EP0674951B1 - Process for coating metallic workpieces or structure with a thermosetting powder and metallic product thus obtained - Google Patents

Process for coating metallic workpieces or structure with a thermosetting powder and metallic product thus obtained Download PDF

Info

Publication number
EP0674951B1
EP0674951B1 EP94400639A EP94400639A EP0674951B1 EP 0674951 B1 EP0674951 B1 EP 0674951B1 EP 94400639 A EP94400639 A EP 94400639A EP 94400639 A EP94400639 A EP 94400639A EP 0674951 B1 EP0674951 B1 EP 0674951B1
Authority
EP
European Patent Office
Prior art keywords
coating
metal
layer
varnish
process according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP94400639A
Other languages
German (de)
French (fr)
Other versions
EP0674951A1 (en
Inventor
Alice Joseph
Alain Le Marchand
Pierre-Noel Rollin
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ateliers Reunis Caddie SA
Original Assignee
Ateliers Reunis SA
Ateliers Reunis Caddie SA
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority to FR9211868A priority Critical patent/FR2696371B1/en
Priority to US08/200,951 priority patent/US6242105B1/en
Application filed by Ateliers Reunis SA, Ateliers Reunis Caddie SA filed Critical Ateliers Reunis SA
Priority to EP94400639A priority patent/EP0674951B1/en
Priority to ES94400639T priority patent/ES2122183T3/en
Priority to AT94400639T priority patent/ATE169249T1/en
Priority to DK94400639T priority patent/DK0674951T3/en
Priority to DE69412233T priority patent/DE69412233T2/en
Priority to ZA942181A priority patent/ZA942181B/en
Priority to IL109176A priority patent/IL109176A/en
Priority to AU59311/94A priority patent/AU679718B2/en
Priority to HU9400978A priority patent/HU213992B/en
Priority to CZ94801A priority patent/CZ285173B6/en
Priority to JP6092964A priority patent/JPH07275797A/en
Priority to CN94104602A priority patent/CN1087664C/en
Publication of EP0674951A1 publication Critical patent/EP0674951A1/en
Application granted granted Critical
Publication of EP0674951B1 publication Critical patent/EP0674951B1/en
Priority to HK98114811A priority patent/HK1013406A1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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
    • B05D7/54—No clear coat specified
    • B05D7/546—No clear coat specified each layer being cured, at least partially, separately
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • 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
    • B05D7/14—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 to metal, e.g. car bodies
    • B05D7/16—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 to metal, e.g. car bodies using synthetic lacquers or varnishes
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • 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
    • B05D2350/00—Pretreatment of the substrate
    • B05D2350/60—Adding a layer before coating
    • B05D2350/65—Adding a layer before coating metal layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2502/00—Acrylic polymers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12375—All metal or with adjacent metals having member which crosses the plane of another member [e.g., T or X cross section, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12535—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.] with additional, spatially distinct nonmetal component
    • Y10T428/12542—More than one such component
    • Y10T428/12549—Adjacent to each other
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12535—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.] with additional, spatially distinct nonmetal component
    • Y10T428/12556—Organic component
    • Y10T428/12569—Synthetic resin
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12771—Transition metal-base component
    • Y10T428/12785—Group IIB metal-base component
    • Y10T428/12792—Zn-base component
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12771—Transition metal-base component
    • Y10T428/12785—Group IIB metal-base component
    • Y10T428/12792—Zn-base component
    • Y10T428/12799—Next to Fe-base component [e.g., galvanized]

Definitions

  • the present invention relates to methods of recovery of metal parts or structures at by means of a powder coating thermosetting, based on polyester or epoxy resin or a mixture of the two, as well as metal products thus coated.
  • Such a coating has in particular for aim of improving the aesthetic appearance of the pieces and ensure their protection against risk of corrosion.
  • the application of the coating as well provided is produced by spraying the powder thermosetting, by means of an electrostatic gun, on the parts to be covered, then passage of the latter in an oven heated to a temperature of about 220 ° C to cure the coating.
  • the coating thus applied has the disadvantage of having insufficient resistance to against shocks as well as abrasion. It is therefore particularly inconvenient when such a coating is provided on objects essentially made up of assembled wires, liable to undergo shock or friction as is the case, for example, for supermarket trolleys, baskets transport, etc ... In addition, this type of coating has insufficient resistance against risk of corrosion from chemicals or even simply atmospheric agents.
  • FR-A-2341374 a method for cover metallic articles, mainly zippers, zinc alloy or aluminum, polymer resin powder (epoxy, polyester or polymethacrylate) which is then heated to form a coherent film.
  • the article metallic can be previously covered with one or several coats of phenol aldehyde primer or polyester.
  • the outer polymer film is intended for facilitate the adhesion of dyes (dye baths).
  • the subject of the present invention is a process for coating metal parts or metallic structures essentially made up of wires assembled, which is designed to significantly improve the adhesion conditions of the coating of the type in question and therefore its impact resistance and resistance to abrasion.
  • this underbend has the advantage, not only to ensure a very strong bond of the coating external with the corresponding metal part, but also to improve considerably the resistance of the external coating to impacts and risk of abrasion.
  • the coating can more easily withstand the risks of cracking, breaking or peeling existing in the case direct application of such a coating to a part metallic.
  • the intermediate layer thus constituted can effectively play its role, it its thickness should be between 5 and 25 microns, if the thickness of the external coating is itself of the order of 50 to 200 microns.
  • the layer should intermediate has a lower hardness than metal zinc plated so that it is a good sufficient bonding agent to avoid the risk of cracking, breaking or peeling of the coating, when the corresponding parts are subject to impact or abrasion.
  • the external coating can be achieved by means of thermosetting powders such as powder marketed under the brand "POLYDROX” by the Company Industrielle de Voisins (69). But this is only a indicative example because it is possible to use many other types of powder composition thermosetting coating, resin-based polyester or epoxy resin, or a mixture of both.

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Paints Or Removers (AREA)
  • Laminated Bodies (AREA)
  • Chemically Coating (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Coating By Spraying Or Casting (AREA)

Abstract

In coating metal units or structures with a heat-hardening powder based on a polyester resin and/or an epoxy resin, which is sprayed on by means of an electrostatic spray gun and then polymerised in an oven, the pieces to be coated are pre-treated by: (a) an electrolytic zinc plating; and (b) application of a coat of varnish, followed by drying, baking or polymerisation of the varnish. This coating acts as a bonding underlayer between the metal and the polyester and/or epoxy resin outer coating. Pref. the varnish is acrylic and is polymerised in an oven. The thickness of the varnish layer is 2-30 (5-15) microns. The varnish is applied by dipping or spraying.

Description

La présente invention concerne les procédés de recouvrement de pièces ou de structures métalliques au moyen d'un revêtement constitué par une poudre thermodurcissable, à base de résine polyester ou époxy ou d'un mélange des deux, ainsi que les produits métalliques ainsi revêtus.The present invention relates to methods of recovery of metal parts or structures at by means of a powder coating thermosetting, based on polyester or epoxy resin or a mixture of the two, as well as metal products thus coated.

L'adjonction d'un tel revêtement a notamment pour but d'améliorer l'aspect esthétique des pièces correspondantes et d'assurer leur protection à l'encontre des risques de corrosion. Dans ce double but, il est courant de prévoir un tel revêtement sur de nombreuses pièces ou structures métalliques, par exemple sur des chariots de supermarchés, des corbeilles de transport, des éléments de rayonnages... L'application du revêtement ainsi prévu est réalisé par projection de la poudre thermodurcissable, au moyen d'un pistolet électrostatique, sur les pièces a recouvrir, puis passage de ces dernières dans un four chauffé a une température de l'ordre de 220° C pour assurer la polymérisation du revêtement.The addition of such a coating has in particular for aim of improving the aesthetic appearance of the pieces and ensure their protection against risk of corrosion. For this dual purpose, it is common to provide such a coating on many metal parts or structures, for example on supermarket trolleys, transport baskets, shelving elements ... The application of the coating as well provided is produced by spraying the powder thermosetting, by means of an electrostatic gun, on the parts to be covered, then passage of the latter in an oven heated to a temperature of about 220 ° C to cure the coating.

Cependant, le revêtement ainsi appliqué a l'inconvénient de présenter une résistance insuffisante à l'encontre des chocs ainsi qu'a l'abrasion. Il s'agit donc là d'un inconvénient particulièrement gênant lorsqu'un tel revêtement est prévu sur des objets essentiellement constitués de fils assemblés, susceptibles de subir des chocs ou des frottements comme cela est le cas, par exemple, pour des chariots de supermarchés, des corbeilles de transport, etc... Par ailleurs, ce type de revêtement présente une résistance insuffisante à l'encontre des risques de corrosion sous l'effet de produits chimiques ou même simplement des agents atmosphériques. However, the coating thus applied has the disadvantage of having insufficient resistance to against shocks as well as abrasion. It is therefore particularly inconvenient when such a coating is provided on objects essentially made up of assembled wires, liable to undergo shock or friction as is the case, for example, for supermarket trolleys, baskets transport, etc ... In addition, this type of coating has insufficient resistance against risk of corrosion from chemicals or even simply atmospheric agents.

Il est connu de FR-A-2182987, pour protéger des intempéries des tôles métalliques galvanisées, de les recouvrir d'un apprêt liquide (sous forme d'une dispersion dans une grande quantité de solvant) appliqué par des rouleaux, qui après séchage du solvant et durcissage du film par chauffage, est lui-même revêtu, toujours a l'aide de rouleaux, d'une résine de polyester à l'état fondu à chaud, qui est ensuite laissée à l'air pour s'oxyder et se transformer en une matière réticulée thermodurcie.It is known from FR-A-2182987, to protect from weathering of galvanized metal sheets, cover with a liquid primer (in the form of a dispersion in a large amount of solvent) applied by rollers, which after drying the solvent and hardening the film by heating, is itself coated, always using rolls, polyester resin in the molten state at hot, which is then left in the air to oxidize and transform into a crosslinked thermoset material.

Il est aussi connu de FR-A-2341374 un procédé pour recouvrir des articles métalliques, principalement des fermetures à glissières, en alliage a base de zinc ou d'aluminium, d'une poudre de résine de polymère (époxy, polyester ou polyméthacrylate) qui est ensuite chauffée pour former un film cohérent. Selon une variante, l'article métallique peut être préalablement recouvert d'une ou plusieurs couches d'apprêt à base d'aldéhyde de phénol ou de polyester. Le film polymère extérieur est destiné à faciliter l'adhésion des colorants (bains de teintures).It is also known from FR-A-2341374 a method for cover metallic articles, mainly zippers, zinc alloy or aluminum, polymer resin powder (epoxy, polyester or polymethacrylate) which is then heated to form a coherent film. According to a variant, the article metallic can be previously covered with one or several coats of phenol aldehyde primer or polyester. The outer polymer film is intended for facilitate the adhesion of dyes (dye baths).

C'est pourquoi, la présente invention a pour objet un procédé de revêtement de pièces métalliques ou de structures métalliques essentiellement constituées de fils assemblés, qui est conçu de façon a améliorer sensiblement les conditions d'adhérence du revêtement du type en cause et par conséquent sa tenue aux chocs et sa résistance à l'abrasion.This is why, the subject of the present invention is a process for coating metal parts or metallic structures essentially made up of wires assembled, which is designed to significantly improve the adhesion conditions of the coating of the type in question and therefore its impact resistance and resistance to abrasion.

A cet effet, le procédé objet de l'invention est un procédé de revêtement de pièces métalliques, ou de structures métalliques essentiellement constituées de fils assemblés, où l'on applique à l'aide d'un pistolet électrostatique, une poudre thermodurcissable, à base d'une résine polyester, d'une résine époxy ou d'un mélange des deux, que l'on polymérise ensuite dans un four, et où l'on, avant la projection de cette poudre, effectue successivement les deux opérations suivantes :

  • a.- un traitement initial de zingage de la pièce ou structure métallique par un procédé électrolytique,
  • b.- application une couche d'un vernis acrylique, suivie d'un séchage, d'une cuisson ou d'une polymérisation de ce revêtement de vernis, ce revêtement intermédiaire étant apte à servir de sous-couche de liaison entre le métal et le revêtement externe à base de résine polyester, de résine époxy, ou d'un mélange des deux.
    • To this end, the process which is the subject of the invention is a process for coating metal parts, or metal structures essentially consisting of assembled wires, where a thermosetting powder is applied using an electrostatic gun, to base of a polyester resin, an epoxy resin or a mixture of both, which is then polymerized in an oven, and where one, before the projection of this powder, successively performs the following two operations:
  • a.- an initial treatment of zinc coating of the metal part or structure by an electrolytic process,
  • b.- application of a layer of an acrylic varnish, followed by drying, curing or polymerization of this varnish coating, this intermediate coating being able to serve as a bonding sublayer between the metal and the external coating based on polyester resin, epoxy resin, or a mixture of the two.

    • Selon des modes de réalisation préférés de l'invention :

    • l'épaisseur du revêtement est comprise entre 2 et 30 micromètres et de préférence entre 5 et 25 micromètres,
    • l'application de la couche d'un vernis acrylique est effectuée au trempé, par trempage des pièces dans un bain dudit vernis,
    • l'application de la couche d'un vernis acrylique est effectuée par pulvérisation,
    • la polymérisation du vernis acrylique est faite dans un four.
    L'invention a également pour objet un produit métallique, notamment assemblé par soudage de filsmétalliques, revêtu par le procédé de revêtement de la présente invention.According to preferred embodiments of the invention:
    • the thickness of the coating is between 2 and 30 micrometers and preferably between 5 and 25 micrometers,
    • the application of the layer of an acrylic varnish is carried out by dipping, by dipping the parts in a bath of said varnish,
    • the application of the layer of an acrylic varnish is carried out by spraying,
    • the acrylic varnish is polymerized in an oven.
    The invention also relates to a metal product, in particular assembled by welding of metallic wires, coated by the coating process of the present invention.

    Cependant, cette sous-coude a pour avantage, non seulement d'assurer une liaison très forte du revêtement externe avec la pièce métallique correspondante, mais également d'améliorer dans des proportions considérables la tenue du revêtement externe à l'égard des chocs et des risques d'abrasion. Ceci est dû notamment au fait que cette couche intermédiaire qui est nettement moins dure que le métal zingué seul, sert en quelque sorte de tampon amortisseur entre le revêtement externe et la pièce métallique porteuse. Ainsi, en cas de choc, le revêtement externe peut plus facilement résister aux risques de fendillage, de cassure ou de pelage existant dans le cas d'une application directe d'un tel revêtement sur une pièce métallique.However, this underbend has the advantage, not only to ensure a very strong bond of the coating external with the corresponding metal part, but also to improve considerably the resistance of the external coating to impacts and risk of abrasion. This is due in particular to the fact that this middle layer which is significantly less hard than the galvanized metal alone, serves as a sort of buffer shock absorber between the external coating and the part metallic carrier. Thus, in the event of an impact, the coating can more easily withstand the risks of cracking, breaking or peeling existing in the case direct application of such a coating to a part metallic.

    D'une façon générale, les avantages des pièces comportant un revêtement réalisé par le procédé selon l'invention portent essentiellement sur les trois points suivants :

  • a.- excellente tenue du revêtement externe à l'égard des chocs et de l'abrasion, pour les raisons indiquées précédemment.
  • b.- très forte liaison du revêtement externe avec les pièces revêtues et ce, du fait de la qualité de la liaison de ce revêtement avec le vernis acrylique intermédiaire qui présente lui-même une très forte liaison avec les pièces métalliques préalablement zinguées.
  • c.- très bonne tenue de l'ensemble à l'encontre des risques de corrosion résultant de produits chimiques ainsi que de l'action des agents atmosphériques.
    • In general, the advantages of parts comprising a coating produced by the method according to the invention relate essentially to the following three points:
  • a.- excellent resistance of the external coating with regard to impact and abrasion, for the reasons indicated above.
  • b.- very strong bond of the external coating with the coated parts and this, due to the quality of the bond of this coating with the intermediate acrylic varnish which itself has a very strong bond with the previously galvanized metal parts.
  • c.- very good performance of the assembly against the risks of corrosion resulting from chemicals as well as the action of atmospheric agents.

    • Ces avantages ont du reste été mis en évidence par des essais comparatifs qui ont été effectués avec trois lots distincts des pièces métalliques comportant respectivement : l'application directe d'un revêtement externe du type en cause, l'application de ce revêtement sur des pièces ayant seulement reçu un traitement préalable de zingage et l'application d'un tel revêtement sur des pièces ayant préalablement subi à la fois un traitement de zingage et leur revêtement au moyen d'un vernis acrylique. En effet, ces essais comparatifs ont démontré que les pièces de ce dernier lot présentent des avantages très nets sur ces différents points par rapport aux pièces des deux autres lots.These advantages have moreover been highlighted by comparative tests that have been carried out with three separate lots of metal parts including respectively: the direct application of a coating external of the type in question, the application of this coating on parts that have only received prior treatment of zinc plating and the application of such a coating on parts having previously undergone both a treatment of zinc plating and coating with an acrylic varnish. Indeed, these comparative tests have shown that the pieces of this last batch have very clear advantages on these different points compared to the pieces of the two other lots.

    Pour la mise en oeuvre du procédé selon l'invention, on effectue successivement les opérations suivantes :

  • 1.- les pièces à recouvrir sont tout d'abord revêtues d'un zingage par procédé électrolytique et ce, après avoir subi les traitements préalables nécessaires tels que décapage, dégraissage, etc...
  • 2. - les pièces zinguées sont pourvues d'un revêtement en vernis acrylique, et ce par trempage dans un bain d'un tel vernis. Puis ces pièces sont transférées dans un four chauffé à une température de l'ordre de 220°C afin d'assurer la polymérisation du vernis acrylique.
  • 3.- les pièces à recouvrir reçoivent ensuite leur revêtement externe par projection de celui-ci au moyen d'un pistolet électrostatique. Ce revêtement externe consiste en une poudre thermodurcissable à base de résine polyester ou résine époxy ou d'un mélange des deux. Enfin, les pièces sont à nouveau transférées dans un four chauffé à une température de l'ordre de 220°C pour assurer la polymérisation de ce revêtement externe.
    • For the implementation of the method according to the invention, the following operations are carried out successively:
  • 1.- the parts to be covered are first coated with zinc plating by electrolytic process and this, after having undergone the necessary preliminary treatments such as pickling, degreasing, etc ...
  • 2. - the galvanized parts are provided with a coating of acrylic varnish, and this by soaking in a bath of such a varnish. Then these parts are transferred to an oven heated to a temperature of about 220 ° C to ensure the polymerization of the acrylic varnish.
  • 3.- the parts to be covered then receive their external coating by projection of it by means of an electrostatic gun. This external coating consists of a thermosetting powder based on polyester resin or epoxy resin or a mixture of the two. Finally, the parts are again transferred to an oven heated to a temperature of the order of 220 ° C. to ensure the polymerization of this external coating.

    • La composition du vernis acrylique utilisé comme couche intermédiaire peut être par exemple la composition suivante :

    BUTANOL
    13,4%
    XYLENE
    35%
    The composition of the acrylic varnish used as an intermediate layer may for example be the following composition:
    BUTANOL
    13.4%
    XYLENE
    35%

    De préférence pour que la couche intermédiaire ainsi constituée puisse jouer efficacement son rôle, il convient que son épaisseur soit comprise entre 5 et 25 microns, si l'épaisseur du revêtement externe est lui-même de l'ordre de 50 à 200 microns.Preferably so that the intermediate layer thus constituted can effectively play its role, it its thickness should be between 5 and 25 microns, if the thickness of the external coating is itself of the order of 50 to 200 microns.

    En tout état de cause, il convient que la couche intermédiaire ait une dureté inférieure à celle du métal zingué afin qu'elle soit un bon agent de liaison suffisante pour éviter des risques de fendillage, de cassure ou de pelage du revêtement, lorsque les pièces correspondantes sont soumises à des chocs ou à une abrasion.In any event, the layer should intermediate has a lower hardness than metal zinc plated so that it is a good sufficient bonding agent to avoid the risk of cracking, breaking or peeling of the coating, when the corresponding parts are subject to impact or abrasion.

    Le revêtement externe peut être réalisé au moyen de poudres thermodurcissables telles que la poudre commercialisée sous la marque "POLYDROX" par la Société Industrielle de Voisins (69). Mais il ne s'agit là que d'un exemple indicatif car il est possible d'utiliser de nombreux autres types de composition de poudres thermodurcissantes de revêtement, à base de résine polyester ou de résine époxy, ou d'un mélange des deux.The external coating can be achieved by means of thermosetting powders such as powder marketed under the brand "POLYDROX" by the Company Industrielle de Voisins (69). But this is only a indicative example because it is possible to use many other types of powder composition thermosetting coating, resin-based polyester or epoxy resin, or a mixture of both.

    Claims (6)

    1. Process for coating metal parts or metal structures essentially formed from joined wires, wherein by means of an electrostatic gun a thermosetting powder based on a polyester resin, an epoxy resin or a mixture of the two, is applied, which is polymerised subsequently in an oven, and wherein the two following operations are performed successively prior to projection of this powder;
      a.- initial galvanising treatment of the metal part or structure using an electrolytic process,
      b.- application of a layer of acrylic lacquer, and after this lacquer coating has been dried, baked or polymerised, this intermediate coating is then suitable to serve as bonding sub-layer between the metal and the external coating based on polyester resin, epoxy resin or a mixture of the two.
    2. Coating process according to Claim 1, characterised in that the acrylic lacquer is polymerised in an oven.
    3. Coating process according to Claim 1 or 2, characterised in that the thickness of the intermediate layer of acrylic lacquer is in the range of between 2 and 30 micrometers, preferably between 5 and 25 micrometers.
    4. Coating process according to one of Claims 1 to 3, characterised in that application of the layer of acrylic lacquer is performed using the immersion technique by dipping the parts into a bath of said lacquer.
    5. Coating process according to one of Claims 1 to 3, characterised in that application of the layer of acrylic lacquer is performed by spraying.
    6. Metal product, especially assembled by welding metal wires, coated by means of a process according to any one of Claims 1 to 5.
    EP94400639A 1992-10-07 1994-03-25 Process for coating metallic workpieces or structure with a thermosetting powder and metallic product thus obtained Expired - Lifetime EP0674951B1 (en)

    Priority Applications (15)

    Application Number Priority Date Filing Date Title
    FR9211868A FR2696371B1 (en) 1992-10-07 1992-10-07 Process for coating metal parts or structures using a thermosetting powder, based on polyester or epoxy resin or a mixture of the two and metal product thus coated.
    US08/200,951 US6242105B1 (en) 1992-10-07 1994-02-23 Process for coating metallic parts and metallic product thus coated
    EP94400639A EP0674951B1 (en) 1992-10-07 1994-03-25 Process for coating metallic workpieces or structure with a thermosetting powder and metallic product thus obtained
    ES94400639T ES2122183T3 (en) 1992-10-07 1994-03-25 PROCEDURE FOR COATING PARTS OR METALLIC STRUCTURES WITH A THERMO-CURE POWDER AND METAL PRODUCT SO OBTAINED.
    AT94400639T ATE169249T1 (en) 1992-10-07 1994-03-25 METHOD FOR COATING ON METAL MATERIALS OR STRUCTURES, A HOME SETTING POWDER AND ITEMS SO PRODUCED
    DK94400639T DK0674951T3 (en) 1992-10-07 1994-03-25 Process for coating metallic articles or structures with a thermosetting powder, and thus obtained metal
    DE69412233T DE69412233T2 (en) 1992-10-07 1994-03-25 Process for coating on metallic materials or structures, a thermosetting powder and objects manufactured in this way
    ZA942181A ZA942181B (en) 1992-10-07 1994-03-28 Process for coating metallic parts and metallic product thus coasted
    IL109176A IL109176A (en) 1992-10-07 1994-03-30 Process for coating metallic parts and metallic product thus coated
    AU59311/94A AU679718B2 (en) 1992-10-07 1994-04-06 Process for coating metallic parts and metallic product thuscoated
    HU9400978A HU213992B (en) 1992-10-07 1994-04-06 Process for coating metallic parts and metallic product thus coated
    CZ94801A CZ285173B6 (en) 1992-10-07 1994-04-06 Process of coating metallic parts and a metallic product coated in such a manner
    JP6092964A JPH07275797A (en) 1992-10-07 1994-04-06 Method of coating metal part and metal article coated by said method
    CN94104602A CN1087664C (en) 1992-10-07 1994-04-07 Process for coating metallic parts and metallic product thus coated
    HK98114811A HK1013406A1 (en) 1992-10-07 1998-12-22 Process for coating metallic workpieces or structure with a thermosetting powder and metallic product thus obtained

    Applications Claiming Priority (9)

    Application Number Priority Date Filing Date Title
    FR9211868A FR2696371B1 (en) 1992-10-07 1992-10-07 Process for coating metal parts or structures using a thermosetting powder, based on polyester or epoxy resin or a mixture of the two and metal product thus coated.
    US08/200,951 US6242105B1 (en) 1992-10-07 1994-02-23 Process for coating metallic parts and metallic product thus coated
    EP94400639A EP0674951B1 (en) 1992-10-07 1994-03-25 Process for coating metallic workpieces or structure with a thermosetting powder and metallic product thus obtained
    ZA942181A ZA942181B (en) 1992-10-07 1994-03-28 Process for coating metallic parts and metallic product thus coasted
    IL109176A IL109176A (en) 1992-10-07 1994-03-30 Process for coating metallic parts and metallic product thus coated
    CZ94801A CZ285173B6 (en) 1992-10-07 1994-04-06 Process of coating metallic parts and a metallic product coated in such a manner
    AU59311/94A AU679718B2 (en) 1992-10-07 1994-04-06 Process for coating metallic parts and metallic product thuscoated
    JP6092964A JPH07275797A (en) 1992-10-07 1994-04-06 Method of coating metal part and metal article coated by said method
    CN94104602A CN1087664C (en) 1992-10-07 1994-04-07 Process for coating metallic parts and metallic product thus coated

    Publications (2)

    Publication Number Publication Date
    EP0674951A1 EP0674951A1 (en) 1995-10-04
    EP0674951B1 true EP0674951B1 (en) 1998-08-05

    Family

    ID=27575638

    Family Applications (1)

    Application Number Title Priority Date Filing Date
    EP94400639A Expired - Lifetime EP0674951B1 (en) 1992-10-07 1994-03-25 Process for coating metallic workpieces or structure with a thermosetting powder and metallic product thus obtained

    Country Status (15)

    Country Link
    US (1) US6242105B1 (en)
    EP (1) EP0674951B1 (en)
    JP (1) JPH07275797A (en)
    CN (1) CN1087664C (en)
    AT (1) ATE169249T1 (en)
    AU (1) AU679718B2 (en)
    CZ (1) CZ285173B6 (en)
    DE (1) DE69412233T2 (en)
    DK (1) DK0674951T3 (en)
    ES (1) ES2122183T3 (en)
    FR (1) FR2696371B1 (en)
    HK (1) HK1013406A1 (en)
    HU (1) HU213992B (en)
    IL (1) IL109176A (en)
    ZA (1) ZA942181B (en)

    Families Citing this family (9)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    FR2696371B1 (en) * 1992-10-07 1994-10-28 Caddie Atel Reunis Process for coating metal parts or structures using a thermosetting powder, based on polyester or epoxy resin or a mixture of the two and metal product thus coated.
    US6174426B1 (en) 1999-08-12 2001-01-16 Usx Corporation Tin-plated steel with adhesion promoter
    JP2001300407A (en) * 2000-04-27 2001-10-30 Dainippon Toryo Co Ltd Method for coating wire material assembly
    DE60122520T2 (en) * 2000-06-28 2007-04-05 N.V. Bekaert S.A. REINFORCED WIPER ELEMENT
    CN1321747C (en) * 2005-09-06 2007-06-20 贵州科盛彩色喷涂有限公司 Outdoor metal surface double coating antiseptic chromatic spray painting method
    CN101108942B (en) * 2007-08-14 2011-02-09 上海造漆厂 Process for producing solvent resistant static electricity spraying propenoic acid stoving enamel
    UA117592C2 (en) * 2013-08-01 2018-08-27 Арселорміттал PAINTED GALVANIZED STEEL SHEET AND METHOD OF MANUFACTURING
    CN105080808A (en) * 2015-07-02 2015-11-25 柳州市亿瑞物资有限责任公司 Coating method for polyurethane paint
    CN110624787A (en) * 2019-09-11 2019-12-31 中山市天青色厨卫科技有限公司 Manufacturing process of environment-friendly anhydrous electroplating base material

    Family Cites Families (9)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    AU476311B2 (en) * 1972-05-01 1976-09-16 Robertson Bauelemente G.M.B.H. Method of making protected galvanized steel sheeting
    US3891471A (en) 1972-05-01 1975-06-24 Robertson Bauelemente Gmbh Method of making protected galvanized steel sheeting
    US4251582A (en) 1974-08-28 1981-02-17 Textron Inc. Dyeable and dyed polymer-coated articles
    US3953644A (en) * 1974-12-20 1976-04-27 Ford Motor Company Powa--method for coating and product
    DE2706167A1 (en) * 1976-02-19 1977-08-25 Textron Inc PAINTABLE OBJECTS COVERED WITH A POLYMER AND PROCESS FOR MANUFACTURING SUCH OBJECTS
    US4401523A (en) * 1980-12-18 1983-08-30 Republic Steel Corporation Apparatus and method for plating metallic strip
    JPS602186B2 (en) * 1980-12-24 1985-01-19 日本鋼管株式会社 Surface treated steel sheet for painting base
    JPS60121293A (en) * 1983-12-03 1985-06-28 Kawasaki Steel Corp Manufacture of zn-fe alloy galvanized steel plate consisting essentially of zn-fe alloy
    FR2696371B1 (en) 1992-10-07 1994-10-28 Caddie Atel Reunis Process for coating metal parts or structures using a thermosetting powder, based on polyester or epoxy resin or a mixture of the two and metal product thus coated.

    Also Published As

    Publication number Publication date
    CN1087664C (en) 2002-07-17
    HK1013406A1 (en) 1999-08-27
    FR2696371B1 (en) 1994-10-28
    AU5931194A (en) 1995-10-26
    HUT70995A (en) 1995-11-28
    CZ80194A3 (en) 1996-01-17
    US6242105B1 (en) 2001-06-05
    HU9400978D0 (en) 1994-06-28
    IL109176A (en) 1998-06-15
    IL109176A0 (en) 1994-06-24
    EP0674951A1 (en) 1995-10-04
    ATE169249T1 (en) 1998-08-15
    DK0674951T3 (en) 1999-05-03
    DE69412233T2 (en) 1999-01-21
    CN1110195A (en) 1995-10-18
    ES2122183T3 (en) 1998-12-16
    CZ285173B6 (en) 1999-06-16
    FR2696371A1 (en) 1994-04-08
    HU213992B (en) 1997-11-28
    AU679718B2 (en) 1997-07-10
    ZA942181B (en) 1995-01-16
    DE69412233D1 (en) 1998-09-10
    JPH07275797A (en) 1995-10-24

    Similar Documents

    Publication Publication Date Title
    EP0674951B1 (en) Process for coating metallic workpieces or structure with a thermosetting powder and metallic product thus obtained
    US6896970B2 (en) Corrosion resistant coating giving polished effect
    FR2708289A1 (en) System for producing shiny aluminium articles
    FR2465794A2 (en) MULTILAYER PLATING TO GIVE FERROUS METAL SUPPORT AN IMPROVED CORROSION RESISTANCE
    CA2871672A1 (en) Method for producing a metal sheet having oiled zn-al-mg coatings, and corresponding metal sheet
    EP1084768B1 (en) Bright Surface structure and a manufacturing method thereof
    CA2871561C (en) Methods for producing a pre-lacquered metal sheet having zn-al-mg coatings, and corresponding metal sheet
    FR2670158A1 (en) Process for decorating substrates of any kind or shape
    EP0774366B1 (en) Process for making decorative objects having the appearance of wrought iron, and products obtained by the said process
    CN101457358A (en) Metallic coating on substrate
    EP0285593B1 (en) Method for increasing the corrosion resistance of a quenched and self-tempered reinforcement bar made of steel
    US20110039116A1 (en) Colored plating structure and method thereof
    EP0042636A2 (en) Surface treatment of surfaces protected by a metallic coating
    FR2655996A1 (en) PROCESS PROTECTION LAYER FOR PREVENTING FRAGILIZATION BY OXYGEN OF TITANIUM CONSTRUCTION PARTS.
    BE1007507A6 (en) Metal parts using a surface coating for metal baths in merger and metal parts for bathroom use as.
    US20230304139A1 (en) Methods for applying decorative metal films on polymeric surfaces
    FI107376B (en) Method for coating metal parts and metal product coated by the method
    BE1013517A3 (en) Galvanizing process for steel plates.
    US5976634A (en) Gold plating process for plastic substrates
    BE849581A (en) PROCESS FOR APPLYING A COATING ON A HOLLOW METAL OBJECT
    JP3263746B2 (en) Iron manhole cover
    BE897788A (en) Zinc:aluminium:iron coating - made esp. by immersing substrate in molten zinc contg. aluminium and then using diffusion treatment
    FR2827615A1 (en) Hot galvanization of steel sheet involves pretreatment with zinc and ammonium chloride to form an interface layer followed by galvanization in a bath of zinc containing aluminum and bismuth
    FR2687693A1 (en) Process for treating the surface of a product made up of a metal substrate comprising a multilayer metal coating and an organic coating and products obtained by this process
    EP0056498A1 (en) Process for coating ferrous metals to improve corrosion resistance, and ferrous metal articles thus obtained

    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: A1

    Designated state(s): AT BE CH DE DK ES GB IT LI LU MC NL PT SE

    17P Request for examination filed

    Effective date: 19951026

    R17P Request for examination filed (corrected)

    Effective date: 19951026

    17Q First examination report despatched

    Effective date: 19961212

    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

    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

    GRAH Despatch of communication of intention to grant a patent

    Free format text: ORIGINAL CODE: EPIDOS IGRA

    RAP1 Party data changed (applicant data changed or rights of an application transferred)

    Owner name: ATELIERS REUNIS CADDIE

    RAP1 Party data changed (applicant data changed or rights of an application transferred)

    Owner name: ATELIERS REUNIS CADDIE

    GRAA (expected) grant

    Free format text: ORIGINAL CODE: 0009210

    AK Designated contracting states

    Kind code of ref document: B1

    Designated state(s): AT BE CH DE DK ES GB IT LI LU MC NL PT SE

    REF Corresponds to:

    Ref document number: 169249

    Country of ref document: AT

    Date of ref document: 19980815

    Kind code of ref document: T

    REG Reference to a national code

    Ref country code: CH

    Ref legal event code: EP

    REF Corresponds to:

    Ref document number: 69412233

    Country of ref document: DE

    Date of ref document: 19980910

    REG Reference to a national code

    Ref country code: CH

    Ref legal event code: NV

    Representative=s name: PATENTANWALTSBUERO JEAN HUNZIKER

    GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)

    Effective date: 19981013

    REG Reference to a national code

    Ref country code: ES

    Ref legal event code: FG2A

    Ref document number: 2122183

    Country of ref document: ES

    Kind code of ref document: T3

    REG Reference to a national code

    Ref country code: PT

    Ref legal event code: SC4A

    Free format text: AVAILABILITY OF NATIONAL TRANSLATION

    Effective date: 19981022

    REG Reference to a national code

    Ref country code: DK

    Ref legal event code: T3

    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

    26N No opposition filed
    REG Reference to a national code

    Ref country code: GB

    Ref legal event code: IF02

    PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

    Ref country code: DK

    Payment date: 20040123

    Year of fee payment: 11

    PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

    Ref country code: BE

    Payment date: 20040209

    Year of fee payment: 11

    PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

    Ref country code: LU

    Payment date: 20040211

    Year of fee payment: 11

    PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

    Ref country code: AT

    Payment date: 20040312

    Year of fee payment: 11

    PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

    Ref country code: MC

    Payment date: 20040323

    Year of fee payment: 11

    PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

    Ref country code: CH

    Payment date: 20040325

    Year of fee payment: 11

    PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

    Ref country code: NL

    Payment date: 20040331

    Year of fee payment: 11

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: LU

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20050325

    Ref country code: AT

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20050325

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: MC

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20050331

    Ref country code: LI

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20050331

    Ref country code: DK

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20050331

    Ref country code: CH

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20050331

    Ref country code: BE

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20050331

    BERE Be: lapsed

    Owner name: ATELIERS REUNIS *CADDIE

    Effective date: 20050331

    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: 20051001

    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: 20051001

    REG Reference to a national code

    Ref country code: DK

    Ref legal event code: EBP

    PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

    Ref country code: PT

    Payment date: 20060222

    Year of fee payment: 13

    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: 20070326

    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: 20070925

    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: 20070925

    EUG Se: european patent has lapsed
    BERE Be: lapsed

    Owner name: ATELIERS REUNIS *CADDIE

    Effective date: 20050331

    PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

    Ref country code: SE

    Payment date: 20060317

    Year of fee payment: 13

    PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

    Ref country code: ES

    Payment date: 20110322

    Year of fee payment: 18

    Ref country code: GB

    Payment date: 20110321

    Year of fee payment: 18

    Ref country code: DE

    Payment date: 20110325

    Year of fee payment: 18

    PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

    Ref country code: IT

    Payment date: 20110329

    Year of fee payment: 18

    GBPC Gb: european patent ceased through non-payment of renewal fee

    Effective date: 20120325

    REG Reference to a national code

    Ref country code: DE

    Ref legal event code: R119

    Ref document number: 69412233

    Country of ref document: DE

    Effective date: 20121002

    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: 20120325

    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

    Effective date: 20120325

    REG Reference to a national code

    Ref country code: ES

    Ref legal event code: FD2A

    Effective date: 20130710

    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: 20120326

    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: 20121002