EP0700452B1 - Traitement de revetement par conversion sans chrome pour l'aluminium - Google Patents

Traitement de revetement par conversion sans chrome pour l'aluminium Download PDF

Info

Publication number
EP0700452B1
EP0700452B1 EP94916970A EP94916970A EP0700452B1 EP 0700452 B1 EP0700452 B1 EP 0700452B1 EP 94916970 A EP94916970 A EP 94916970A EP 94916970 A EP94916970 A EP 94916970A EP 0700452 B1 EP0700452 B1 EP 0700452B1
Authority
EP
European Patent Office
Prior art keywords
aluminium
treatment
aluminum
concentrations
pretreatment
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
EP94916970A
Other languages
German (de)
English (en)
Other versions
EP0700452A1 (fr
Inventor
Uwe Karmaschek
Achim Roland
Hubert Vennschott
Harald Wennemann
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.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
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
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP0700452A1 publication Critical patent/EP0700452A1/fr
Application granted granted Critical
Publication of EP0700452B1 publication Critical patent/EP0700452B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • 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
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/78—Pretreatment of the material to be coated
    • C23C22/80—Pretreatment of the material to be coated with solutions containing titanium or zirconium compounds
    • 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
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
    • 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
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/73—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals characterised by the process
    • 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
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/73—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals characterised by the process
    • C23C22/76—Applying the liquid by spraying
    • 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
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/78—Pretreatment of the material to be coated

Definitions

  • the invention is in the field of chemical surface treatment of aluminum for the purpose of corrosion protection, the so-called passivation. It describes chrome-free treatment processes for aluminum strips and molded aluminum parts to achieve temporary corrosion protection while maintaining weldability and bondability as well as the suitability of the material for a further conversion step, for example phosphating, chromating or chrome-free conversion treatment.
  • aluminum means not only pure aluminum but also alloys whose main component is aluminum.
  • frequently used alloy elements are silicon, magnesium, copper, manganese, chromium and nickel, the total weight fraction of these alloy elements in the alloy usually not exceeding 10%.
  • Aluminum is increasingly used in vehicle construction for a variety of reasons, such as weight, rigidity or recyclability. While engine and transmission parts, wheels, seat frames etc. are already largely made of aluminum, use in body construction is currently limited to parts such as the radiator hood, trunk lid, interior door parts and various small parts, as well as truck cabins, side walls of vans or bodies of caravans . Overall, less than 5% of the metal surface of automobile bodies is made of aluminum worldwide. The increased use of aluminum in this area is being intensively examined by the aluminum and automotive industries.
  • the material is pickled in order to remove the oxide layers formed during transport and storage and to reduce and even out the electrical surface resistance to the low values required for welding.
  • This pickling for which acidic or alkaline aqueous solutions are used, has hitherto mainly occurred in parts plants at short notice before the welding process. The close coordination of time is intended to suppress the build-up of disruptive layers of corrosion and dirt.
  • the aluminum is chemically pretreated in coil systems (coil systems), possibly with subsequent protective coating, currently only for parts that are no longer to be welded.
  • the aluminum parts are often ground after forming to improve the fit.
  • Toxic and carcinogenic chromium (VI) -containing compounds can occur in the grinding dust. Therefore, increased requirements must be placed on measures to maintain occupational safety on site.
  • the aluminum parts pretreated with chromate are joined together with parts made of steel and / or galvanized steel to form a so-called multi-metal body and are passed through the body pre-treatment system.
  • Soluble ones can be used in the usual alkaline cleaning step Chromium (VI) compounds are removed from the layer. On the one hand, this reduces the corrosion protection function of the layer and, on the other hand, the chromate-containing cleaning solution must be subjected to a special detoxification step during disposal.
  • DE-C-19 33 013 discloses treatment baths with a pH above 3.5 which, in addition to complex fluorides of boron, titanium or zirconium, in amounts of 0.1 to 15 g / l, based on the metals, additionally 0.5 up to 30 g / l of oxidizing agents, especially sodium metanitrobenzenesulfonate.
  • DE-C-24 33 704 describes treatment baths for increasing paint adhesion and permanent corrosion protection on, inter alia, aluminum, the 0.1 to 5 g / l polyacrylic acid or its salts or esters and 0.1 to 3.5 g / l ammonium fluorozirconate, calculated as ZrO 2 .
  • the pH values of these baths can fluctuate over a wide range. The best results are generally obtained when the pH is 6-8.
  • a molar ratio between the fluoric acid and phosphate of about 2.5: 1 to about 1:10 must be observed.
  • DE-A-27 15 292 discloses treatment baths for the chromium-free pretreatment of aluminum cans which contain at least 10 ppm titanium and / or zirconium, between 10 and 1000 ppm phosphate and a sufficient amount of fluoride to form complex fluorides of the titanium and / or zirconium present however, contain 13 ppm and have pH values between 1.5 and 4.
  • WO 92/07973 teaches a chromium- free treatment process for aluminum, the essential components in acidic aqueous solution being 0.01 to about 18% by weight of H 2 ZrF 6 and 0.01 to about 10% by weight of one 3- (NC 1-4 alkyl-N-2-hydroxyethylaminomethyl) -4-hydroxystyrene polymer used.
  • Optional components are 0.05-10% by weight of dispersed SiO 2 , 0.06-0.6% by weight of a solubilizer for the polymer and surfactant.
  • the polymer mentioned falls under the group of the "reaction products of poly (vinylphenol) with aldehydes and organic hydroxyl group-containing amines" which can be used in the context of the present invention.
  • DE-C-12 85 830 describes a process for the pretreatment of a surface of aluminum and its alloys before the application of chemically bound coatings by pickling in an aqueous acidic solution, characterized in that the surface with a cleaning solution which has a pH has from 1.8 to 3.2 and phosphate ions, fluoride ions and ions of one or more of the metals zinc, manganese, iron, sodium, potassium and ammonium are brought into contact.
  • the invention is based on the object not previously made in the art of providing a chromium-free process for the pretreatment of surfaces made of aluminum or its alloys, in which the surfaces are provided with a temporary corrosion protection by a first chemical pretreatment process, then a non-cutting and / or cutting Subjected to the forming process and / or to one another or to parts made of steel and / or galvanized and / or alloy-galvanized steel by gluing and / or welding and in a subsequent second chemical treatment step being provided with a permanently corrosion-protective coating.
  • Conversion methods to achieve permanent corrosion protection include, in particular, phosphating with acidic zinc-containing phosphating baths, chromating or chromium-free conversion treatment in accordance with the literature mentioned above, for example with reactive organic polymers and / or with compounds, in particular fluorocomplexes, the elements titanium, zirconium and / or hafnium into consideration.
  • the pretreatment according to the task must ensure temporary protection against corrosion for a longer storage period, for example two to three months, without the material being bondable or weldable being adversely affected, for example by electrical resistance welding.
  • the electrical surface resistance is as uniform as possible, does not exceed a value of approximately 400 mOhm and is preferably below approximately 100 mOhm. After alkaline pickling and subsequent storage for 4 weeks, on the other hand, sprinkle the electrical surface resistances locally very strong and cover a range of 100 to 1500 ⁇ Ohm.
  • the surface resistance is measured in accordance with the DVS 2929 data sheet in the form of a single sheet measurement with iron electrodes with a diameter of 20 mm.
  • a multi-metal body is a body that is made from at least two of the materials: aluminum, steel, galvanized, alloy-galvanized, aluminized or alloy-aluminized steel.
  • Suitable multimetal phosphating processes are known to the person skilled in the field of conversion treatment, for example from DE-A-39 18 136 and EP-A-106 459 , and do not constitute an object of this invention.
  • Conversion treatments in question which must not be hindered by the first conversion step according to the invention. Examples include chromating with treatment baths containing Cr (VI) and / or Cr (III) or the above-mentioned chromium-free conversion processes.
  • a thin conversion coating which consists of (mixed) oxides, (mixed) fluorides and / or oxyfluorides of aluminum and at least one of the elements boron, silicon, titanium, zirconium or hafnium and which includes organic polymers of the polyacrylate type Acrylate-containing copolymers or reaction products of poly (vinylphenol) with aldehydes and organic hydroxyl-containing amines can be modified.
  • the feature "thin” should be understood to mean that the concentration of the layer-forming elements boron, silicon, titanium, zirconium and / or hafnium on the aluminum surface together in the range 1-80 mg / m 2 , in particular is in the range 2 - 20 mg / m 2 .
  • the polymer content of the conversion coating must not exceed 5 mg / m 2 and should preferably be in the range 0 to 3 mg / m 2 .
  • the invention accordingly describes a Process for the pretreatment of surfaces made of aluminum or its alloys before a second, permanently corrosion-protective conversion treatment, preferably chromating, a chromium-free conversion treatment with reactive organic polymers and / or with compounds of the elements titanium, zirconium and / or hafnium, or phosphating with acidic zinc-containing Phosphating baths, characterized in that the surfaces are brought into contact with acidic aqueous treatment solutions, the complex fluorides of the elements boron, silicon, titanium, zirconium or hafnium individually or in a mixture with one another in concentrations of the fluoro anions of in total between 100 and 4000, preferably Contain 200 to 2000 mg / l and have a pH between 0.3 and 3.5, preferably between 1 and 3, and that between the pretreatment of the surfaces made of aluminum or its alloys and the permanent anti-corrosion conversion treatment Aluminum or its alloys are subjected to a non-cutting and / or metal-forming process and / or are connected
  • the treatment solutions can additionally contain polymers of the type of the polyacrylates and / or the reaction products of poly (vinylphenol) with aldehydes and organic hydroxyl-containing amines in concentrations below 500 mg / l, preferably below 200 mg / l. If the treatment solution contains Zr, the concentration of the reaction products of poly (vinylphenol) with aldehydes and organic hydroxyl-containing amines should be less than 100 mg / l.
  • the complex fluorides of the elements boron, silicon, titanium, zircon or hafnium, ie the anions BF 4 - , SiF 6 2- , TiF 6 2- , ZrF 6 2- or HfF 6 2- can be in the form of the free acids or as Salts are introduced.
  • Counterions are in particular alkali metal and ammonium ions.
  • This also applies to the optional components free fluoride and polyhydroxycarboxylic acids. If these components are not used or are not used exclusively in the form of the acids, the pH of the treatment baths may need to be adjusted to the range from 0.3 to 3.5 according to the invention. Phosphoric acid, nitric acid and sulfuric acid are particularly suitable for this.
  • pH value of the treatment solution is preferred.
  • Polymers of the acrylate type, including acrylate-containing copolymers, suitable as optional additives in concentrations below 500 mg / l are known as commercial products in the prior art.
  • Water-soluble polyacrylic acids in the molecular weight range between 20,000 and 100,000 daltons are particularly suitable, in particular those with an average molecular weight of about 50,000 to 60,000 daltons, the 5% strength by weight aqueous solution of which has a pH of about 2.
  • Suitable polymers of the type of the reaction products of polyvinylphenol with aldehydes and organic amines are known as agents for the surface treatment of metals and in particular for passivating rinsing of conversion-treated metal surfaces, for example from EP-A-319 016 and EP-A-319 017 . These are polymers with molecular weights up to 2,000,000 daltons with a preferred molecular weight range between 7,000 and 70,000 daltons.
  • the optionally substituted phenol rings in the chains can be linked via one or two carbon atoms, it being possible for the chains to have been subjected to a post-crosslinking process. Characteristically, at least some of the phenol rings are bonded via a carbon atom to a nitrogen atom which bears a further alkyl substituent which has at least one hydroxyl function. This structure gives the polymer chelating properties against metal ions.
  • the treatment solutions should have temperatures between 15 and 60 ° C and can be applied to the aluminum surfaces by spraying, dipping or using the no rinse process. In the case of spray or immersion applications, the required treatment times are between 5 and 90 seconds.
  • the no-rinse process which can be carried out, for example, by roller application (so-called chemcoater)
  • the setting of a specific wet film thickness by squeezing rolls is a process-relevant step.
  • the wet film thickness should be between 2 and 10 ml / m 2 , preferably between 4 and 6 ml / m 2 .
  • water rinsing with demineralized water can optionally take place after the immersion or spray treatment, the temperature of the rinsing water being between 10 and 40 ° C.
  • Aluminum sheets of size 100 x 200 mm and thickness 1.1 mm of various alloys from the AA 6000 group from different manufacturers and of different ages (cf. Table 2) were coated with a 1% aqueous alkaline cleaning solution (Ridoline R C 72, from Henkel ) freed from corrosion protection greasing at 65 ° C for 10-12 s, rinsed in process water for 5 s at room temperature and then rinsed in demineralized (demineralized) water for 5 s at room temperature.
  • This was followed by the conversion treatment with treatment solutions according to the invention and comparison solutions according to Table 1 and the process according to Table 2. This was carried out either by immersion, spraying or spin coating (simulation of the order in the chemcoater no rinse).
  • the results obtained depend on the alloy selected and on the history of the material (storage time). The better results are generally obtained with the AC120 alloy. In all cases, conversion treatment according to the invention However, the findings regarding surface resistance and phosphatability are within the technically required framework.
  • the test for bondability was carried out with tensile shear tests in accordance with DIN 53 283 using a commercially available two-component epoxy adhesive in accordance with the instructions for use (Terokal R 5045, Teroson, Heidelberg).
  • the alloy AC 120 was used as the substrate, which was treated according to the method in Table 2 and then stored open for 30 days. There was no further pretreatment before the adhesive strength was determined. For comparison, the values for a degreased sample and for a green chromated sample were measured after the same storage period. The results are shown in Table 3.

Landscapes

  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Treatment Of Metals (AREA)

Abstract

Procédé de traitement préalable de surfaces en aluminium ou en alliage d'aluminium avant un traitement de revêtement par conversion assurant une protection permanente contre la corrosion, en particulier une phosphatation avec des bains de phosphatation contenant du zinc, une chromatation ou un traitement de revêtement par conversion sans chrome, procédé caractérisé en ce que les surfaces sont mises en contact avec des solutions de traitement aqueuses et acides, qui comprennent des fluorures complexes des éléments bore, silicium, titane, zirconium ou hafnium, isolés ou en mélange, avec des concentrations totales comprises entre 100 et 4000 mg/l et un pH compris entre 0,3 et 3,5. Après le traitement préalable, les pièces en aluminium ou en alliage d'aluminium, éventuellement après un formage, peuvent être assemblées, par collage et/ou par soudage, entre elles ou avec des pièces en acier et/ou en acier zingué et/ou recouvert d'alliage de zinc et/ou en acier aluminé et/ou recouvert d'un alliage d'aluminium.

Claims (8)

  1. Procédé pour le prétraitement de surfaces en aluminium ou en ses alliages avant un second traitement par conversion conférant une protection permanente contre la corrosion, caractérisé en ce qu'on amène les surfaces en contact avec des solutions de traitement aqueuses acides qui contiennent des fluorures complexes des éléments comprenant le bore, le silicium, le titane, le zirconium ou le hafnium, individuellement ou en mélange l'un avec l'autre dans des concentrations des anions fluoro au total entre 100 et 4000 mg/l, et qui présentent une valeur de pH entre 0,3 et 3,5, et er ce que, entre le prétraitement des surfaces en aluminium ou en ses alliages et le traitement par conversion conférant une protection permanente contre la corrosion, on soumet les éléments en aluminium ou en ses alliages à un procédé de formage sans enlèvement de copeaux et/ou par enlèvement des copeaux, et/ou on les relie par collage et/ou par soudage l'un à l'autre ou avec des éléments en acier et/ou en acier galvanisé et/ou galvanisé à l'aide d'un alliage.
  2. Procédé selon la revendication 1, caractérisé en ce que les solutions de traitement contiennent en outre des polymères du type des polyacrylates et/ou des produits réactionnels de poly(vinylphénol) avec des aldéhydes et des amines organiques contenant des groupes hydroxyle dans des concentrations inférieures à 500 mg/l, et en ce que, en présence de zirconium dans la solution de traitement, la concentration des produits réactionnels de poly(vinylphénol) avec des aldéhydes et des amines organiques contenant des groupes hydroxyle est inférieure à 100 mg/l.
  3. Procédé selon une des revendications 1 et 2 ou selon les deux, caractérisé en ce que les solutions de traitement contiennent en outre des ions fluorure libres dans des concentrations allant jusqu'à 500 mg/l.
  4. Procédé selon une ou plusieurs des revendications 1 à 3, caractérisé en ce que les solutions de traitement contiennent en outre des acides polyhydroxy-carboxyliques ou leurs anions dans des concentrations allant jusqu'à 500 mg/l.
  5. Procédé selon une ou plusieurs des revendications 1 à 4, caractérisé en ce que les solutions de traitement contiennent en outre des ions sulfate dans des concentrations allant jusqu'à 50 g/l.
  6. Procédé selon une ou plusieurs des revendications 1 à 5, caractérisé en ce que les solutions de traitement présentent des températures entre 15 et 60°C et sont appliquées par pulvérisation, par immersion ou encore dans le procédé "No-Rinse" sur les surfaces en aluminium.
  7. Procédé selon la revendication 6, caractérisé en ce que les surfaces en aluminium sont séchées après leur traitement à des températures entre 40 et 85°C.
  8. Procédé selon une ou plusieurs des revendications 1 à 7, caractérisé en ce que, entre le prétraitement des surfaces en aluminium ou en ses alliages et le traitement par conversion conférant une protection permanente contre la corrosion, on intercale encore des étapes de nettoyage et des rinçages intermédiaires avec de l'eau et/ou avec des bains de rinçage d'activation.
EP94916970A 1993-05-24 1994-05-17 Traitement de revetement par conversion sans chrome pour l'aluminium Expired - Lifetime EP0700452B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4317217 1993-05-24
DE4317217A DE4317217A1 (de) 1993-05-24 1993-05-24 Chromfreie Konversionsbehandlung von Aluminium
PCT/EP1994/001600 WO1994028193A1 (fr) 1993-05-24 1994-05-17 Traitement de revetement par conversion sans chrome pour l'aluminium

Publications (2)

Publication Number Publication Date
EP0700452A1 EP0700452A1 (fr) 1996-03-13
EP0700452B1 true EP0700452B1 (fr) 1997-07-23

Family

ID=6488772

Family Applications (1)

Application Number Title Priority Date Filing Date
EP94916970A Expired - Lifetime EP0700452B1 (fr) 1993-05-24 1994-05-17 Traitement de revetement par conversion sans chrome pour l'aluminium

Country Status (9)

Country Link
US (1) US5584946A (fr)
EP (1) EP0700452B1 (fr)
JP (1) JP3476824B2 (fr)
KR (1) KR100326612B1 (fr)
AU (1) AU675328B2 (fr)
CA (1) CA2163621C (fr)
DE (2) DE4317217A1 (fr)
ES (1) ES2104390T3 (fr)
WO (1) WO1994028193A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000068458A1 (fr) * 1999-05-11 2000-11-16 Chemetall Gmbh Traitement prealable de surfaces d'aluminium a l'aide de solutions exemptes de chrome
WO2006084491A1 (fr) 2005-02-08 2006-08-17 Henkel Kommanditgesellschaft Auf Aktien Procede de revetement de toles metalliques, notamment de toles de zinc
DE102014225237B3 (de) * 2014-12-09 2016-04-28 Henkel Ag & Co. Kgaa Verfahren zur nasschemischen Vorbehandlung einer Vielzahl von Eisen- und Aluminiumbauteilen in Serie
DE102016217507A1 (de) 2015-09-15 2017-03-16 Chemetall Gmbh Vorbehandlung von Aluminiumoberflächen mit zirkon- und molybdänhaltigen Zusammensetzungen
US10125424B2 (en) 2012-08-29 2018-11-13 Ppg Industries Ohio, Inc. Zirconium pretreatment compositions containing molybdenum, associated methods for treating metal substrates, and related coated metal substrates

Families Citing this family (68)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5356490A (en) * 1992-04-01 1994-10-18 Henkel Corporation Composition and process for treating metal
DE4412138A1 (de) * 1994-04-08 1995-10-12 Henkel Kgaa Chromfreies Verfahren zur No-Rinse Behandlung von Aluminium und seinen Legierungen sowie hierfür geeignete wäßrige Badlösungen
DE19508126A1 (de) * 1995-03-08 1996-09-12 Henkel Kgaa Chromfreies Verfahren zur Verbesserung der Lackhaftung nach Dünnschicht-Anodisierung
DE19733972A1 (de) * 1997-08-06 1999-02-11 Henkel Kgaa Alkalische Bandpassivierung
US6720032B1 (en) 1997-09-10 2004-04-13 Henkel Kommanditgesellschaft Auf Aktien Pretreatment before painting of composite metal structures containing aluminum portions
BR9813045A (pt) * 1997-10-14 2000-11-21 Henkel Corp Processo para formação sobre uma superfìcie metálica de um revestimento sólido aderente, e, composição de concentrado de reposição primária
US6802913B1 (en) 1997-10-14 2004-10-12 Henkel Kommanditgesellschaft Aut Aktien Composition and process for multi-purpose treatment of metal surfaces
CN100549231C (zh) * 1997-10-31 2009-10-14 铃木株式会社 滑动部件
JP3491811B2 (ja) * 1997-10-31 2004-01-26 スズキ株式会社 摺動部材及びピストン
US5858282A (en) * 1997-11-21 1999-01-12 Ppg Industries, Inc. Aqueous amine fluoride neutralizing composition for metal pretreatments containing organic resin and method
US6312812B1 (en) 1998-12-01 2001-11-06 Ppg Industries Ohio, Inc. Coated metal substrates and methods for preparing and inhibiting corrosion of the same
US6217674B1 (en) 1999-05-11 2001-04-17 Ppg Industries Ohio, Inc. Compositions and process for treating metal substrates
US6168868B1 (en) 1999-05-11 2001-01-02 Ppg Industries Ohio, Inc. Process for applying a lead-free coating to untreated metal substrates via electrodeposition
US6440580B1 (en) 1998-12-01 2002-08-27 Ppg Industries Ohio, Inc. Weldable, coated metal substrates and methods for preparing and inhibiting corrosion of the same
DE19856613A1 (de) * 1998-12-08 2000-06-15 Emhart Inc Anschweißteil aus Aluminium oder einer Aluminiumlegierung mit einer Beschichtung
US6860687B1 (en) * 1998-12-08 2005-03-01 Newfrey Llc Weldable aluminum stud
US6569537B1 (en) * 1999-04-28 2003-05-27 Suzuki Motor Corporation Surface treatment method sliding member and piston
DE10010758A1 (de) * 2000-03-04 2001-09-06 Henkel Kgaa Korrosionsschutzverfahren für Metalloberflächen
DE10030462A1 (de) * 2000-06-21 2002-01-03 Henkel Kgaa Haftvermittler in Konversionslösungen
DE10035351C2 (de) * 2000-07-20 2002-06-06 Nelson Bolzenschweis Technik G Aluminiumschweißteil, insbesondere Aluminiumbolzen für das Bolzenschweißen, und Verfahren zum Verschweißen desselben
US6488990B1 (en) * 2000-10-06 2002-12-03 Chemetall Gmbh Process for providing coatings on a metallic surface
EP1368507B1 (fr) 2001-02-16 2014-03-26 Henkel AG & Co. KGaA Procede de traitement d'articles polymetalliques
DE10110833B4 (de) * 2001-03-06 2005-03-24 Chemetall Gmbh Verfahren zum Aufbringen eines Phosphatüberzuges und Verwendung der derart phosphatierten Metallteile
US6524403B1 (en) 2001-08-23 2003-02-25 Ian Bartlett Non-chrome passivation process for zinc and zinc alloys
CN1306064C (zh) * 2001-12-04 2007-03-21 新日本制铁株式会社 金属氧化物和/或金属氢氧化物涂敷的金属材料及其生产方法
US7294211B2 (en) 2002-01-04 2007-11-13 University Of Dayton Non-toxic corrosion-protection conversion coats based on cobalt
FR2835533B1 (fr) * 2002-02-05 2004-10-08 Pechiney Rhenalu TOLE EN ALLIAGE Al-Si-Mg POUR PEAU DE CARROSSERIE AUTOMOBILE
US6841251B2 (en) * 2002-02-19 2005-01-11 Ppg Industries Ohio, Inc. Composition having sealing and sound dampening properties and methods related thereto
US6749939B2 (en) 2002-02-19 2004-06-15 Ppg Industries, Ohio, Inc. Composition having sealing and sound dampening properties and methods related thereto
DE10210133A1 (de) * 2002-03-08 2003-09-18 Behr Gmbh & Co Flussmittel zum Löten von Aluminium
WO2004046421A1 (fr) * 2002-11-15 2004-06-03 Henkel Kommanditgesellschaft Auf Aktien Composition et procede de passivation pour surfaces zinciferes et aluniferes
EP1566467B1 (fr) * 2002-11-25 2015-03-18 Toyo Seikan Kaisha, Ltd. Matériau métallique traité en surface, procédé de traitement de ladite surface, et matériau métallique revêtu de résine, boite de conserve métallique et son couvercle
JP4205939B2 (ja) * 2002-12-13 2009-01-07 日本パーカライジング株式会社 金属の表面処理方法
ES2316707T3 (es) * 2002-12-24 2009-04-16 Chemetall Gmbh Agente de revestimiento de conversion quimica y metal tratado en superficie.
US6881491B2 (en) * 2003-05-16 2005-04-19 Alcoa Inc. Protective fluoride coatings for aluminum alloy articles
DE10339165A1 (de) 2003-08-26 2005-03-24 Henkel Kgaa Farbige Konversionsschichten auf Metalloberflächen
WO2005047565A1 (fr) 2003-11-07 2005-05-26 Henkel Kommanditgesellschaft Auf Aktien Couches de conversion colorees sans chrome formees sur des surfaces metalliques
DE10358310A1 (de) * 2003-12-11 2005-07-21 Henkel Kgaa Zweistufige Konversionsbehandlung
DE10358590A1 (de) * 2003-12-12 2005-07-07 Newfrey Llc, Newark Verfahren zur Vorbehandlung von Oberflächen von Schweissteilen aus Aluminium oder seinen Legierungen und entsprechende Schweissteile
US20050145303A1 (en) * 2003-12-29 2005-07-07 Bernd Schenzle Multiple step conversion coating process
JP5456223B2 (ja) * 2004-02-20 2014-03-26 日本ペイント株式会社 表面調整剤調製用の濃厚液、表面調整剤及び表面調整方法
US20080057336A1 (en) * 2004-06-22 2008-03-06 Toyo Seikan Kaisha, Ltd Surface-Treated Metal Materials, Method of Treating the Surfaces Thereof, Resin-Coated Metal Materials, Cans and Can Lids
US20060261137A1 (en) * 2005-05-17 2006-11-23 Kabushiki Kaisha Kobe Seiko Sho (Kobe Steel, Ltd.) Dissimilar metal joint member with good corrosion resistance and method for manufacturing same
DE102005035704A1 (de) * 2005-07-27 2007-02-01 Behr Gmbh & Co. Kg Zu verlötende Oberfläche
TWI340770B (en) * 2005-12-06 2011-04-21 Nippon Steel Corp Composite coated metal sheet, treatment agent and method of manufacturing composite coated metal sheet
DE502006000960D1 (de) 2006-04-19 2008-07-31 Ropal Ag Verfahren zur Herstellung eines korrosionsgeschützten und hochglänzenden Substrats
US20080023527A1 (en) * 2006-07-11 2008-01-31 Gerhard Brenninger Method of permanently joining components formed from metallic materials
EP2067881B1 (fr) * 2006-09-08 2017-11-15 Chemetall GmbH Procédé de traitement de surface d'une base métallique, matériau métallique traité par ce procédé de traitement de surface et procédé de revêtement de ce matériau métallique
DE102007043479A1 (de) * 2007-09-12 2009-03-19 Valeo Schalter Und Sensoren Gmbh Verfahren zur Oberflächenbehandlung von Aluminium und ein Schichtaufbau eines Bauteils aus Aluminium mit einer elektrischen Kontaktierung
TWI354713B (en) * 2007-12-03 2011-12-21 Ya Thai Chemical Co Ltd Chrome-free corrosion inhibitors and applications
BRPI0909501B1 (pt) 2008-03-17 2019-03-26 Henkel Ag & Co. Kgaa Método
DE102008014465B4 (de) 2008-03-17 2010-05-12 Henkel Ag & Co. Kgaa Mittel zur optimierten Passivierung auf Ti-/Zr-Basis für Metalloberflächen und Verfahren zur Konversionsbehandlung
GB2469115B (en) 2009-04-03 2013-08-21 Keronite Internat Ltd Process for the enhanced corrosion protection of valve metals
US8486203B2 (en) * 2009-06-11 2013-07-16 Metalast International, Inc. Conversion coating and anodizing sealer with no chromium
WO2011090691A2 (fr) * 2009-12-28 2011-07-28 Henkel Ag & Co. Kgaa Composition de prétraitement d'un métal contenant du zirconium, du cuivre, du zinc et un nitrate, et revêtements correspondants appliqués sur des substrats métalliques
JP5734008B2 (ja) * 2010-10-18 2015-06-10 株式会社神戸製鋼所 アルミニウム合金板、これを用いた接合体および自動車用部材
ES2872342T3 (es) * 2010-12-07 2021-11-02 Henkel Ag & Co Kgaa Composición para pretratamiento para metales que contiene zirconio, cobre y agentes quelantes de metales y recubrimientos relacionados sobre sustratos metálicos
US9284460B2 (en) 2010-12-07 2016-03-15 Henkel Ag & Co. Kgaa Metal pretreatment composition containing zirconium, copper, and metal chelating agents and related coatings on metal substrates
EP2532769A1 (fr) 2011-06-10 2012-12-12 Amcor Flexibles Kreuzlingen Ltd. Procédé de production dune couche de conversion sur une surface dune bande d'aluminium ou d'alliage d'aluminium
CN102321881A (zh) * 2011-10-17 2012-01-18 湖南创高铝业集团有限公司 一种铝材无铬钝化表面处理工艺
RU2609585C2 (ru) 2012-08-29 2017-02-02 Ппг Индастриз Огайо, Инк. Циркониевые композиции для предварительной обработки, содержащие литий, соответствующие способы обработки металлических субстратов и соответствующие металлические субстраты с покрытиями
US20140255608A1 (en) 2013-03-11 2014-09-11 Ppg Industries Ohio, Inc. Coatings that exhibit a tri-coat appearance, related coating methods and substrates
JP5969086B2 (ja) * 2015-05-07 2016-08-10 株式会社神戸製鋼所 表面処理アルミニウム合金板およびその製造方法
DE102015215651B4 (de) * 2015-08-17 2020-10-08 Vacuumschmelze Gmbh & Co. Kg Verfahren und Behandlungslösung zur Behandlung von Aluminiumbeschichtungen vor der Passivierung mit Chrom(III)-haltigen Lösungen
MX2019001874A (es) 2016-08-24 2019-06-06 Ppg Ind Ohio Inc Composicion limpiadora que contiene hierro.
US11261531B2 (en) 2017-09-14 2022-03-01 Chemetall Gmbh Method for pretreating aluminum materials, particularly aluminum wheels
HUE048447T2 (hu) 2017-09-18 2020-08-28 Henkel Ag & Co Kgaa Pácolási és konverziós kezelést alkalmazó kétlépéses alumínium, különösen alumíniumötvözet elõkezelés
CN107653449B (zh) * 2017-10-12 2020-03-17 佛山市顺德区美硕金属表面技术有限公司 无铬钝化组合物、无铬钝化剂及其制备方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4017334A (en) * 1973-10-04 1977-04-12 Oxy Metal Industries Corporation Process for treating aluminum cans
WO1990012902A1 (fr) * 1989-04-21 1990-11-01 Henkel Corporation Procede et composition servant au revetement d'aluminium

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2705500A (en) * 1953-11-04 1955-04-05 Leon L Deer Cleaning aluminum
US3331710A (en) * 1963-08-23 1967-07-18 Hooker Chemical Corp Method for coating aluminum
DE2031358C3 (de) * 1970-06-25 1981-10-15 Gerhard Collardin GmbH, 5000 Köln Verfahren zur Erzeugung von Schutzschichten auf Aluminium, Eisen und Zink mittels saurer, komplexe Fluoride enthaltender, Lösungen
US4191596A (en) * 1978-09-06 1980-03-04 Union Carbide Corporation Method and compositions for coating aluminum
NZ195810A (en) * 1979-12-26 1983-07-15 Amchem Prod Acidic aqueous solution forming a corrosion-resistant coating on aluminium
US4391652A (en) * 1982-01-29 1983-07-05 Chemical Systems, Inc. Surface treatment for aluminum and aluminum alloys
US4457790A (en) * 1983-05-09 1984-07-03 Parker Chemical Company Treatment of metal with group IV B metal ion and derivative of polyalkenylphenol
US4921552A (en) * 1988-05-03 1990-05-01 Betz Laboratories, Inc. Composition and method for non-chromate coating of aluminum
DE4017187A1 (de) * 1990-05-29 1991-12-05 Metallgesellschaft Ag Verfahren zur nachspuelung von konversionsschichten
US5294266A (en) * 1989-07-28 1994-03-15 Metallgesellschaft Aktiengesellschaft Process for a passivating postrinsing of conversion layers
US5122202A (en) * 1990-07-05 1992-06-16 Elf Atochem North America, Inc. Method and compositions for coating non-ferrous metals
US5089064A (en) * 1990-11-02 1992-02-18 Henkel Corporation Process for corrosion resisting treatments for aluminum surfaces
EP0600982A1 (fr) * 1991-08-30 1994-06-15 Henkel Corporation Procede de traitement de metaux a l'aide d'une composition aqueuse acide pratiquement exempte de chrome (vi)
US5242714A (en) * 1991-12-20 1993-09-07 Henkel Corporation Process for forming protective base coatings on metals

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4017334A (en) * 1973-10-04 1977-04-12 Oxy Metal Industries Corporation Process for treating aluminum cans
WO1990012902A1 (fr) * 1989-04-21 1990-11-01 Henkel Corporation Procede et composition servant au revetement d'aluminium

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000068458A1 (fr) * 1999-05-11 2000-11-16 Chemetall Gmbh Traitement prealable de surfaces d'aluminium a l'aide de solutions exemptes de chrome
WO2006084491A1 (fr) 2005-02-08 2006-08-17 Henkel Kommanditgesellschaft Auf Aktien Procede de revetement de toles metalliques, notamment de toles de zinc
US7709058B2 (en) 2005-02-08 2010-05-04 Henkel Kgaa Process for coating metal sheet, especially zinc sheet
US10125424B2 (en) 2012-08-29 2018-11-13 Ppg Industries Ohio, Inc. Zirconium pretreatment compositions containing molybdenum, associated methods for treating metal substrates, and related coated metal substrates
US10920324B2 (en) 2012-08-29 2021-02-16 Ppg Industries Ohio, Inc. Zirconium pretreatment compositions containing molybdenum, associated methods for treating metal substrates, and related coated metal substrates
DE102014225237B3 (de) * 2014-12-09 2016-04-28 Henkel Ag & Co. Kgaa Verfahren zur nasschemischen Vorbehandlung einer Vielzahl von Eisen- und Aluminiumbauteilen in Serie
DE102016217507A1 (de) 2015-09-15 2017-03-16 Chemetall Gmbh Vorbehandlung von Aluminiumoberflächen mit zirkon- und molybdänhaltigen Zusammensetzungen
WO2017046139A1 (fr) 2015-09-15 2017-03-23 Chemetall Gmbh Prétraitement de surfaces en aluminium avec des compositions contenant du zircon et du molybdène

Also Published As

Publication number Publication date
KR960702539A (ko) 1996-04-27
EP0700452A1 (fr) 1996-03-13
JPH08510505A (ja) 1996-11-05
ES2104390T3 (es) 1997-10-01
WO1994028193A1 (fr) 1994-12-08
CA2163621A1 (fr) 1994-12-08
US5584946A (en) 1996-12-17
JP3476824B2 (ja) 2003-12-10
DE4317217A1 (de) 1994-12-01
CA2163621C (fr) 2004-10-26
AU6844294A (en) 1994-12-20
KR100326612B1 (ko) 2002-11-30
DE59403473D1 (de) 1997-08-28
AU675328B2 (en) 1997-01-30

Similar Documents

Publication Publication Date Title
EP0700452B1 (fr) Traitement de revetement par conversion sans chrome pour l'aluminium
EP1200641B1 (fr) Traitement prealable de surfaces d'aluminium a l'aide de solutions exemptes de chrome
EP0774016B1 (fr) Procede de phosphatage sans rin age final
DE69706161T2 (de) Zinkphosphat- und wolfram enthaltende überzugsmittel mit beschleuniger
EP2817434B1 (fr) Prétraitement de surfaces en zinc avant une passivation
EP3350357B1 (fr) Prétraitement de surfaces en aluminium avec des compositions contenant du zircon et du molybdène
EP2255026A1 (fr) Passivation optimisée à base de ti-zr de surfaces métalliques
DE3689442T2 (de) Saure, wässrige Phosphatüberzugslösungen für ein Verfahren zum Phosphatbeschichten metallischer Oberfläche.
EP1235949B1 (fr) Procede de phosphatation utilisation des pieces en metal ainsi phosphatees
WO2005061761A1 (fr) Traitement de conversion en deux etapes
WO2001059181A2 (fr) Anticorrosif et procede de protection contre la corrosion destine a des surfaces metalliques
EP2215285B1 (fr) Phosphatation au zirconium de pièces métalliques, en particulier en fer
DE102019134298A1 (de) Verfahren zum Herstellen eines Stahlflachprodukts mit einer metallischen Schutzschicht auf Basis von Zink und einer auf einer Oberfläche der metallischen Schutzschicht erzeugten Phosphatierschicht und derartiges Stahlflachprodukt
EP0111223B1 (fr) Procédé de phosphatation de surfaces métalliques et compositions appropriées à ce procédé
DE19933189A1 (de) Verfahren zur korrosionsschützenden Behandlung oder Nachbehandlung von Metalloberflächen
DE3875459T2 (de) Verfahren zum phosphatieren von metalloberflaechen.
DE3016576A1 (de) Verfahren zur phosphatierung von metalloberflaechen sowie dessen anwendung
DE19639597C2 (de) Verfahren zur Phosphatierung von laufenden Bändern aus kalt- oder warmgewalztem Stahl in schnellaufenden Bandanlagen
WO2001040546A1 (fr) Procede de phosphatation, de rinçage et d'electrolaquage par immersion cathodique
WO2001016397A1 (fr) Procede de phosphatation au zinc faisant intervenir des epoxydes

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

17P Request for examination filed

Effective date: 19951115

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): BE DE ES FR GB IT NL PT SE

17Q First examination report despatched

Effective date: 19960223

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

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): BE DE ES FR GB IT NL PT SE

ET Fr: translation filed
REF Corresponds to:

Ref document number: 59403473

Country of ref document: DE

Date of ref document: 19970828

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2104390

Country of ref document: ES

Kind code of ref document: T3

ITF It: translation for a ep patent filed

Owner name: STUDIO JAUMANN

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

Effective date: 19971001

REG Reference to a national code

Ref country code: PT

Ref legal event code: SC4A

Free format text: AVAILABILITY OF NATIONAL TRANSLATION

Effective date: 19970911

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: PT

Payment date: 20020508

Year of fee payment: 9

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

Ref country code: NL

Payment date: 20020529

Year of fee payment: 9

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: 20031130

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: 20031201

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 20031201

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: 20031130

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

Ref country code: SE

Payment date: 20050506

Year of fee payment: 12

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

Ref country code: BE

Payment date: 20050715

Year of fee payment: 12

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: 20060518

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

Ref country code: BE

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

Effective date: 20060531

EUG Se: european patent has lapsed
BERE Be: lapsed

Owner name: *HENKEL K.G.A.A.

Effective date: 20060531

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

Ref country code: ES

Payment date: 20120607

Year of fee payment: 19

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

Ref country code: DE

Payment date: 20130515

Year of fee payment: 20

Ref country code: GB

Payment date: 20130515

Year of fee payment: 20

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

Ref country code: IT

Payment date: 20130520

Year of fee payment: 20

Ref country code: FR

Payment date: 20130531

Year of fee payment: 20

REG Reference to a national code

Ref country code: DE

Ref legal event code: R071

Ref document number: 59403473

Country of ref document: DE

REG Reference to a national code

Ref country code: GB

Ref legal event code: PE20

Expiry date: 20140516

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 EXPIRATION OF PROTECTION

Effective date: 20140516

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 EXPIRATION OF PROTECTION

Effective date: 20140520

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20140926

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 EXPIRATION OF PROTECTION

Effective date: 20140518