied the prior art conventionally used for the final coating hardness temperatures for example from about 70 ° C to 170 0 C for periods of from about 10 to 40 minutes, in general, the duration of the stoving is inversely proportional to the temperature employed.
- 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 heated to moderate temperatures of not more than about 80 ° C. All three layers of paint are cured.
- the dry film thickness of the clear coat layer is suitably 15 to 50 / um, which are for the lower limit of 20 / um and for the upper limit of 40 / um are preferred.
- the term “acrylic” is also understood to mean methacrylic resin systems, as are also used in this field according to the prior art (cf., inter alia, US Pat. No. 3,639,147, GB Pat. No. 1,284,755, DE-OS 28 12 397).
- the proportion of mica platelets coated with titanium dioxide in the effect lacquer layer is expediently 0.5 to 8% by weight, preferably at least approximately 1% by weight and at most approximately 6% by weight, calculated on the total weight of the lacquer 3 to 40% by weight, preferably 4 to 30% by weight, depending on the color of the substrate.
- those of the resin systems described above are preferably used which physically dry in 1 to 15 minutes, preferably 2 to 12 minutes, 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 minutes, preferably 2 to 12 minutes, particularly preferably 3 to 8 minutes.
- the layers applied in front of it must, as stated above, be physically dried within the stated time to such an extent that substantial mixing or greater swelling of the varnish layers applied to them is avoided during application.
- the above-mentioned drying times for the effect lacquer 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. If, however, the mica platelets can move, in particular rotate, for a long 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
- 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.
- the paints used according to the invention naturally contain the usual paint additives and solvents.
- a colored lacquer layer is applied to the provided in conventional manner with anticorrosive coatings body parts / um applied in a dry film thickness of 20, which contains an oil-free polyester resin and melamine resin, a content of 40 wt .-% cellulose acetate butyrate, based on the binder content of this layer, and contains 35% Bayferrox 3920 FF (inorganic brown pigment), calculated on the total solid content, as well as conventional paint additives and solvents.
- Bayferrox 3920 FF inorganic brown pigment
- an effect paint layer is applied in a dry film thickness of 10 / um, which contains an oil-free polyester and melamine resin as a binder , having a content of about 32 wt .-% cellulose acetate butyrate, based on the binder content of this layer and 2 wt .-% titanium dioxide in rutile form coated mica flakes, relative to the varnish, and the usual L ackzu accounts and contains solvent.
- 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 about 30 / um. Then baked at about 140 0 C for 20 minutes.
- a motor vehicle with a conventional filler paint is sanded. Then a layer of colored paint is applied by the usual spraying process with a dry film thickness of 25 / um, 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 Contains paint additives and solvents.
- the effect coating is applied to a dry film thickness of 15 / by means of an electrostatic hand spray gun. 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 as the binder.
- an acrylic-Isocyanatharzkombination is coated as a binder in a dry film thickness of 30 / um with a clear lacquer, schauend. The mixture is then heated to 80 ° C for 10 minutes or 50 ° C for 1 hour or 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.
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- Life Sciences & Earth Sciences (AREA)
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Abstract
Description
Kraftfahrzeug mit mehrschichtiger Lackierung und Verfahren zum mehrschichtigen LackierenMotor vehicle with multi-layer painting and method for multi-layer painting
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. -halbester als 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 half-esters as a binder, and a clear lacquer layer thereon containing 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.The invention also relates to a method for multi-layer painting of motor vehicles.
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 Silber-Metalliceffekt 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 Celluloseacetobutyrat enthalten ( vergl. US-PS 3 639 147). Es ist nach diesem Stand der Technik auch möglich die Metallic-Lackschicht und die Klarlackschicht nach dem sogenannten Naß-in-NaßVerfahren aufzubringen, d.h.die Metallic-Lackschicht wird nicht ausgehärtet, bevor die Klarlackschicht aufgetragen wird, und beide Schichten werden dann gemeinsam gehärtet.It is known to provide motor vehicles with a multilayer coating on one or more corrosion protection layers, in particular when the coating is said 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 involves 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 plates 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 (see US Pat. No. 3,639,147). 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 lacquer layer is not cured before the clear lacquer layer is applied, and both layers are then cured together.
Die DE-OS 30 35 917 beschreibt ein Verfahren zum Aufbringen einer mehrschichtigen Lackierung 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 elektrostatisches Auftragsverfahren aufgebracht. Voraussetzung für die Durchführung dieses Verfahrens ist, daß die Farblackschicht eingebrannt wird, bevor die Effektlackschicht aufgebracht werden kann.DE-OS 30 35 917 describes a method for applying a multilayer coating to a motor vehicle, according to which an effect coating layer is applied to a color coating layer, which contains titanium dioxide-coated mica platelets as an interference pigment, and optionally a clear coating layer thereon is applied. 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 muß. 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 baking 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, the parts that are not to be painted must be protected by masking before applying a paint. After the stoving process, the masking must 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 paint layer and, if appropriate, the clear coat layer are applied and baked. This process is technically very complicated.
Der vorliegenden Effindung liegt die Aufgabenstellung zugrunde, Kraftfahrzeuge mit einer Effektlackschicht zu schaffen, die wie gemäß DE-OS 30 35 917 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 task of creating motor vehicles with an effect lacquer layer which, as in DE-OS 30 35 917, has a more iridescent effect or different effects at different angles 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 de finished composition.
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 binders, and one thereon located clearcoat layer containing heat-curable acrylic-melamine-resin combinations or air-drying acrylic-isocyanate-resin combinations as a binder, which is characterized in that the colored lacquer layer is 15 to 60% by weight, 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 luftrocknende 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 ether and / or ester or half-ester as binder, 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 proportion of binder in this layer Contains cellulose ethers and / or esters or half-esters, and that all three layers mentioned wet-on-wet applied and ge can be cured together in one operation, the effect lacquer layer being applied by an electrostatic application process.
Bevorzugt hat die Farblackschicht eine Trockenfilmdicke von 10 bis 30 /um.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 Kraftfahrzeug-Lackierungen 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 Farblackschicht enthält 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 i!:. 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 Farblackschicht wird 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 usually 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 cellulose ethers, etc. According to the prior art, such cellulose ethers were added to the metallic lacquers in order to bring about a rapid fixation of the metallic flakes. Since this problem cannot occur with colored lacquer layers, it was not obvious to add the cellulose ethers etc. to any colored lacquer layers, and i ! :. in practice, this has not yet been done. 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 zumindestens teilweise Transparenz verstanden, wie sie erhalten wird, wenn man als Pigmente mit Titandioxid beschichtete Glimmerplättchen als Interferenzpigmente verwendet. Diese Pigmente sind bekannt (vergl. z.B. DE-OS 19 59 998 und DE-AS 14 67 468). 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 /um. Die untere Grenze liegt vorzugsweise bei etwa 10/um, während die obere Grenze vorzugsweise bei etwa 15/um liegt.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 it is obtained when mica platelets coated with titanium dioxide are used as interference pigments. These pigments are known (see, for example, DE-OS 19 59 998 and DE-AS 14 67 468). 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, and advantageously 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 μm . The lower limit is preferably about 10 / µm, while the upper limit is preferably about 15 / µm.
Überraschenderweise lassen sich einwandfreie und zufriedenstellende Effekt-Lackierungen 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.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 paints 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 process 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 (eingetragenes Warenzeichen)-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 lufttrockende Acryl-Isocyanat-Harz-Kombinationen aufweist. Beide Lacksysteme sind auf dem Gebiet der Lackierung 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 1700C für Zeiträume von etwa 10 bis 40 Minuten, 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 (registered trademark) 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. There are applied the prior art conventionally used for the final coating hardness temperatures, for example from about 70 ° C to 170 0 C for periods of from about 10 to 40 minutes, in general, the duration of the stoving is inversely proportional to the temperature employed.
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 UmweltBedingungen 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 heated to moderate temperatures of not more than about 80 ° C. All three layers of paint are cured.
Die Trockenfilmstärke der Klarlackschicht beträgt zweckmäßig 15 bis 50/um, wobei für die untere Grenze 20/um und für die obere Grenze 40/um bevorzugt sind.The dry film thickness of the clear coat layer is suitably 15 to 50 / um, which are for the lower limit of 20 / um and for the upper limit of 40 / um are preferred.
Unter dem Begriff "Acryl" werden gemäß der Erfindung auch Methacryl-Harzsysteme verstanden, wie diese auch gemäß dem Stand der Technik auf diesem Gebiet eingesetzt werden (vergl. u.a. US-PS 3 639 147, GB-PS 1 284 755, DE-OS 28 12 397).According to the invention, the term “acrylic” is also understood to mean methacrylic resin systems, as are also used in this field according to the prior art (cf., inter alia, US Pat. No. 3,639,147, GB Pat. No. 1,284,755, DE-OS 28 12 397).
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 Lackes.(Berechnet auf Festkörper etwa 3 bis 40 Gew.-%, vorzugsweise 4 bis 30 Gew.-%, je nach Farbe des Untergrunds.)The proportion of mica platelets coated with titanium dioxide in the effect lacquer layer is expediently 0.5 to 8% by weight, preferably at least approximately 1% by weight and at most approximately 6% by weight, calculated on the total weight of the lacquer 3 to 40% by weight, preferably 4 to 30% by weight, 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 Minuten, vorzugsweise 2 bis 12 Minuten, besonders bevorzugt 3 bis 8 Minuten 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 minutes, preferably 2 to 12 minutes, particularly preferably 3 to 8 minutes.
Es ist zweckmäßig, auf die Farblacklackschicht die Effektlackschicht nach 1 bis 15 Minuten, vorzugsweise 2 bis 12 Minuten, besonders bevorzugt 3 bis 8 Minuten, 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 Effekt-Lack 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 minutes, preferably 2 to 12 minutes, particularly preferably 3 to 8 minutes. The same applies analogously to the application of the Clear varnish layer on the effect varnish layer The layers applied in front of it must, as stated above, be physically dried within the stated time to such an extent that substantial mixing or greater swelling of the varnish layers applied to them is avoided during application. The above-mentioned drying times for the effect lacquer 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. If, however, the mica platelets can move, in particular rotate, for a long 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 paints used according to the invention naturally contain the usual paint additives and solvents.
Bei der Serienlackierung von Kraftfahrzeugen wird auf die in üblicher Weise mit Korrosionsschutzschichten versehenen Karosserieteile eine Farblackschicht in einer Trockenfilmstärke von 20/um aufgebracht, die einen öl-freien Polyester und Melaminharz enthält, einen Gehalt von 40 Gew.-% Celluloseacetobutyrat, bezogen auf den Bindemittelgehalt dieser Schicht, aufweist und 35% Bayferrox 3920 FF (anorganisches Braunpigment) , berechnet auf Gesamtfestanteil, sowie übliche Lackzusätze und Lösemittel enthält.In the series lacquering of motor vehicles, a colored lacquer layer is applied to the provided in conventional manner with anticorrosive coatings body parts / um applied in a dry film thickness of 20, which contains an oil-free polyester resin and melamine resin, a content of 40 wt .-% cellulose acetate butyrate, based on the binder content of this layer, and contains 35% Bayferrox 3920 FF (inorganic brown pigment), calculated on the total solid content, as well as conventional paint additives and solvents.
Nach 5 Minuten 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 Trockenfilmstärke von 10/um 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 Minuten, wird hierauf die Klarlackschicht aufgebracht, die eine in der Kraftfahrzeuglackierung übliche Acryl-Melaminharzkombination in einem üblichen Lösungsmittelgemisch enthält. Die Trockenfilmstärke dieser Schicht beträgt etwa 30/um. Danach wird 20 Minuten bei etwa 1400C eingebrannt.After 5 minutes flash-off time, without grinding, wet-on-wet with the help of a stationary system for electrostatic painting using a rotating bell in an electrostatic field, an effect paint layer is applied in a dry film thickness of 10 / um, which contains an oil-free polyester and melamine resin as a binder , having a content of about 32 wt .-% cellulose acetate butyrate, based on the binder content of this layer and 2 wt .-% titanium dioxide in rutile form coated mica flakes, relative to the varnish, and the usual L ackzusätze and contains solvent. 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 about 30 / um. Then baked at about 140 0 C for 20 minutes.
Ein Kraftfahrzeug mit einer üblichen Füllerlackierung wird angeschliffen. Hierauf wird eine Farblackschicht nach den üblichen Spritzverfahren mit einer Trockenfilmstärke von 25/um 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 paint is sanded. Then a layer of colored paint is applied applied by the usual spraying process with a dry film thickness of 25 / um, 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 Contains paint additives and solvents.
Nach einer Ablüftzeit von 8 Minuten wird mittels einer elektrostatischen Handspritzpistole der Effektlack in einer Trockenfilmstärke von 15/um 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 Minuten wird mit einem Klarlack, enthältend eine Acryl-Isocyanatharzkombination als Bindemittel in einer Trockenfilmstärke von 30/um beschichtet. Danach wird 10 Minuten auf 80°C oder 1 Stunde lang auf 50°C erwärmt oder auch unter Umweltbedingungen ge- trocknet.After a drying time of 8 minutes, the effect coating is applied to a dry film thickness of 15 / by means of an electrostatic hand spray gun. 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 as the binder. After 5 minutes, an acrylic-Isocyanatharzkombination is coated as a binder in a dry film thickness of 30 / um with a clear lacquer, enthältend. The mixture is then heated to 80 ° C for 10 minutes or 50 ° C for 1 hour or 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)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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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 |
Publications (2)
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EP0061165A1 true EP0061165A1 (en) | 1982-09-29 |
EP0061165B1 EP0061165B1 (en) | 1984-08-01 |
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EP82102250A Expired EP0061165B1 (en) | 1981-03-24 | 1982-03-19 | Motor vehicle with multi-layer varnish coating, and process for multi-layer varnish coating |
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EP (1) | EP0061165B1 (en) |
JP (1) | JPS57171473A (en) |
AU (1) | AU8185682A (en) |
BR (1) | BR8201616A (en) |
DE (2) | DE3111478A1 (en) |
ES (1) | ES8308231A1 (en) |
ZA (1) | ZA821928B (en) |
Cited By (4)
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DE3524831A1 (en) * | 1984-07-11 | 1986-01-16 | Kansai Paint Co., Ltd., Amagasaki, Hyogo | METALLIC PAINTING PROCESS |
EP0169796A2 (en) * | 1984-07-23 | 1986-01-29 | BASF Corporation | Opalescent coating |
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 |
Families Citing this family (7)
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JPS59160571A (en) * | 1983-03-02 | 1984-09-11 | Toyota Motor Corp | Finishing method for painting |
ZA854963B (en) * | 1984-07-23 | 1986-02-26 | Inmont Corp | Opalescent coating |
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 |
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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DE2818100A1 (en) * | 1977-04-25 | 1978-11-09 | Ici Ltd | METHOD FOR PRODUCING A SURFACE COATING |
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DE1805196C3 (en) * | 1968-10-25 | 1978-07-20 | Chemische Werke Huels Ag, 4370 Marl | Coating agents |
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DE2013702B2 (en) * | 1970-03-21 | 1974-10-24 | Chemische Werke Huels Ag, 4370 Marl | Coating agents |
US3869305A (en) * | 1971-08-10 | 1975-03-04 | Aluminum Co Of America | Method for producing an opaque coating |
DE2163503A1 (en) * | 1971-12-21 | 1973-07-19 | Reichhold Albert Chemie Ag | COATING AGENTS |
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DE2702986A1 (en) * | 1977-01-26 | 1978-07-27 | Bayer Ag | CROSS-LINKING AQUATIC COATING AGENTS |
DE2806497C2 (en) * | 1978-02-16 | 1982-02-18 | Basf Farben + Fasern Ag, 2000 Hamburg | Multi-layer painting with a clear coat as the final layer |
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- 1981-03-24 DE DE19813111478 patent/DE3111478A1/en not_active Withdrawn
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1982
- 1982-03-19 EP EP82102250A patent/EP0061165B1/en not_active Expired
- 1982-03-19 DE DE8282102250T patent/DE3260489D1/en not_active Expired
- 1982-03-22 ES ES510621A patent/ES8308231A1/en not_active Expired
- 1982-03-22 ZA ZA821928A patent/ZA821928B/en unknown
- 1982-03-23 JP JP57044780A patent/JPS57171473A/en active Pending
- 1982-03-23 BR BR8201616A patent/BR8201616A/en unknown
- 1982-03-24 AU AU81856/82A patent/AU8185682A/en not_active Abandoned
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DE2818100A1 (en) * | 1977-04-25 | 1978-11-09 | Ici Ltd | METHOD FOR PRODUCING A SURFACE COATING |
GB2012191A (en) * | 1977-09-29 | 1979-07-25 | Kodak Ltd | Coating process utilising cellulose esters such as cellulose acetate butyrate |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
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DE3524831A1 (en) * | 1984-07-11 | 1986-01-16 | Kansai Paint Co., Ltd., Amagasaki, Hyogo | METALLIC PAINTING PROCESS |
EP0169796A2 (en) * | 1984-07-23 | 1986-01-29 | BASF Corporation | Opalescent coating |
EP0169796A3 (en) * | 1984-07-23 | 1986-07-16 | Inmont Corporation | Opalescent coating |
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 |
Also Published As
Publication number | Publication date |
---|---|
JPS57171473A (en) | 1982-10-22 |
DE3260489D1 (en) | 1984-09-06 |
ES510621A0 (en) | 1983-08-16 |
DE3111478A1 (en) | 1982-10-07 |
ES8308231A1 (en) | 1983-08-16 |
EP0061165B1 (en) | 1984-08-01 |
AU8185682A (en) | 1982-09-30 |
ZA821928B (en) | 1983-01-26 |
BR8201616A (en) | 1983-02-08 |
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