EP0787536A2 - Weather resistant polyamide powder coating - Google Patents
Weather resistant polyamide powder coating Download PDFInfo
- Publication number
- EP0787536A2 EP0787536A2 EP96110037A EP96110037A EP0787536A2 EP 0787536 A2 EP0787536 A2 EP 0787536A2 EP 96110037 A EP96110037 A EP 96110037A EP 96110037 A EP96110037 A EP 96110037A EP 0787536 A2 EP0787536 A2 EP 0787536A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- polyamide
- colored
- weather
- layer
- polyamide powder
- 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.)
- Granted
Links
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
-
- 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
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/18—Processes for applying liquids or other fluent materials performed by dipping
- B05D1/22—Processes for applying liquids or other fluent materials performed by dipping using fluidised-bed technique
- B05D1/24—Applying particulate materials
Definitions
- the invention relates to weather-resistant, colored polyamide coatings, processes for their production and their preferred use.
- a powder coating is generally understood to be the coating of surfaces by applying and sintering meltable powders.
- Various methods for powder coating are known. Among these processes, the vortex sintering process is considered to be an easy method to carry out, a plastic coating made of thermoplastics such as. B. polyamides, polyesters or polyethylene, for example, on metals or glass.
- a method variant is also known in which the powder coating produced is smoothed by melting in a second furnace.
- polyamides 11 and 12 which have been used for many years, have proven to be tried and tested plastics for whirl sintering. The use of these polyamides is known, for. B. for powder coating of insert baskets in dishwashers because of the high resistance to cleaning agents, acids and alkalis.
- Polyamide coatings can be colored by adding pigments.
- the way in which the pigments are added to the polyamide is based solely on the powder production process.
- Z. B. the extrusion into the polyamide granules with subsequent grinding, the addition during a precipitation process or the mixing of the unpigmented polyamide powder with the pigments in the dry blend process. It is also possible to combine the processes with one another, for example to add some of the pigments before precipitation or extrusion, and to adjust the final color by adding further pigments.
- Conventional polyamide coating powders suitable processes for their production and suitable pigmentation processes are e.g. B. from DE-PS 28 55 920 known.
- the step describes, inter alia, both suitable particle size distributions for special coating processes and also suitable additives for pigmenting and for stabilizing the powders in relation to Aging, warmth or light.
- the polyamides 11 and 12 customary in the vortex sintering process are partially crystalline materials, the crystalline portion of which causes that vortex sinter coatings made of polyamide 11 and polyamide 12 are opaque.
- the crystallinity can be reduced by immersing the coatings in water shortly after solidification at temperatures a little below their melting points and thereby cooling them further very quickly. In this case, fewer crystals form because the morphological state is frozen. Coatings cooled in water are also opaque.
- polyamides are degraded by UV light. This can be prevented by suitable stabilizers such as phenolic antioxidants and HALS stabilizers. However, if the stabilized polyamides are mixed with colored pigments, rapid degradation nevertheless occurs, which makes the use of colored polyamides out of the way does not appear to make sense.
- polyamide coatings that are exposed to outdoor weathering show cracks that allow moisture to penetrate to the surface. As a result, they lose their most important function, adequate corrosion protection.
- the stabilizers mentioned above only give the coatings sufficient stability if no pigments or only pigments based on titanium dioxide and / or carbon black have been incorporated. Pigments are particularly troublesome when they are mixed into the finished fluidized bed powders using the dry blend process. A homogeneous distribution of the colored pigments in the polymer matrix also counteracts the protection of the UV stabilizers. This can be demonstrated on coated test panels which are either weathered outdoors or which are subjected to a weather-o-meter test.
- Colored polyamide coatings are therefore generally not used in outdoor areas, despite their other advantageous application properties.
- the object of the present invention is therefore to provide weather-resistant colored polyamide coatings which are also suitable for outdoor use are and at the same time meet the high optical requirements, as they are customary on the market, for. B. be provided by users of everyday objects.
- weather-resistant, colored polyamide powder coatings produced using conventional polyamide powders, according to claim 1, comprising at least one pigmented polyamide layer initially applied to the object to be coated and at least one unpigmented polyamide layer applied with weather stabilizers and Top layer. Double polyamide coatings of a pigmented and an unpigmented layer are preferred according to the invention.
- Polyamide coatings according to the invention can be made by all known methods of powder coating such as. B. by vortex sintering, spraying on hot surfaces or electrostatic coating.
- the vortex sintering method is preferred.
- the workpiece to be coated is preferably first heated in an oven to the usual coating temperature of approx. 250 ° C. to 450 ° C. and then successively for at least 2 to 5 seconds in at least one pigmented and then in at least one unpigmented polyamide mixed with weathering stabilizers -Powder also immersed for about 2 to 5 seconds. Finally, the coating is melted and smoothed in a conventional manner.
- a combination of coating processes for producing the multiple coatings according to the invention is also possible, for. B. by vortex sintering and spraying a second layer.
- Conventional powders of partially crystalline polyamides with melting points of less than or equal to 220 ° C. are preferably suitable for producing the polyamide coatings according to the invention; Polyamide 11, polyamide 12, polyamide 12.12 and / or polyamide 10.12 are particularly preferably used.
- the thickness of the individual layers applied is preferably between 100 and 300 ⁇ m.
- the weather stabilizers used are the stabilizers known from the prior art, that is to say e.g. B. HALS stabilizers, sterically hindered phenols, triazines, Phosphites and the like.
- the layers are preferably applied immediately one after the other without intermediate process steps.
- the layers are preferably applied immediately one after the other without intermediate process steps.
- a double polyamide coating according to the invention has an apparently somewhat darker, but more brilliant color tone than a single coating of the same thickness only with the same colored powder.
- This effect is particularly noticeable when platelet-shaped mica pigments are used for coloring, which give the coating a metallic sheen.
- the color effect increases when the coating is cooled with water.
- This advantageous color effect which leads to an appealing appearance of powder-coated objects, is particularly surprising because unpigmented polyamide layers are opaque and therefore a fading of the color tone due to the at least double coating had to be expected.
- the color effect is achieved regardless of the coating process, so even if e.g. B. only a colored layer is applied in the vortex sintering process and the top layer is applied with a spray gun.
- the polyamide coatings according to the invention are also very weather-stable due to the unpigmented top layer (or top layers), since the protective effect of the stabilizers is not canceled out by the pigments. This applies both in comparison with single coatings, the underlying powders of which were pigmented using the dryblend process and in which a small proportion of the pigments are embedded in the surface of the coating, as well as for the comparison with coatings made from melted polyamide powders, in which the colored pigments are only slightly better protected so that they can still catalyze the degradation of polyamides.
- the powder coatings according to the invention can also be produced inexpensively, since colored coatings which are stable against UV light are obtained in a simple process, starting from unpigmented or so-called stock powders.
- the polyamide coatings according to the invention are moreover - like polyamide coatings in general - abrasion-resistant, impact-resistant, noise-damping, resistant to cleaning agents, acids and alkalis, easy to clean and environmentally friendly in production and disposal. Since the polyamide coatings according to the invention are also weatherproof and visually appealing in their appearance, there are many new possible uses for polyamide coatings in outdoor use (outdoor area).
- a white polylaurine lactam powder is produced by precipitation, which contains the heat stabilizers and titanium dioxide which are customary for fluidized bed sinter powders, as white pigment, by adding the substances mentioned to the polyamide solution before the precipitation.
- the product is colored yellow by adding 1.0 part of Sicotangelb K1011 (manufacturer BASF) and 0.9 part of Cromophthalgelb AGR (manufacturer Ciba Geigy).
- This powder is used to coat sandblasted sheets measuring 50 x 200 x 2 mm in a whirl sintering process.
- the sheets are heated in a convection oven at 380 ° C. for 10 minutes, immersed in the yellow whirling sinter powder for 2 seconds and immediately thereafter in a colorless polyamide 12 whirling sinter powder and cooled in cold water 30 seconds after immersion.
- the second vortex sinter powder contains 0.3% by weight of the commercially available UV stabilizers Tinuvin 234 and Tinuvin 770 (manufacturer Ciba Geigy).
- the coatings were measured photometrically without load and after 1000 hours of exposure in a Weather-O-meter test according to DIN 53387 by determining the Lab values.
- the color difference ⁇ E was 1.6 units for the double-coated and 46.8 units for the single-coated sample.
- a color difference of ⁇ E ⁇ 2 means that the sample has not visually discolored. The weather resistance of the sheets coated according to the invention has thus been demonstrated.
- a commercially available shopping cart with a capacity of 150 l was partially degreased and then coated.
- the upper part and child seat were heated in a 400 ° C convection oven for 4 minutes, then immersed in the swirling yellow pigmented polyamide 12 powder from Example 1 for 3.5 seconds with vigorous movement and immediately afterwards for 2.5 seconds in a second whirl sintered vessel with colorless polyamide 12 -Powder dipped.
- the colorless powder contains the weather stabilizers described. After the part was removed from the second bath, it was allowed to air for 15 seconds to allow the powders to run smoothly. It was then immersed in a water bath at approximately 60 ° C. for 30 seconds.
- the base was coated in the same way, heating the oven to 420 ° C and letting the part stay in the oven for 5 minutes.
- the diving time in the first pool was only 2.5 seconds.
- the coatings were dyed through homogeneously, even at critical crossing points of wires of different thicknesses without pores.
- the thickness of the coating averaged 280 ⁇ m.
- a commercially available park bench consisting of a tubular steel frame, which is filled with a wire mesh, was degreased and sandblasted. It was then heated in a 400 ° C oven for 6 minutes, immersed in a sintering pool with green polyamide 12 powder and colorless polyamide 12 powder for 3 seconds in a row, and heated to approx. 30 ° C 30 seconds after removal from the second pool Water submerged.
- the green powder was obtained by mixing colorless, heat-stabilized polyamide 12 powder with 2 parts Sicopalthough K 9610 (manufacturer BASF), 0.14 part cromophthal yellow AGR (manufacturer Ciba-Geigy) and 0.05 part Bayferrox 130 (manufacturer Bayer).
- the colorless polyamide powder contained 0.2% by weight of Tinuvin 324 and Tinuvin 770 (manufacturer Ciba Geigy).
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Paints Or Removers (AREA)
- Materials For Medical Uses (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
Abstract
Description
Die Erfindung betrifft witterungsstabile, farbige Polyamidbeschichtungen, Verfahren zu ihrer Herstellung und ihre bevorzugte Verwendung.The invention relates to weather-resistant, colored polyamide coatings, processes for their production and their preferred use.
Unter einer Pulverbeschichtung versteht man im allgemeinen die Beschichtung von Oberflächen durch Auftragen und Sintern von schmelzfähigen Pulvern. Verschiedene Verfahren zur Pulverbeschichtung sind bekannt. Unter diesen Verfahren gilt insbesondere das Wirbelsinterverfahren als einfach durchzuführende Methode, einen Kunststoffüberzug aus Thermoplasten wie z. B. Polyamiden, Polyestern oder Polyethylen beispielsweise auf Metalle oder Glas aufzubringen. Bekannt ist hierbei auch eine Verfahrensvariante, bei der die erzeugte Pulverbeschichtung durch Aufschmelzen in einem zweiten Ofen geglättet wird. Als für das Wirbelsintern bewährte Kunststoffe haben sich insbesondere die Polyamide 11 und 12 erwiesen, die seit vielen Jahren eingesetzt werden. Bekannt ist die Verwendung dieser Polyamide z. B. zur Pulverbeschichtung von Einsatzkörben in Geschirrspülmaschinen wegen der hohen Beständigkeit gegen Reinigungsmittel, Säuren und Laugen.A powder coating is generally understood to be the coating of surfaces by applying and sintering meltable powders. Various methods for powder coating are known. Among these processes, the vortex sintering process is considered to be an easy method to carry out, a plastic coating made of thermoplastics such as. B. polyamides, polyesters or polyethylene, for example, on metals or glass. A method variant is also known in which the powder coating produced is smoothed by melting in a second furnace. In particular, polyamides 11 and 12, which have been used for many years, have proven to be tried and tested plastics for whirl sintering. The use of these polyamides is known, for. B. for powder coating of insert baskets in dishwashers because of the high resistance to cleaning agents, acids and alkalis.
Polyamidbeschichtungen können durch Zugabe von Pigmenten eingefärbt werden. Die Art der Zugabe der Pigmente zum Polyamid richtet sich dabei lediglich nach dem Verfahren der Pulverherstellung. Üblich sind z. B. das Extrudieren in das Polyamidgranulat mit anschließender Vermahlung, die Zugabe während eines Fällprozesses oder das Vermischen des unpigmentierten Polyamidpulvers mit den Pigmenten im Dryblend-Verfahren. Es ist auch möglich, die Verfahren miteinander zu kombinieren, beispielsweise einen Teil der Pigmente vor der Fällung oder der Extrusion zuzusetzen und den endgültigen Farbton durch Zugabe weiterer Pigmente einzustellen. Herkömmliche Polyamid-Beschichtungspulver, geeignete Verfahren zu ihrer Herstellung sowie geeignete Pigmentierungsverfahren sind z. B. aus DE-PS 28 55 920 bekannt. Die Schritt beschreibt für herkömmliche Polyamid-Beschichtungspulver u. a. sowohl geeignete Korngrößeverteilungen für spezielle Beschichtungsverfahren als auch geeignete Zusätze zur Pigmentierung sowie zur Stabilisierung der Pulver in bezug auf Alterung, Wärme oder Licht.Polyamide coatings can be colored by adding pigments. The way in which the pigments are added to the polyamide is based solely on the powder production process. Z. B. the extrusion into the polyamide granules with subsequent grinding, the addition during a precipitation process or the mixing of the unpigmented polyamide powder with the pigments in the dry blend process. It is also possible to combine the processes with one another, for example to add some of the pigments before precipitation or extrusion, and to adjust the final color by adding further pigments. Conventional polyamide coating powders, suitable processes for their production and suitable pigmentation processes are e.g. B. from DE-PS 28 55 920 known. For conventional polyamide coating powders, the step describes, inter alia, both suitable particle size distributions for special coating processes and also suitable additives for pigmenting and for stabilizing the powders in relation to Aging, warmth or light.
Die beim Wirbelsinterverfahren gebräuchlichen Polyamide 11 und 12 sind teilkristalline Werkstoffe, deren kristalliner Anteil bewirkt, daß Wirbelsinterbeschichtungen aus Polyamid 11 und Polyamid 12 opak sind. Die Kristallinität kann reduziert werden, indem die Beschichtungen kurz nach dem Erstarren bei Temperaturen wenig unterhalb ihrer Schmelzpunkte in Wasser eingetaucht und dadurch sehr schnell weiter abgekühlt werden. In diesem Fall bilden sich weniger Kristalle, da der morphologische Zustand eingefroren wird. Aber auch in Wasser abgekühlte Beschichtungen sind opak.The polyamides 11 and 12 customary in the vortex sintering process are partially crystalline materials, the crystalline portion of which causes that vortex sinter coatings made of polyamide 11 and polyamide 12 are opaque. The crystallinity can be reduced by immersing the coatings in water shortly after solidification at temperatures a little below their melting points and thereby cooling them further very quickly. In this case, fewer crystals form because the morphological state is frozen. Coatings cooled in water are also opaque.
Polyamide werden bekanntermaßen durch UV-Licht abgebaut. Dies kann durch geeignete Stabilisatoren wie phenolische Antioxidantien und HALS-Stabilisatoren bedingt verhindert werden. Werden die stabilisierten Polyamide aber mit Buntpigmenten versetzt, tritt trotzdem ein rascher Abbau ein, der den Außeneinsatz von eingefärbten Polyamiden als nicht sinnvoll erscheinen läßt.It is known that polyamides are degraded by UV light. This can be prevented by suitable stabilizers such as phenolic antioxidants and HALS stabilizers. However, if the stabilized polyamides are mixed with colored pigments, rapid degradation nevertheless occurs, which makes the use of colored polyamides out of the way does not appear to make sense.
Polyamidbeschichtungen, die der Freibewitterung ausgesetzt werden, weisen nach einiger Zeit Risse auf, durch die Feuchtigkeit bis zum Untergrund vordringen kann. Damit verlieren sie ihre wichtigste Funktion, den ausreichenden Korrosionsschutz. Die oben erwähnten Stabilisatoren verleihen den Beschichtungen nur dann eine ausreichende Stabilität, wenn keine Pigmente oder nur Pigmente auf Basis Titandioxid und/oder Ruß eingearbeitet sind. Pigmente sind besonders störend, wenn sie nach dem Dryblend-Verfahren den fertigen Wirbelsinterpulvern zugemischt werden. Aber auch eine homogene Verteilung der Buntpigmente in der Polymermatrix wirkt dem Schutz der UV-Stabilisatoren entgegen. Dies läßt sich an beschichteten Testblechen, die entweder im Freien bewittert oder die einem Weather-O-meter-Test unterworfen werden, demonstrieren.After some time, polyamide coatings that are exposed to outdoor weathering show cracks that allow moisture to penetrate to the surface. As a result, they lose their most important function, adequate corrosion protection. The stabilizers mentioned above only give the coatings sufficient stability if no pigments or only pigments based on titanium dioxide and / or carbon black have been incorporated. Pigments are particularly troublesome when they are mixed into the finished fluidized bed powders using the dry blend process. A homogeneous distribution of the colored pigments in the polymer matrix also counteracts the protection of the UV stabilizers. This can be demonstrated on coated test panels which are either weathered outdoors or which are subjected to a weather-o-meter test.
Farbige Polyamidbeschichtungen werden daher in Außenbereichen in der Regel trotz ihrer sonstigen vorteilhaften anwendungstechnischen Eigenschaften nicht eingesetzt.Colored polyamide coatings are therefore generally not used in outdoor areas, despite their other advantageous application properties.
Aufgabe der vorliegenden Erfindung ist es daher, witterungsbeständige farbige Polyamidbeschichtungen bereitzustellen, die auch für den Einsatz im Freien geeignet sind und die zugleich den hohen optischen Anforderungen gerecht werden, wie sie marktüblich z. B. von Benutzern von Gebrauchsgegenständen gestellt werden.The object of the present invention is therefore to provide weather-resistant colored polyamide coatings which are also suitable for outdoor use are and at the same time meet the high optical requirements, as they are customary on the market, for. B. be provided by users of everyday objects.
Diese Aufgabe wird erfindungsgemäß gelöst durch witterungsbeständige, farbige Polyamid-Pulverbeschichtungen, hergestellt unter Verwendung von herkömmlichen Polyamidpulvern, gemäß Patentanspruch 1 aus zumindest einer zunächst auf den zu beschichtenden Gegenstand aufgetragenen, pigmentierten Polyamid-Schicht und zumindest einer darüber aufgebrachten unpigmentierten, mit Witterungsstabilisatoren versetzten Polyamid-Deckschicht. Bevorzugt sind erfindungsgemäße zweifache Polyamidbeschichtungen aus einer pigmentierten und einer unpigmentierten Schicht.This object is achieved according to the invention by weather-resistant, colored polyamide powder coatings, produced using conventional polyamide powders, according to claim 1, comprising at least one pigmented polyamide layer initially applied to the object to be coated and at least one unpigmented polyamide layer applied with weather stabilizers and Top layer. Double polyamide coatings of a pigmented and an unpigmented layer are preferred according to the invention.
Erfindungsgemäße Polyamidbeschichtungen können nach allen bekannten Verfahren der Pulverbeschichtung wie z. B. durch Wirbelsintern, Sprühen auf heiße Oberflächen oder Elektrostatikbeschichtung hergestellt werden. Bevorzugt wird jedoch das Wirbelsinterverfahren. Dabei wird das zu beschichtende Werkstück vorzugsweise zunächst in einem Ofen auf die übliche Beschichtungstemperatur von ca. 250 °C bis 450 °C erwärmt und anschließend nacheinander zunächst etwa 2 bis 5 Sekunden in zumindest ein pigmentiertes und danach in zumindest ein unpigmentiertes, mit Witterungsstabilisatoren versetztes Polyamid-Pulver für ebenfalls etwa 2 bis 5 Sekunden eingetaucht. Abschließend erfolgt das Aufschmelzen und Glätten der Beschichtung in herkömmlicher Weise. Auch eine Kombination von Beschichtungsverfahren zur Herstellung der erfindungsgemäßen Mehrfachbeschichtungen ist möglich, z. B. durch Wirbelsintern und Aufsprühen einer zweiten Schicht.Polyamide coatings according to the invention can be made by all known methods of powder coating such as. B. by vortex sintering, spraying on hot surfaces or electrostatic coating. However, the vortex sintering method is preferred. The workpiece to be coated is preferably first heated in an oven to the usual coating temperature of approx. 250 ° C. to 450 ° C. and then successively for at least 2 to 5 seconds in at least one pigmented and then in at least one unpigmented polyamide mixed with weathering stabilizers -Powder also immersed for about 2 to 5 seconds. Finally, the coating is melted and smoothed in a conventional manner. A combination of coating processes for producing the multiple coatings according to the invention is also possible, for. B. by vortex sintering and spraying a second layer.
Zur Herstellung der erfindungsgemäßen Polyamidbeschichtungen sind bevorzugt herkömmliche, dem Fachmann geläufige Pulver aus teilkristallinen Polyamiden mit Schmelzpunkten von kleiner oder gleich 220 °C (gemessen nach der Differentialthermoanalyse [DSC]) geeignet; besonders bevorzugt werden Polyamid 11, Polyamid 12, Polyamid 12.12 und/oder Polyamid 10.12 eingesetzt. Die Dicke der einzelnen aufgetragenen Schichten beträgt vorzugsweise zwischen 100 und 300 µm. Als Witterungsstabilisatoren dienen die aus dem Stand der Technik bekannten Stabilisatoren, also z. B. HALS-Stabilisatoren, sterisch gehinderte Phenole, Triazine, Phosphite und dergleichen.Conventional powders of partially crystalline polyamides with melting points of less than or equal to 220 ° C. (measured according to differential thermal analysis [DSC]) are preferably suitable for producing the polyamide coatings according to the invention; Polyamide 11, polyamide 12, polyamide 12.12 and / or polyamide 10.12 are particularly preferably used. The thickness of the individual layers applied is preferably between 100 and 300 μm. The weather stabilizers used are the stabilizers known from the prior art, that is to say e.g. B. HALS stabilizers, sterically hindered phenols, triazines, Phosphites and the like.
Unabhängig vom Beschichtungsverfahren erfolgt der Auftrag der Schichten vorzugsweise unmittelbar nacheinander ohne zwischengelagerte Verfahrensschritte. Zur Verbesserung des Haftverbundes zwischen den Schichten kann es aber - insbesondere bei Werkstücken mit sehr unterschiedlichen Geometrien und infolgedessen sehr unterschiedlichen Wärmekapazitäten - vorteilhaft und/oder zur Erzielung des erfindungsgemäßen Effektes notwendig sein, nach dem Aufbringen der zweiten bzw. nächsten Schicht deren Aufschmelzen in einem Ofen zu unterstützen.Regardless of the coating process, the layers are preferably applied immediately one after the other without intermediate process steps. In order to improve the adhesive bond between the layers, however - especially in the case of workpieces with very different geometries and, consequently, very different heat capacities - it may be advantageous and / or to achieve the effect according to the invention, after the second or next layer has been applied, its melting in an oven to support.
Überraschenderweise besitzt beispielsweise eine erfindungsgemäße zweifache Polyamidbeschichtung einen zwar scheinbar etwas dunkleren, aber brillanteren Farbton als eine Einfachbeschichtung gleicher Dicke nur mit dem gleichen farbigen Pulver. Dieser Effekt ist besonders auffällig, wenn zur Einfärbung plättchenförmige Glimmerpigmente verwendet werden, die der Beschichtung einen metallischen Glanz verleihen. Der Farbeffekt tritt verstärkt auf wenn die Beschichtung mit Wasser abgekühlt wird. Dieser vorteilhafte Farbeffekt, der zu einem ansprechenden Aussehen pulverbeschichteter Gegenstände führt, ist insbesondere deshalb überraschend, weil unpigmentierte Polyamidschichten opak sind und deshalb eher mit einem Verblassen des Farbtons durch die zumindest doppelte Beschichtung gerechnet werden mußte. Der Farbeffekt wird unabhängig vom Beschichtungsverfahren erzielt, also auch, wenn z. B. nur eine farbige Schicht im Wirbelsinterverfahren aufgebracht und die Deckschicht mit einer Sprühpistole aufgebracht wird.Surprisingly, for example, a double polyamide coating according to the invention has an apparently somewhat darker, but more brilliant color tone than a single coating of the same thickness only with the same colored powder. This effect is particularly noticeable when platelet-shaped mica pigments are used for coloring, which give the coating a metallic sheen. The color effect increases when the coating is cooled with water. This advantageous color effect, which leads to an appealing appearance of powder-coated objects, is particularly surprising because unpigmented polyamide layers are opaque and therefore a fading of the color tone due to the at least double coating had to be expected. The color effect is achieved regardless of the coating process, so even if e.g. B. only a colored layer is applied in the vortex sintering process and the top layer is applied with a spray gun.
Die erfindungsgemäßen Polyamidbeschichtungen sind aufgrund der unpigmentierten Deckschicht (oder Deckschichten) außerdem sehr witterungsstabil, da die schützende Wirkung der Stabilisatoren nicht durch die Pigmente wieder aufgehoben wird. Dies gilt sowohl im Vergleich mit Einfachbeschichtungen, deren zugrunde liegende Pulver im Dryblend-Verfahren pigmentiert wurden und in denen ein geringer Teil der Pigmente in die Oberfläche der Beschichtung eingebettet ist, als auch für den Vergleich mit Beschichtungen aus in der Schmelze pigmentierten Polyamidpulvern, in denen die Buntpigmente nur geringfügig besser geschützt sind, so daß sie dennoch den Polyamidabbau katalysieren können.The polyamide coatings according to the invention are also very weather-stable due to the unpigmented top layer (or top layers), since the protective effect of the stabilizers is not canceled out by the pigments. This applies both in comparison with single coatings, the underlying powders of which were pigmented using the dryblend process and in which a small proportion of the pigments are embedded in the surface of the coating, as well as for the comparison with coatings made from melted polyamide powders, in which the colored pigments are only slightly better protected so that they can still catalyze the degradation of polyamides.
Die erfindungsgemäßen Pulverbeschichtungen sind ferner kostengünstig hergestellbar, da ausgehend von unpigmentierten oder nur mit Titandioxid versetzten sogenannten Stammpulvern in einem einfachen Verfahren gegen UV-Licht stabile farbige Beschichtungen erhalten werden.The powder coatings according to the invention can also be produced inexpensively, since colored coatings which are stable against UV light are obtained in a simple process, starting from unpigmented or so-called stock powders.
Die erfindungsgemäßen Polyamidbeschichtungen sind darüber hinaus - wie Polyamidbeschichtungen im allgemeinen - abriebfest, schlagfest, geräuschdämpfend, beständig gegen Reinigungsmittel, Säuren und Laugen, leicht zu reinigen und umweltfreundlich in Herstellung und Entsorgung. Da die erfindungsgemäßen Polyamidbeschichtungen auch witterungsbeständig und optisch ansprechend in ihrem Aussehen sind, ergeben sich vielfältige neue Einsatzmöglichkeiten für Polyamidbeschichtungen im Außeneinsatz (Freiluftbereich).The polyamide coatings according to the invention are moreover - like polyamide coatings in general - abrasion-resistant, impact-resistant, noise-damping, resistant to cleaning agents, acids and alkalis, easy to clean and environmentally friendly in production and disposal. Since the polyamide coatings according to the invention are also weatherproof and visually appealing in their appearance, there are many new possible uses for polyamide coatings in outdoor use (outdoor area).
So ist z. B. die Verwendung von erfindungsgemäßen Polyamidbeschichtungen aus dem Polyamid VESTOSINT (Hüls AG) bei Einkaufswagen oder -körben möglich und bietet hier eine Vielzahl von Vorteilen. Einkaufswagen sind bekanntlich sowohl hohen mechanischen Belastungen als auch der Freibewitterung ausgesetzt. Zusammen mit dem oben genannten vorteilhaften anwendungstechnischen Eigenschaften von Polyamidbeschichtungen ermöglicht die erfindungsgemäße Beschichtungsweise mit z. B. VESTOSINT eine Herstellung robuster, witterungsbeständiger, farbiger Einkaufswagen aus herkömmlichen Baustählen auf im Vergleich zu herkömmlichen, galvanisch verzinkten und einbrennlackierten Einkaufswagen umweltschonendere Weise bei annähernd gleichem Preis. Die Polyamidbeschichtung hat dabei auch vorteilhaften Einfluß auf die Konstruktion von Einkaufswagen, da dauerhafte Kantenbeschichtungen möglich sind, die z. B. Aufsatzschweißungen der Drähte ohne zusätzlichen Deckrahmen erlauben.. Aufgrund der optischen und anwendungstechnischen Eigenschaften ist ferner mit einer hohen Akzeptanz des Nutzers zu rechnen. Auch eine Einfärbung der Einkaufswagen in den Firmenfarben z. B. der Supermarktkette ist möglich.So z. B. the use of polyamide coatings according to the invention from the polyamide VESTOSINT (Hüls AG) in shopping carts or baskets is possible and offers a multitude of advantages here. Shopping carts are known to be exposed to both high mechanical loads and exposure to the weather. Together with the above-mentioned advantageous application properties of polyamide coatings, the coating method according to the invention with z. B. VESTOSINT is a production of robust, weather-resistant, colored shopping trolleys made of conventional structural steels in a more environmentally friendly manner compared to conventional, galvanized and stove-enamelled shopping trolleys at approximately the same price. The polyamide coating also has an advantageous influence on the construction of shopping trolleys, since permanent edge coatings are possible which, for. B. allow welding of the wires without an additional cover frame. Due to the optical and technical properties, a high level of user acceptance can also be expected. Also a coloring of the shopping trolley in the company colors e.g. B. the supermarket chain is possible.
Weitere Anwendungsmöglichkeiten für die erfindungsgemäßen Beschichtungen bieten z. B. Gartenmöbel, Geräte für Kinderspielplätze oder Verkehrseinrichtungen wie Straßenpfosten u. ä.. Erfindungsgemäß beschichtete Artikel zeichnen sich durch eine hohe Lebensdauer aus.Further applications for the coatings according to the invention offer z. B. garden furniture, devices for children's playgrounds or traffic facilities such as street posts and. Ä .. Articles coated according to the invention are characterized by a long service life.
Der Erfindungsgegenstand wird durch die nachfolgenden Beispiele näher erläutert, ohne jedoch darauf beschränkt zu sein:The subject matter of the invention is explained in more detail by the following examples, but without being limited thereto:
Durch Fällung wird ein weißes Polylaurinlactampulver hergestellt, das die für Wirbelsinterpulver üblichen Wärmestabilisatoren und Titandioxid als Weißpigment enthält, indem die genannten Stoffe der Polyamidlösung vor der Fällung zugesetzt werden. Das Produkt wird durch Zugabe von 1,0 Teilen Sicotangelb K1011 (Hersteller BASF) und 0,9 Teilen Cromophthalgelb AGR (Hersteller Ciba Geigy) gelb eingefärbt.A white polylaurine lactam powder is produced by precipitation, which contains the heat stabilizers and titanium dioxide which are customary for fluidized bed sinter powders, as white pigment, by adding the substances mentioned to the polyamide solution before the precipitation. The product is colored yellow by adding 1.0 part of Sicotangelb K1011 (manufacturer BASF) and 0.9 part of Cromophthalgelb AGR (manufacturer Ciba Geigy).
Mit diesem Pulver werden gesandstrahlte Bleche der Abmessung 50 x 200 x 2 mm im Wirbelsinterverfahren beschichtet. Dazu werden die Bleche 10 Minuten in einem 380 °C heißen Umluftofen erwärmt, 2 Sekunden in das gelbe Wirbelsinterpulver und unmittelbar danach 2 Sekunden in ein farbloses Polyamid 12-Wirbelsinterpulver getaucht und 30 Sekunden nach dem Tauchen in kaltem Wasser abgekühlt. Das zweite Wirbelsinterpulver enthält jeweils 0,3 Gew.-% der handelsüblichen UV-Stabilisatoren Tinuvin 234 und Tinuvin 770 (Hersteller Ciba Geigy).This powder is used to coat sandblasted sheets measuring 50 x 200 x 2 mm in a whirl sintering process. For this purpose, the sheets are heated in a convection oven at 380 ° C. for 10 minutes, immersed in the yellow whirling sinter powder for 2 seconds and immediately thereafter in a colorless polyamide 12 whirling sinter powder and cooled in cold water 30 seconds after immersion. The second vortex sinter powder contains 0.3% by weight of the commercially available UV stabilizers Tinuvin 234 and Tinuvin 770 (manufacturer Ciba Geigy).
Zum Vergleich wurden Bleche der oben genannten Ausführung wie oben erwärmt, 4 Sekunden in das gleiche farbige Wirbelsinterpulver getaucht und 30 Sekunden später mit kaltem Wasser abgekühlt. In beiden Fällen waren die Beschichtungen etwa 350 µm dick. Die Doppelbeschichtung ließ sich leicht und eindeutig durch eine größere Brillanz von der Einfachbeschichtung unterscheiden.For comparison, sheets of the above-mentioned design were heated as above, immersed in the same colored whirl sinter powder for 4 seconds and cooled with cold water 30 seconds later. In both cases the coatings were about 350 µm thick. The double coating was easily and clearly distinguished from the single coating by its greater brilliance.
Die Beschichtungen wurden ohne Belastung und nach 1000 Stunden Exposition in einem Weather-O-meter-Test nach DIN 53387 durch Bestimmung der Lab-Werte photometrisch vermessen. Der Farbabstand ΔE betrug 1,6 Einheiten für die doppelt beschichtete und 46,8 Einheiten für die einfach beschichtete Probe. Ein Farbabstand von ΔE<2 bedeutet, daß sich die Probe visuell nicht verfärbt hat. Die Witterungsbeständigkeit der erfindungsgemäß beschichteten Bleche ist somit nachgewiesen.The coatings were measured photometrically without load and after 1000 hours of exposure in a Weather-O-meter test according to DIN 53387 by determining the Lab values. The color difference ΔE was 1.6 units for the double-coated and 46.8 units for the single-coated sample. A color difference of ΔE <2 means that the sample has not visually discolored. The weather resistance of the sheets coated according to the invention has thus been demonstrated.
Ein handelsüblicher Einkaufswagen mit 150 l Korbinhalt wurde in Teilen entfettet und anschließend beschichtet. Oberteil und Kindersitz wurden im 400 °C heißen Umluftofen 4 Minuten erwärmt, danach 3,5 Sekunden unter heftiger Bewegung in das wirbelnde gelb pigmentierte Polyamid 12-Pulver aus Beispiel 1 eingetaucht und unmittelbar danach 2,5 Sekunden in ein zweites Wirbelsintergefäß mit farblosem Polyamid 12-Pulver getaucht. Das farblose Pulver enthält die beschriebenen Witterungsstabilisatoren. Nachdem das Teil aus dem zweiten Bad entnommen war, wurde es 15 Sekunden an der Luft gelassen, damit die Pulver zu einer glatten Schicht verlaufen konnten. Anschließend wurde es 30 Sekunden in ein etwa 60 °C warmes Wasserbad getaucht.A commercially available shopping cart with a capacity of 150 l was partially degreased and then coated. The upper part and child seat were heated in a 400 ° C convection oven for 4 minutes, then immersed in the swirling yellow pigmented polyamide 12 powder from Example 1 for 3.5 seconds with vigorous movement and immediately afterwards for 2.5 seconds in a second whirl sintered vessel with colorless polyamide 12 -Powder dipped. The colorless powder contains the weather stabilizers described. After the part was removed from the second bath, it was allowed to air for 15 seconds to allow the powders to run smoothly. It was then immersed in a water bath at approximately 60 ° C. for 30 seconds.
Das Untergestell wurde in der gleichen Weise beschichtet, wobei der Ofen auf 420 °C erhitzt wurde und das Teil 5 Minuten im Ofen verweilte. Die Tauchzeit im ersten Becken betrug hier nur 2,5 Sekunden.The base was coated in the same way, heating the oven to 420 ° C and letting the part stay in the oven for 5 minutes. The diving time in the first pool was only 2.5 seconds.
Die Beschichtungen waren homogen durchgefärbt, auch an kritischen Kreuzungsstellen von Drähten unterschiedlicher Dicke porenfrei. Die Dicke der Beschichtung betrug im Durchschnitt 280 µm.The coatings were dyed through homogeneously, even at critical crossing points of wires of different thicknesses without pores. The thickness of the coating averaged 280 µm.
Eine handelsübliche Parkbank bestehend aus einem Stahlrohrrahmen, der mit einem Drahtgitter ausgefüllt ist, wurde entfettet und gesandstrahlt. Anschließend wurde sie in einem 400 °C heißen Ofen 6 Minuten erwärmt, jeweils 3 Sekunden nacheinander in Wirbelsinterbecken mit grünem Polyamid 12-Pulver und farblosem Polyamid 12-Pulver getaucht und 30 Sekunden nach der Herausnahme aus dem zweiten Becken in ca. 30 °C warmes Wasser getaucht.A commercially available park bench consisting of a tubular steel frame, which is filled with a wire mesh, was degreased and sandblasted. It was then heated in a 400 ° C oven for 6 minutes, immersed in a sintering pool with green polyamide 12 powder and colorless polyamide 12 powder for 3 seconds in a row, and heated to approx. 30 ° C 30 seconds after removal from the second pool Water submerged.
Der grüne Pulver wurde erhalten durch Vermischen von farblosem, wärmestabilisiertem Polyamid 12-Pulver mit 2 Teilen Sicopalgrün K 9610 (Hersteller BASF), 0,14 Teilen Cromophthalgelb AGR (Hersteller Ciba-Geigy) und 0,05 Teilen Bayferrox 130 (Hersteller Bayer). Das farblose Polyamidpulver enthielt neben den Wärmestabilisatoren jeweils 0,2 Gew.-% Tinuvin 324 und Tinuvin 770 (Hersteller Ciba Geigy).The green powder was obtained by mixing colorless, heat-stabilized polyamide 12 powder with 2 parts Sicopalgrün K 9610 (manufacturer BASF), 0.14 part cromophthal yellow AGR (manufacturer Ciba-Geigy) and 0.05 part Bayferrox 130 (manufacturer Bayer). In addition to the heat stabilizers, the colorless polyamide powder contained 0.2% by weight of Tinuvin 324 and Tinuvin 770 (manufacturer Ciba Geigy).
Claims (9)
gekennzeichnet durch
zumindest eine einzige zunächst auf den zu beschichtenden Gegenstand aufgetragene pigmentierte Polyamid-Schicht und zumindest eine einzige darüber aufgebrachte unpigmentierte, mit Witterungsstabilisatoren versetzte Polyamid-Deckschicht.Weatherproof, colored polyamide powder coating, made using conventional polyamide powders,
marked by
at least one pigmented polyamide layer initially applied to the object to be coated and at least one single unpigmented polyamide top layer applied with weather stabilizers.
gekennzeichnet durch
eine einzige zunächst auf den zu beschichtenden Gegenstand aufgetragene pigmentierte Polyamid-Schicht und eine einzige darüber aufgebrachte unpigmentierte, mit Witterungsstabilisatoren versetzte Polyamid-Deckschicht.Weatherproof, colored polyamide powder coating according to claim 1,
marked by
a single pigmented polyamide layer initially applied to the article to be coated and a single unpigmented polyamide cover layer applied with weathering stabilizers applied thereover.
dadurch gekennzeichnet,
daß als Polyamide teilkristalline Polyamide mit Schmelzpunkten von kleiner oder gleich 220 °C (gemessen nach der Differentialthermoanalyse) eingesetzt werden.Weatherproof, colored polyamide powder coating according to claim 1 or 2,
characterized,
that partially crystalline polyamides with melting points of less than or equal to 220 ° C. (measured according to differential thermal analysis) are used as polyamides.
dadurch gekennzeichnet,
daß Polyamid 11, Polyamid 12, Polyamid 12.12 und/oder Polyamid 10.12 verwendet werden.Weather-stable, colored polyamide powder coating according to claim 3,
characterized,
that polyamide 11, polyamide 12, polyamide 12.12 and / or polyamide 10.12 are used.
gekennzeichnet durch Wirbelsintern der pigmentierten Schicht oder Schichten.Process for producing weatherproof, colored polyamide powder coatings according to Claims 1 to 4,
characterized by vortex sintering of the pigmented layer or layers.
dadurch gekennzeichnet,
daß die unpigmentierte Deckschicht oder die unpigmentierten Deckschichten durch Wirbelsintern oder Pulversprühen aufgebracht werden.A method according to claim 5 for the production of weather-stable, colored polyamide powder coatings according to claims 1 to 4,
characterized,
that the unpigmented cover layer or the unpigmented cover layers are applied by fluidized bed sintering or powder spraying.
gekennzeichnet durch das Aufschmelzen einer weiteren aufgetragenen Schicht in einem Ofen.Process according to claims 5 or 6 for producing weather-stable, colored polyamide powder coatings according to claims 1 to 4,
characterized by melting another applied layer in an oven.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19603842 | 1996-02-05 | ||
| DE19603842A DE19603842A1 (en) | 1996-02-05 | 1996-02-05 | Weatherproof polyamide powder coatings |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0787536A2 true EP0787536A2 (en) | 1997-08-06 |
| EP0787536A3 EP0787536A3 (en) | 1997-12-03 |
| EP0787536B1 EP0787536B1 (en) | 2001-02-21 |
Family
ID=7784386
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP96110037A Expired - Lifetime EP0787536B1 (en) | 1996-02-05 | 1996-06-21 | Weather resistant polyamide powder coating |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP0787536B1 (en) |
| AT (1) | ATE199223T1 (en) |
| DE (2) | DE19603842A1 (en) |
| DK (1) | DK0787536T3 (en) |
| ES (1) | ES2156237T3 (en) |
| GR (1) | GR3035335T3 (en) |
| PT (1) | PT787536E (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1193418A1 (en) * | 2000-09-27 | 2002-04-03 | Tokai Rubber Industries, Ltd. | Vibration damper including polyamide-resin member covered by elastic layer, and method of producing the same |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2302941A1 (en) * | 1973-01-22 | 1974-07-25 | Forsch Pigmente Und Lacke Ev | Powder-coated, corrosion resistant metal articles - having directly bonded coating of crosslinkable resin and outer thermoplastic coating applied in one treatment |
| JPS58196873A (en) * | 1982-05-11 | 1983-11-16 | Seitetsu Kagaku Co Ltd | Multilayer coating method |
| WO1994001500A1 (en) * | 1992-07-14 | 1994-01-20 | Zeneca Limited | Powder coating composition |
-
1996
- 1996-02-05 DE DE19603842A patent/DE19603842A1/en not_active Withdrawn
- 1996-06-21 ES ES96110037T patent/ES2156237T3/en not_active Expired - Lifetime
- 1996-06-21 DK DK96110037T patent/DK0787536T3/en active
- 1996-06-21 PT PT96110037T patent/PT787536E/en unknown
- 1996-06-21 EP EP96110037A patent/EP0787536B1/en not_active Expired - Lifetime
- 1996-06-21 AT AT96110037T patent/ATE199223T1/en not_active IP Right Cessation
- 1996-06-21 DE DE59606465T patent/DE59606465D1/en not_active Expired - Fee Related
-
2001
- 2001-02-22 GR GR20010400281T patent/GR3035335T3/en not_active IP Right Cessation
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2302941A1 (en) * | 1973-01-22 | 1974-07-25 | Forsch Pigmente Und Lacke Ev | Powder-coated, corrosion resistant metal articles - having directly bonded coating of crosslinkable resin and outer thermoplastic coating applied in one treatment |
| JPS58196873A (en) * | 1982-05-11 | 1983-11-16 | Seitetsu Kagaku Co Ltd | Multilayer coating method |
| WO1994001500A1 (en) * | 1992-07-14 | 1994-01-20 | Zeneca Limited | Powder coating composition |
Non-Patent Citations (1)
| Title |
|---|
| PATENT ABSTRACTS OF JAPAN vol. 8, no. 34 (C-210), 1984 & JP 58 196873 A (SEITETSU) * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1193418A1 (en) * | 2000-09-27 | 2002-04-03 | Tokai Rubber Industries, Ltd. | Vibration damper including polyamide-resin member covered by elastic layer, and method of producing the same |
| US6599640B2 (en) | 2000-09-27 | 2003-07-29 | Tokai Rubber Industries, Ltd. | Vibration damper including polyamide-resin member covered by elastic layer, and method of producing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| ES2156237T3 (en) | 2001-06-16 |
| EP0787536B1 (en) | 2001-02-21 |
| DK0787536T3 (en) | 2001-04-02 |
| DE19603842A1 (en) | 1997-08-07 |
| PT787536E (en) | 2001-05-31 |
| GR3035335T3 (en) | 2001-05-31 |
| EP0787536A3 (en) | 1997-12-03 |
| ATE199223T1 (en) | 2001-03-15 |
| DE59606465D1 (en) | 2001-03-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| DE3913014C2 (en) | ||
| EP0803549B1 (en) | Brilliant coloured pigments | |
| EP0045851B1 (en) | Process for preparing micaceous pigments coated with metal oxides, and their use | |
| EP0088269B1 (en) | Coating process using nacreous pigments | |
| DE69821920T2 (en) | POWDER MIXTURE FOR THERMAL DIFFUSION COATING | |
| DE3134587C2 (en) | Plastic or other material coated with a gold-colored film applied in a vacuum | |
| DE60010604T2 (en) | Glossy surface structure and process for its preparation | |
| EP3120939B1 (en) | Coated substrates, and their use and systems for the production of coated substrates | |
| DE3200730C2 (en) | ||
| EP0491170B1 (en) | Molded plastic articles | |
| AT403910B (en) | MIRROR AND METHOD FOR THE PRODUCTION THEREOF | |
| DE2152770C3 (en) | Primer based on an aqueous dispersion of a fluorocarbon polymer resin and its use | |
| DE1621435A1 (en) | Process for the production of a colored surface on a zinc or tin alloy | |
| EP0787536B1 (en) | Weather resistant polyamide powder coating | |
| EP0544867A1 (en) | Platelet-like coated pigments, their production and their use. | |
| DE2817027C2 (en) | Process for the production of transparent coating powders from copolyamides | |
| EP0439111B1 (en) | Opalescent coatings containing foamed metal oxides | |
| DE2609552A1 (en) | METHOD OF ELECTROLYTIC COLORING OF ALUMINUM AND ALUMINUM ALLOYS | |
| DE2855920C3 (en) | Process for the production of powder-form coating compositions for coating metallic objects by the melt-coating process on the basis of polylaurolactam powder | |
| EP2296829B1 (en) | Coated substrate and method for its production | |
| DE2205367A1 (en) | Tarnish-resistant products made of silver | |
| EP3054033B1 (en) | Method for producing coloured surfaces on aluminium and zinc | |
| DE1533306B1 (en) | Process for the production of aluminum sheets similar to type AIMg 1 for the coloring anodic oxidation | |
| DE1769867C3 (en) | Powder coating agent | |
| DE4227023C1 (en) | Colouring anodised coatings on aluminium@ objects - using 1st soln. contg. organic colouring agent and 2nd soln. contg. metal salt in which electrolytic treatment is carried out |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
| AK | Designated contracting states |
Kind code of ref document: A2 Designated state(s): AT BE CH DE DK ES FR GB GR IE IT LI NL PT SE |
|
| PUAL | Search report despatched |
Free format text: ORIGINAL CODE: 0009013 |
|
| AK | Designated contracting states |
Kind code of ref document: A3 Designated state(s): AT BE CH DE DK ES FR GB GR IE IT LI NL PT SE |
|
| RHK1 | Main classification (correction) |
Ipc: B05D 1/22 |
|
| 17P | Request for examination filed |
Effective date: 19971120 |
|
| RAP1 | Party data changed (applicant data changed or rights of an application transferred) |
Owner name: DEGUSSA-HUELS AKTIENGESELLSCHAFT |
|
| GRAG | Despatch of communication of intention to grant |
Free format text: ORIGINAL CODE: EPIDOS AGRA |
|
| GRAG | Despatch of communication of intention to grant |
Free format text: ORIGINAL CODE: EPIDOS AGRA |
|
| GRAH | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOS IGRA |
|
| 17Q | First examination report despatched |
Effective date: 20000420 |
|
| GRAH | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOS IGRA |
|
| GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
| ITF | It: translation for a ep patent filed |
Owner name: SOCIETA' ITALIANA BREVETTI S.P.A. |
|
| AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AT BE CH DE DK ES FR GB GR IE IT LI NL PT SE |
|
| REF | Corresponds to: |
Ref document number: 199223 Country of ref document: AT Date of ref document: 20010315 Kind code of ref document: T |
|
| REG | Reference to a national code |
Ref country code: CH Ref legal event code: NV Representative=s name: SCHMAUDER & PARTNER AG PATENTANWALTSBUERO Ref country code: CH Ref legal event code: EP |
|
| GBT | Gb: translation of ep patent filed (gb section 77(6)(a)/1977) |
Effective date: 20010223 |
|
| REG | Reference to a national code |
Ref country code: IE Ref legal event code: FG4D Free format text: GERMAN |
|
| REF | Corresponds to: |
Ref document number: 59606465 Country of ref document: DE Date of ref document: 20010329 |
|
| REG | Reference to a national code |
Ref country code: DK Ref legal event code: T3 |
|
| RAP2 | Party data changed (patent owner data changed or rights of a patent transferred) |
Owner name: DEGUSSA AG |
|
| REG | Reference to a national code |
Ref country code: PT Ref legal event code: SC4A Free format text: AVAILABILITY OF NATIONAL TRANSLATION Effective date: 20010223 |
|
| ET | Fr: translation filed | ||
| REG | Reference to a national code |
Ref country code: ES Ref legal event code: FG2A Ref document number: 2156237 Country of ref document: ES Kind code of ref document: T3 |
|
| NLT2 | Nl: modifications (of names), taken from the european patent patent bulletin |
Owner name: DEGUSSA AG |
|
| PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
| REG | Reference to a national code |
Ref country code: GB Ref legal event code: IF02 |
|
| 26N | No opposition filed | ||
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: IE Payment date: 20020516 Year of fee payment: 7 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: CH Payment date: 20020517 Year of fee payment: 7 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: PT Payment date: 20020523 Year of fee payment: 7 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DK Payment date: 20020529 Year of fee payment: 7 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: SE Payment date: 20020531 Year of fee payment: 7 Ref country code: NL Payment date: 20020531 Year of fee payment: 7 Ref country code: GR Payment date: 20020531 Year of fee payment: 7 Ref country code: AT Payment date: 20020531 Year of fee payment: 7 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: BE Payment date: 20020612 Year of fee payment: 7 |
|
| REG | Reference to a national code |
Ref country code: GB Ref legal event code: 732E |
|
| BECA | Be: change of holder's address |
Owner name: DEGUSSA A.G.BENNIGSENPLATZ 1, D-40474 DUESSELDORF Effective date: 20021217 |
|
| REG | Reference to a national code |
Ref country code: PT Ref legal event code: PC4A Free format text: DEGUSSA AKTIENGESELLSCHAFT DE Effective date: 20030110 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: AT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20030621 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20030622 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20030623 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20030630 Ref country code: DK Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20030630 Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20030630 Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20030630 |
|
| NLS | Nl: assignments of ep-patents |
Owner name: DEGUSSA AG |
|
| REG | Reference to a national code |
Ref country code: FR Ref legal event code: TP |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20030724 Year of fee payment: 8 Ref country code: DE Payment date: 20030724 Year of fee payment: 8 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20030729 Year of fee payment: 8 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: ES Payment date: 20030730 Year of fee payment: 8 |
|
| BERE | Be: lapsed |
Owner name: *DEGUSSA A.G. Effective date: 20030630 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: PT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20031231 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20040101 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20040107 |
|
| REG | Reference to a national code |
Ref country code: DK Ref legal event code: EBP |
|
| EUG | Se: european patent has lapsed | ||
| REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
| NLV4 | Nl: lapsed or anulled due to non-payment of the annual fee |
Effective date: 20040101 |
|
| REG | Reference to a national code |
Ref country code: PT Ref legal event code: MM4A Free format text: LAPSE DUE TO NON-PAYMENT OF FEES Effective date: 20031231 |
|
| REG | Reference to a national code |
Ref country code: IE Ref legal event code: MM4A |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20040621 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: ES Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20040622 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20050101 |
|
| GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20040621 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20050228 |
|
| REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED. Effective date: 20050621 |
|
| REG | Reference to a national code |
Ref country code: ES Ref legal event code: FD2A Effective date: 20040622 |