EP0385448B1 - Verfahren zur Beschichtung von Werkstücken mit Aluminium - Google Patents

Verfahren zur Beschichtung von Werkstücken mit Aluminium Download PDF

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Publication number
EP0385448B1
EP0385448B1 EP19900103924 EP90103924A EP0385448B1 EP 0385448 B1 EP0385448 B1 EP 0385448B1 EP 19900103924 EP19900103924 EP 19900103924 EP 90103924 A EP90103924 A EP 90103924A EP 0385448 B1 EP0385448 B1 EP 0385448B1
Authority
EP
European Patent Office
Prior art keywords
parts
conductive primer
aluminum
coating
steel
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
EP19900103924
Other languages
English (en)
French (fr)
Other versions
EP0385448A1 (de
Inventor
Toshiharu Oshiba
Hisataka Yamamoto
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.)
Nippon Paint Co Ltd
Original Assignee
Nippon Paint Co Ltd
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 claimed from JP18198389A external-priority patent/JPH02290997A/ja
Application filed by Nippon Paint Co Ltd filed Critical Nippon Paint Co Ltd
Publication of EP0385448A1 publication Critical patent/EP0385448A1/de
Application granted granted Critical
Publication of EP0385448B1 publication Critical patent/EP0385448B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B05SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05DPROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/14Processes, 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
    • B05D7/16Processes, 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

Definitions

  • the present invention relates to a method of coating a metal assembly including at least one aluminum part and steel parts, particularly to a method of coating assembled metal members for automobile bodies.
  • Jitsumu Hyomen Gijutsu (Metal Finishing Practice) Vol. 35, No. 1, 1988 discloses a method of coating assembled members consisting of aluminum parts and steel parts in which the aluminum parts and the steel parts are treated separately in their exclusive treatment lines and the treated aluminum parts and the steel parts are combined in a final stage.
  • the exclusive lines are necessary for both of the aluminum parts and the steel parts, and the treated aluminum parts and the steel parts should be handled very carefully in assembling.
  • painted parts may have slightly different finish colors.
  • an object of the present invention is to provide a method of coating a metal assembly including at least one aluminum part in which the aluminum part and the other parts, namely steel parts can be treated simultaneously, thereby effectively coating the aluminum member for automobile bodies, etc.
  • an aluminum part coated with a conductive primer is highly resistant to a treatment with chemical solutions which is necessary for chemically treating steel parts, and that the aluminum part coated with a conductive primer can be easily stamped to provide deep-drawn products, etc. without using lubricating oils.
  • the present invention is based on these findings.
  • the invention as defined in independent claims 1 and 5 comprises a method of coating a metal assembly of Al parts with uncoated and/or zinc or zinc-alloy coated steel parts comprising the steps of : degreasing of the Al part; applying a conductive primer to said aluminum part: baking the primer to form an organic coating layer; combining said aluminium part with the steel part and providing the resulting assembled parts with chemical coatings or with chemical coatings and and electrodeposition coatings.
  • the method of coating a metal assembly comprises also the step of conducting the formation of an intermediate coat and/or top coat after forming electrodeposition coatings.
  • the metal assembly to which the coating method of the present invention can be applied is constituted of at least one aluminum part and at least one other steel part .
  • a typical combination comprising aluminum parts and steel parts (including zinc-plated steel parts).
  • One combination is at least one aluminium part and at least one steel part.
  • a metal assembly of these plates is provided with chemical coatings and electrodeposition coatings, optionally followed by the formation of an intermediate coat and/or a top coat.
  • the aluminum parts are stamped, they are assembled with steel parts and then provided with an intermediate coat and/or a top coat.
  • plastic members may be combined with aluminum parts and steel parts.
  • the conductive primer which may be used in the present invention comprises:
  • the solid content of the conductive primer is 10 to 50 weight %, which makes it possible to form a thin, uniform, conductive primer layer with excellent corrosion resistance, high conductivity in electrodeposition coating, improved formability, and excellent adhesion to an electrodeposition coating layer.
  • binder resin (A) is a bisphenol-type epoxy resin soluble in an organic solvent and having a number average molecular weight of 300 to 100,000, which is excellent in water resistance, alkali resistance, and good adhesion to a substrate material as well as a top coat.
  • examples are the epoxy resins represented by the formula: in which R is H or CH3; A is ⁇ C(CH3)2, -CH2-, -O-,
  • the number average molecular weight of the epoxy resin is less than 300, it is unable to get a high polymer when reacted with a polyisocyanate, making the resulting conductive primer layer deficient in anti-corrosive properties.
  • it is more than 100,000 a cross-linking degree decreases, providing the resulting conductive primer layer with poor anti-corrosive properties.
  • the above bisphenol-type epoxy resin (A) should be 30 weight % or more on a solid basis of the conductive primer layer, because, if otherwise, the resulting conductive primer layer is likely to be brittle and have poor adhesion after stamping.
  • the hardener (B) used in the present invention is selected from the group consisting of polyisocyanates and blocked polyisocyanates.
  • polyisocyanates examples include aliphatic or alicyclic diisocyanates including hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated diphenyl methane diisocyanate and the like; aromatic diisocyanates including tolylene diisocyanate, diphenyl methane-4,4'-diisocyanate and the like, triisocyanates as adducts of 1 mol of trimethylol propane and 3 mol of either one of the above-mentioned diisocyanates, trimers of hexamethylene diisocyanate, trimers of tolylene diioscyanate and the like.
  • any of the above-mentioned polyisocyanates blocked with blocking agents may be used.
  • Such blocking agents must be compounds capable of reacting with an isocyanate group and forming addition products which are stable at a room temperature but dissociated at a high temperature encountered at a baking stage, thereby making the isocyanate group free.
  • the blocking agents are lactam blocking agents such as ⁇ -caprolactam and ⁇ -butyrolactam; oxime blocking agents such as methyl ethyl ketoxime and cyclohexanone oxime; alcohol blocking agents such as methanol, ethanol and isobutyl alcohol; phenol blocking agents such as phenol, p-t-butyl phenol and cresol; and ⁇ -diketone blocking agents such as ethyl acetoacetate, methyl acetoacetate, acetyl acetoacetate, dimethyl malonate and diethyl malonate.
  • lactam blocking agents such as ⁇ -caprolactam and ⁇ -butyrolactam
  • oxime blocking agents such as methyl ethyl ketoxime and cyclohexanone oxime
  • alcohol blocking agents such as methanol, ethanol and isobutyl alcohol
  • phenol blocking agents such as phenol, p-t-butyl phenol and cresol
  • the above-mentioned hardener (B) is contained in the conductive primer in an amount of one-tenth to 2 times the weight of the epoxy resin (A) on a solid basis.
  • the epoxy resin (A) and the hardener (B) react with each other at a relatively low baking temperature in a short period of time, for example, at a maximum temperature of about 100°C or more, preferably at 120°C to 200°C, in 5 to 60 seconds.
  • the mixing ration of (B)/(A) is less than 1/10, the cross-linking reaction is insufficient, resulting in poor corrosion resistance of the conductive primer layer.
  • the ratio (B)/(A) is more than 20/10, the conductive primer layer are provided with poor water resistance, alkali resistance and adhesion to an overlying coat.
  • Particularly preferable mixing ration of the hardener (B) to the epoxy resin (A) is such that NCO equivalent of the hardener (B)/OH equivalent of the epoxy resin (A) is within a range of 0.1/1 - 1.0/1. Under these conditions, excellent anti-corrosion properties can be achieved.
  • the above-mentioned hardener (B) may be used together with a resol-type phenyl resin, if desired. This is especially effective in accelerating the film-forming reaction at a relatively low baking temperature, for example, at a maximum temperature of 100°C to 130°C.
  • Particularly preferable resol-type phenol resins are the compounds of the formula: wherein n is an integer of 0 to 4; W is -CH2- or -CH2-O-CH2-; R is CH3, H, or
  • Such a resol-type phenol resin is preferably added in an amount up to 10 times the weight of the hardener (B) on a solid basis. If the weight ratio of the phenol resin/hardener (B) is more than 10/1, alkali resistance of the resulting conductive primer layer is likely to be lowered.
  • fumed silica (C) having an average particle size of 0.1 to 100 milli- ⁇ m serves to provide the primer layer with electric conductivity, because ions can pass through pores generated by the fumed silica in the primer layer in the processes of chemical coating and electrodeposition coating. If the average particle size of the silica is less than 0.1 milli- ⁇ m, the conductive primer layer is insufficient not only in electric conductivity but also in adhesion to an overlying layer and alkali resistance. On the other hand, when the average particle size of the fumed silica exceeds 100 milli- ⁇ m, the corrosion resistance of the resulting conductive primer layer is lowered.
  • the fumed silica (C) amounts to 5 to 50 weight %, preferably 15 to 30 weight %, on a solid basis of the conductive primer.
  • fumed silica has not been used, because it makes the conductive primer highly viscous.
  • this problem has been solved by the use of particular ketone solvent (D).
  • the fumed silica (C) is less than 5 weight % on a solid basis of the conductive primer, the corrosion resistance of the resulting conductive primer layer becomes poor. On the other hand, if it exceeds 50 weight %, adhesion properties of the conductive primer layer after stamping tend to be undesirably decreased.
  • the epoxy resin (A), the hardener (B) and the fumed silica (C) are dissolved or dispersed in a ketone solvent.
  • the ketone solvent (D) should be 40 weight % or more to adjust the solid content of the conductive primer to 10 to 50 weight %.
  • the solid content of the conductive primer is less than 10 weight %, it is uneconomical because too much solvent is consumed. On the other hand, if it exceeds 50 weight %, it is hardly possible to form a thin, uniform conductive primer layer.
  • ketone solvents (D) are methyl isobutyl ketone, acetone, cyclohexanone and isophorone. If desired, additional solvents other than the ketone solvent may be used together therewith. However, solvents reactive with polyisocyanates, e.g. water and alcohol, should be avoided.
  • the conductive primer may further contain 0.1 to 10 weight %, based on the conductive primer, of such lubricants as polyolefins, carboxylates, metal carboxylates, polyalkylene glycols, molybdenum disulfide, silicone compounds and fluorinated compounds.
  • lubricants are polyethylene waxes having densities of 0.94 or more, molecular weights of 1,000 and 10,000 and acid values of 15 KOH mg/g or less.
  • conductive material powder such as carbon black, graphite powder, zinc oxide powder, titanium oxide powder, aluminum powder, copper powder, etc. may be added in proper proportions.
  • the conductive primer may further contain known anti-corrosive pigments (e.g. chromate pigments, especially zinc chromate, lead chromate and barium chromate, phosphate pigments and plumbate pigments), extender pigments (e.g. carbonate pigments and silicate pigments), coloring pigments (e.g. titanium oxide and carbon black), anti-corrosive agents (e.g. amine compounds and phenolic carboxylic acids and dispersion stabilizers.
  • anti-corrosive pigments e.g. chromate pigments, especially zinc chromate, lead chromate and barium chromate, phosphate pigments and plumbate pigments
  • extender pigments e.g. carbonate pigments and silicate pigments
  • coloring pigments e.g. titanium oxide and carbon black
  • anti-corrosive agents e.g. amine compounds and phenolic carboxylic acids and dispersion stabilizers.
  • the conductive primer used in the present invention forms an organic coating layer which is electrically conductive for the purpose of the present invention.
  • conductive used herein means that the aluminum parts coated with the conductive primer can be provided with chemical coatings and electrodeposition coatings, namely meaning that electric conductivity can be achieved through the conductive primer in the process of electrodeposition coating, etc. The reasons therefor may be considered that since the conductive primer layer is thin and porous, electrodeposition coating composition can be attracted to the aluminum parts via the conductive primer.
  • the conductive primer provides the aluminum parts with excellent workability, thereby making it unnecessary to use lubricating oils. This is an outstanding advantage because the process of removing lubricating oils from the stamped aluminum parts can be omitted.
  • the aluminum parts are coated with the conductive primer on one or both sides thereof, and they conveyed to an automobile body manufacturing line, etc., where the aluminum parts is stamped and combined with steel parts for subsequent treatments.
  • the conductive primer may be applied to the assembled parts by spraying, and then baked.
  • the conductive primer is usually applied to the aluminum parts in a dry film thickness of 10 ⁇ m or less.
  • the dry film thickness exceeds 10 ⁇ m, the conductive primer shows high insulation, making it difficult to provide it with chemical coatings and electrodeposition coatings. Accordingly, the resulting caoted aluminum parts have a poor corrosion resistance, impact resistance and workability.
  • the preferred dry film thickness of the conductive primer layer is 0.1-5 ⁇ m.
  • the conductive primer-coated aluminum parts is vulnerable to erosion in a zinc phosphate treatment bath, permitting a large amount of aluminum to be dissolved into the zinc phosphate treatment bath.
  • the aluminum parts tends to have cracks and strains.
  • the more preferred dry film thickness of the conductive primer layer is 0.5-3 ⁇ m.
  • the chemical coating can be conducted by using known coating chemicals.
  • the preferred coating chemicals for the purpose of the present invention are zinc phosphate chemicals which contain zinc ions, phosphate ions, hydrochloric ions, nitrite ions, and, if necessary, nickel ions, nitrate ions, chlorine ions in proper proportions.
  • a typical example of the coating chemicals consists essentially of about 0.4 to about 1 g/l of zinc, about 5 to about 40 g/l of phosphate, about 0.01 to about 0.2 g/l of nitrite and about 2 to about 5 g/l of chlorate.
  • Such coating chemicals suitable as primers for forming electrodeposition coatings are exemplified in Japanese Patent Laid-Open No. 55-145180.
  • the coating chemicals may be applied to the aluminum parts and the Steel parts separately or in combination. It should be noted that the coating chemicals are not necessarily indispensable for the aluminum parts, but that the coating chemicals can provide the aluminum parts with better corrosion resistance.
  • the precoated aluminum parts is not eroded by the chemical treatment bath so that substantially no aluminum sludge is formed in the bath.
  • the electrodeposition coating composition may be either one of a cation type and an anion type which are known in the art.
  • a uniform electrodeposition coating layer having a good appearance can be formed on the precoated aluminum parts and the chemically treated steel parts.
  • an intermediate coat and/or a top coat can be formed on the assembled members thus treated.
  • electrodeposition coating can be conducted, optionally followed by the formation of an intermediate coat and/or a top coat.
  • oils, dusts, strains, etc. are attached to the conductive primer layers, it is preferable that they are removed by solvents, etc. before subsequent treatments.
  • the steps (a-1), (a-2) may be conducted in aluminum-working lines, and the steps (b-1), (b-2) ... may be conducted in assembly lines of automobile bodies.
  • Example 1 The same coating process as in Example 1 is conducted except for changing the dry film thickness of NIPPE METALCOAT P19 CLEAR to 5 ⁇ m. Various properties are evaluated, and the results are shown in Table 1.
  • a metal assembly including at least one aluminum part member and at least one steel part can be provided with chemical coatings and electrodeposition coatings without suffering from the erosion of the aluminum parts.
  • the aluminum parts coated with the conductive primer can be stamped to any shape, such as a deep-drawn shape without using a lubricating oil. This is greatly advantageous in terms of productivity because the operation of removing a lubricating oil from the stamped aluminum parts usually takes a lot of time and labor.

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

Claims (6)

  1. Verfahren zur Beschichtung einer Metallzusammenstellung aus Al-Teilen mit unbeschichteten und/oder zink- oder zinklegierungsbeschichteten Stahlteilen, umfassend die folgenden Schritte:
    Entfetten des Aluminiumteils;
    Aufbringen einer leitenden Grundierung auf dieses Aluminiumteil und
    Brennen der Grundierung zur Bildung einer organischen Überzugsschicht;
    Kombinieren des Aluminiumteils mit dem Stahlteil und Versehen der resultierenden zusammengesetzten Teile mit chemischen und galvanischen Überzügen.
  2. Verfahren gemäß Anspruch 1, weiterhin umfassend den Schritt der Bildung einer Zwischenschicht und/oder Oberschicht nach der Bildung von galvanischen Überzügen.
  3. Verfahren gemäß Anspruch 1, weiterhin umfassend den Schritt der Bildung von chemischen Überzügen auf dem Aluminiumteil vor dem Aufbringen der leitenden Grundierungsschicht darauf.
  4. Verfahren gemäß Anspruch 1, weiterhin umfassend den Schritt des Stanzens des Aluminiumteils, das mit dieser leitenden Grundierung beschichtet wurde, bevor es mit dem Stahlteil kombiniert wird.
  5. Verfahren zur Beschichtung einer Metallzusammenstellung aus Aluminiumteilen mit unbeschichteten und/oder zink- oder zinklegierungsbeschichteten Stahlteilen, umfassend folgende Schritte:
    Entfetten des Aluminiumteils;
    Aufbringen einer leitenden Grundierung auf dieses Aluminiumteil und Brennen der Grundierung zur Bildung einer organischen Überzugsschicht;
    Stanzen des Aluminiumteils;
    Kombinieren des gestanzten Aluminiumteils mit dem Stahlteil und dann Versehen der resultierenden zusammengesetzten Teile mit chemischen Überzügen.
  6. Verfahren gemäß einem oder mehreren der vorhergehenden Ansprüche, worin die Dicke der leitenden Grundierung, ausgedrückt als die Dicke eines trockenen Films, 0,1 bis 10 µm beträgt.
EP19900103924 1989-02-28 1990-02-28 Verfahren zur Beschichtung von Werkstücken mit Aluminium Expired - Lifetime EP0385448B1 (de)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP4895389 1989-02-28
JP48953/89 1989-02-28
JP181983/89 1989-07-13
JP18198389A JPH02290997A (ja) 1989-02-28 1989-07-13 異種金属などの処理方法

Publications (2)

Publication Number Publication Date
EP0385448A1 EP0385448A1 (de) 1990-09-05
EP0385448B1 true EP0385448B1 (de) 1993-08-04

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Application Number Title Priority Date Filing Date
EP19900103924 Expired - Lifetime EP0385448B1 (de) 1989-02-28 1990-02-28 Verfahren zur Beschichtung von Werkstücken mit Aluminium

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EP (1) EP0385448B1 (de)
DE (1) DE69002481T2 (de)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4036586C2 (de) * 1990-11-16 1994-05-19 Bayerische Motoren Werke Ag Verfahren zur Behandlung von beim Bau von Fahrzeugen zum Einsatz kommenden Aluminiumblech
US5395687A (en) * 1992-02-24 1995-03-07 Kawasaki Steel Corporation Surface-treated aluminum material having improved spot resistance weldability, workability, and corrosion resistance
DE10064733A1 (de) * 2000-12-22 2002-07-11 Doerken Ewald Ag Materialstück, veredelt mit einem Zinküberzug und mit appliziertem Elektrotauchlack sowie Verfahren zu seiner Herstellung

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1251127B (de) * 1959-04-08 1967-09-28 The de Havilland Aircraft Company Limited, Hatfield, Hertfordshire, Norton Grinding Wheel Company Limi ted, Welwyn Garden City, Hertfordshire (Großbritannien) Verfahren zum Überziehen eines metallischen oder nicht metallischen Korpers mit einer erosions bestandigen Schutzschicht durch Flammspritzen
GB2169618A (en) * 1985-01-14 1986-07-16 Sanden Corp Brazing aluminum
US4650696A (en) * 1985-10-01 1987-03-17 Harris Corporation Process using tungsten for multilevel metallization
DE3616567A1 (de) * 1986-05-16 1987-11-19 Gerhart Leuze Verfahren zum herstellen dicker spritzmetallschichten

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DE69002481T2 (de) 1993-12-16
DE69002481D1 (de) 1993-09-09
EP0385448A1 (de) 1990-09-05

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