EP0015021B1 - Procédé de préparation de surfaces métalliques avant dépôt de primaire par immersion électrophorétique - Google Patents

Procédé de préparation de surfaces métalliques avant dépôt de primaire par immersion électrophorétique Download PDF

Info

Publication number
EP0015021B1
EP0015021B1 EP80200097A EP80200097A EP0015021B1 EP 0015021 B1 EP0015021 B1 EP 0015021B1 EP 80200097 A EP80200097 A EP 80200097A EP 80200097 A EP80200097 A EP 80200097A EP 0015021 B1 EP0015021 B1 EP 0015021B1
Authority
EP
European Patent Office
Prior art keywords
solutions
metal surfaces
ions
brought
contact
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
Application number
EP80200097A
Other languages
German (de)
English (en)
Other versions
EP0015021A1 (fr
Inventor
Werner Dr. Rausch
Gerhard Müller
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.)
GEA Group AG
Continentale Parker Ste
Continentale Parker SA
Original Assignee
Metallgesellschaft AG
Continentale Parker Ste
Continentale Parker 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
Application filed by Metallgesellschaft AG, Continentale Parker Ste, Continentale Parker SA filed Critical Metallgesellschaft AG
Publication of EP0015021A1 publication Critical patent/EP0015021A1/fr
Application granted granted Critical
Publication of EP0015021B1 publication Critical patent/EP0015021B1/fr
Expired 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
    • C23C22/05—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
    • C23C22/36—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 containing also phosphates
    • C23C22/362—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 containing also phosphates containing also zinc cations
    • 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
    • C23C22/36—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 containing also phosphates
    • 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
    • C23C22/40—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 molybdates, tungstates or vanadates
    • C23C22/44—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 molybdates, tungstates or vanadates containing also fluorides or complex fluorides

Definitions

  • aqueous phosphating solutions are used for the treatment of surfaces made of ferrous metals and zinc, the essential constituents of which contain phosphate ions, zinc ions, cobalt, copper or nickel ions, magnesium ions, nitrite ions, fluorine and / or chlorine ions and optionally nitrate ions (DE -OS 2 049 350).
  • the solutions have contents of 3 to 20 g phosphate ions, 0.5 to 3 g zinc ions, 0.003 to 0.7 g cobalt ions or 0.003 to 0.04 g copper ions or preferably 0.05 to 3 g nickel ions, 1 to 8 g magnesium ions, 0.01 to 0.25 g of nitrite ions and 0.1 to 3 g of fluorine ions and / or 2 to 30 g of chlorine ions and optionally up to about 40 g of nitrate ions.
  • One of the ways of introducing the fluorine ions can be in the form of fluorosilicate or fluoroborate ions.
  • Paint or other fast-drying organic coatings can then be applied to the phosphate layers produced in this way.
  • a disadvantage of the coatings produced with the known solutions based on zinc phosphate or magnesium and / or calcium phosphate as the basis for the subsequent electrodeposition coating is in particular that a considerable part of the phosphate coating is separated off during the coating process, passes into the coating film and adversely affects it .
  • Essentially free of ferroions means that the treatment of non-ferrous metals does not involve the use of bath solutions that contain substantial amounts of ferroions, and the preferred treatment of steel surfaces brings them into contact with solutions that contain accelerators that oxidize ferroions.
  • Treatment solutions containing chlorate and / or nitrite are particularly suitable. It is sufficient to use as much chlorate and / or nitrite as is necessary to remove excess ferroions by oxidation. The amounts are thus dependent on the throughput and do not need to be specifically matched to the amount of zinc ions and phosphoric acid or to phosphoric acid, as is required in known processes. However, it has been found that the chlorate content should be set to at least 0.1 g / l. Larger quantities are advisable for high throughputs.
  • Solutions are advantageously used which contain vanadium compounds, preferably in amounts of 0.1 to 10 mg / l vanadium, which has proven to be particularly advantageous at high throughputs.
  • Other polyvalent cations such as Ni, Mn or Ca ions, the amount of which, however, should not exceed 0.5 gll, bring about a further improvement.
  • alkali metal ions Na, NH 4 etc.
  • the content of P0 4 is in the usual range and is about 5 to 20 g / l .
  • the phosphate layers achieved with the method according to the invention provide such a high level of corrosion protection (higher sub-walls protection) that a subsequent treatment with the known rinse agents, for. B. Cr (VI) - or Cr (III) ion-containing, practically no additional improvement.
  • the phosphate layers produced with the invention are of a quality that is otherwise only achieved by using additional rinsing agents.
  • the sheets were then rinsed with water and deionized water and then dried.
  • the layer weight achieved was 1.8 g / m 2 .
  • a modified epoxy resin varnish was then cathodically deposited on the steel sheet pretreated in this way.
  • the electrodeposition bath had room temperature, the deposition voltage and duration were 180 volts or 2 minutes.
  • the varnish was then baked at an object temperature of 190 ° C for 25 minutes.
  • the paint film thickness obtained was 15 ⁇ m, the paint layer was uniform and shiny.
  • the paint infiltration determined after the salt spray test was only less than 1 mm.

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)

Claims (7)

1. Procédé de préparation de surfaces métalliques avant dépôt de primaire par immersion élec- trophorétique par application de couches de phosphate au moyen de solutions à base de phosphate de zinc avec addition d'ions alcalins, dans lesquelles le rapport pondéral de Zn:PO4 est de 1:(12 à 110), caractérisé en ce que les surfaces métalliques sont amenées au contact de solutions qui présentent en plus une teneur en fluoborate et sont essentiellement exemptes d'ions ferreux.
2. Procédé suivant la revendication 1, caractérisé en ce que les surfaces métalliques sont amenées au contact de solutions qui contiennent du chlorate et/ou du nitrite comme accélérateur.
3. Procédé suivant la revendication 1 ou 2, caractérisé en ce que les surfaces métalliques sont amenées au contact de solutions qui contiennent des composés du vanadium dans des quantités de 0,1 à 10 mg/I de vanadium.
4. Procédé suivant la revendication 1, 2 ou 3, caractérisé en ce que les surfaces métalliques sont amenées au contact de solutions dans lesquelles le rapport pondéral Zn:PO4 est de 1:(20 à 100).
5. Procédé suivant la revendication 1, 2, 3 ou 4, caractérisé en ce que les surfaces métalliques sont amenées au contact de solutions qui contiennent du fluoborate dans des quantités de 0,3 à 2,0 g/1.
6. Utilisation du procédé selon une ou plusieurs des revendications 1 à 5 pour le traitement de surfaces d'acier.
7. Utilisation suivant la revendication 6, dans laquelle on amène les surfaces d'acier au contact de solutions qui contiennent des accélérateurs oxydant les ions ferreux en ions ferriques.
EP80200097A 1979-02-23 1980-02-05 Procédé de préparation de surfaces métalliques avant dépôt de primaire par immersion électrophorétique Expired EP0015021B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19792907094 DE2907094A1 (de) 1979-02-23 1979-02-23 Phosphatierungsloesungen
DE2907094 1979-02-23

Publications (2)

Publication Number Publication Date
EP0015021A1 EP0015021A1 (fr) 1980-09-03
EP0015021B1 true EP0015021B1 (fr) 1984-10-03

Family

ID=6063755

Family Applications (1)

Application Number Title Priority Date Filing Date
EP80200097A Expired EP0015021B1 (fr) 1979-02-23 1980-02-05 Procédé de préparation de surfaces métalliques avant dépôt de primaire par immersion électrophorétique

Country Status (10)

Country Link
US (1) US4265677A (fr)
EP (1) EP0015021B1 (fr)
JP (1) JPS5914113B2 (fr)
AU (1) AU531900B2 (fr)
CA (1) CA1134246A (fr)
DE (2) DE2907094A1 (fr)
ES (1) ES488871A0 (fr)
GB (1) GB2046312A (fr)
IT (1) IT1141231B (fr)
ZA (1) ZA80915B (fr)

Families Citing this family (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5811514B2 (ja) * 1979-05-02 1983-03-03 日本ペイント株式会社 金属表面の保護方法
JPS5811515B2 (ja) * 1979-05-11 1983-03-03 日本ペイント株式会社 金属表面にリン酸亜鉛皮膜を形成するための組成物
US4330345A (en) * 1980-12-08 1982-05-18 Chemfil Corporation Phosphate coating process and composition
DE3101866A1 (de) * 1981-01-22 1982-08-26 Metallgesellschaft Ag, 6000 Frankfurt Verfahren zur phosphatierung von metallen
DE3118375A1 (de) * 1981-05-09 1982-11-25 Metallgesellschaft Ag, 6000 Frankfurt Verfahren zur phosphatierung von metallen sowie dessen anwendung zur vorbehandlung fuer die elektrotauchlackierung
JPS58224172A (ja) * 1982-06-24 1983-12-26 Nippon Parkerizing Co Ltd カチオン電着塗装前処理方法
US4681641A (en) * 1982-07-12 1987-07-21 Ford Motor Company Alkaline resistant phosphate conversion coatings
DE3244715A1 (de) * 1982-12-03 1984-06-07 Gerhard Collardin GmbH, 5000 Köln Verfahren zur phosphatierung von metalloberflaechen sowie hierfuer geeignete badloesungen
JPS59133375A (ja) * 1983-12-03 1984-07-31 Nippon Paint Co Ltd 金属表面にリン酸亜鉛皮膜を形成するための組成物
DE3408577A1 (de) * 1984-03-09 1985-09-12 Metallgesellschaft Ag, 6000 Frankfurt Verfahren zur phosphatierung von metallen
DE3541997A1 (de) * 1985-11-28 1987-06-04 Collardin Gmbh Gerhard Verbessertes verfahren zur aktivierung von metalloberflaechen vor einer zinkphosphatierung
JPS63100185A (ja) * 1986-10-16 1988-05-02 Nippon Parkerizing Co Ltd 冷延鋼板または亜鉛めっき鋼板のりん酸塩化成処理方法
DE3636390A1 (de) * 1986-10-25 1988-04-28 Metallgesellschaft Ag Verfahren zur erzeugung von phosphatueberzuegen auf metallen
EP0327153B1 (fr) * 1988-02-03 1993-08-04 Metallgesellschaft Ag Procédé pour former des couches de phosphates sur des métaux
DE3814287A1 (de) * 1988-04-28 1989-11-09 Henkel Kgaa Polymere titanphosphate, verfahren zu ihrer herstellung und ihre verwendung zur aktivierung von metalloberflaechen vor einer zinkphosphatierung
KR100197145B1 (ko) * 1989-12-19 1999-06-15 후지이 히로시 금속표면의 인산아연 처리방법
DE4409306A1 (de) * 1994-03-18 1995-09-21 Basf Ag Verfahren zur Modifizierung von Metalloberflächen
DE4443882A1 (de) * 1994-12-09 1996-06-13 Metallgesellschaft Ag Verfahren zum Aufbringen von Phosphatüberzügen auf Metalloberflächen
US6193815B1 (en) * 1995-06-30 2001-02-27 Henkel Corporation Composition and process for treating the surface of aluminiferous metals

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1585660A (fr) * 1967-10-18 1970-01-30
GB1235293A (en) * 1967-12-12 1971-06-09 Canadian Ind Cationic electrodeposition systems
US3597283A (en) * 1969-10-08 1971-08-03 Lubrizol Corp Phosphating solutions for use on ferrous metal and zinc surfaces
US3617393A (en) * 1969-10-08 1971-11-02 Dainippon Toryo Kk Pretreatment before electrophoretic painting
US3676224A (en) * 1970-10-16 1972-07-11 Lubrizol Corp Phosphating solution with scale suppressing characteristics
JPS506418B1 (fr) * 1971-07-06 1975-03-13
DE2143957A1 (de) * 1971-09-02 1973-03-08 Metallgesellschaft Ag Verfahren zum aufbringen eines phosphatueberzuges auf eisen und stahl
US3850700A (en) * 1971-10-18 1974-11-26 Amchem Prod Method and materials for coating metal surfaces

Also Published As

Publication number Publication date
ES8200408A2 (es) 1981-11-01
US4265677A (en) 1981-05-05
ZA80915B (en) 1981-02-25
DE2907094A1 (de) 1980-09-04
DE3069330D1 (en) 1984-11-08
AU5580480A (en) 1980-08-28
JPS5914113B2 (ja) 1984-04-03
CA1134246A (fr) 1982-10-26
GB2046312A (en) 1980-11-12
JPS55131177A (en) 1980-10-11
EP0015021A1 (fr) 1980-09-03
AU531900B2 (en) 1983-09-08
IT1141231B (it) 1986-10-01
IT8020102A0 (it) 1980-02-22
ES488871A0 (es) 1981-11-01

Similar Documents

Publication Publication Date Title
EP0015021B1 (fr) Procédé de préparation de surfaces métalliques avant dépôt de primaire par immersion électrophorétique
DE1933013C3 (de) Verfahren zur Erzeugung von Schutzschichten auf Aluminium, Eisen und Zink mittels komplexe Fluoride enthaltender Lösungen
DE3118375C2 (fr)
EP0056881B1 (fr) Procédé pour la phosphatation de métaux
EP0478648B1 (fr) Procede de production d'enduits en phosphate de zinc contenant du manganese et du magnesium
EP0069950B1 (fr) Procédé de phosphatation de surfaces métalliques
EP0154367B1 (fr) Procédé de phosphatation de métaux
EP0155547B1 (fr) Procédé pour la phosphatation au zinc-calcium de surfaces métalliques à basse température de traitement
DE2232067C3 (de) Verfahren zur Vorbereitung von Metalloberflächen für die elektrophoretische Tauchlackierung
DE3932006A1 (de) Verfahren zum aufbringen von phosphatueberzuegen
EP0713539B1 (fr) Procede de phosphatage d'un feuillard d'acier galvanise sur une face
EP0111246B1 (fr) Procédé pour phosphater des objets métalliques zingués électrolytiquement
EP0134895B1 (fr) Procédé et composés pour l'application accélérée et affinée de couches de phosphate sur des surfaces métalliques
EP0039093B1 (fr) Procédé de phosphatation des surfaces de métaux et application de ce procédé
EP0486576B1 (fr) Procede pour la realisation de revetements de phosphate de zinc comportant du manganese sur de l'acier galvanise
DE2031358C3 (de) Verfahren zur Erzeugung von Schutzschichten auf Aluminium, Eisen und Zink mittels saurer, komplexe Fluoride enthaltender, Lösungen
DE2715291A1 (de) Verfahren zur herstellung amorpher, leichter, festhaftender phosphatueberzuege an eisenmetalloberflaechen
DE1257532B (de) Verfahren zum mehrstufigen Nachspuelen von Metalloberflaechen
EP0215041B1 (fr) Procede de phosphatation de surfaces metalliques
DE2352659A1 (de) Verfahren zum phosphatieren der oberflaechen metallischer gegenstaende
WO1999014397A1 (fr) Procede de phosphatation d'un feuillard d'acier
DE2506349A1 (de) Phosphatierungsmittel und verfahren zu seiner anwendung
DE2043085B2 (de) Verfahren zum Aufbringen von Zinkphosphatschichten auf elektrolytisch verzinktes Material
DE68906651T2 (de) Zusammensetzung und verfahren zur behandlung von metalloberflaechen.
DE1049659B (fr)

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

Designated state(s): BE DE FR SE

17P Request for examination filed

Effective date: 19810211

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Designated state(s): BE DE FR SE

REF Corresponds to:

Ref document number: 3069330

Country of ref document: DE

Date of ref document: 19841108

ET Fr: translation filed
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
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19911217

Year of fee payment: 13

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

Ref country code: SE

Payment date: 19920115

Year of fee payment: 13

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

Ref country code: BE

Payment date: 19920226

Year of fee payment: 13

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

Ref country code: DE

Payment date: 19920302

Year of fee payment: 13

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

Ref country code: SE

Effective date: 19930206

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

Ref country code: BE

Effective date: 19930228

BERE Be: lapsed

Owner name: METALLGESELLSCHAFT A.G.

Effective date: 19930228

Owner name: SOC. CONTINENTALE PARKER

Effective date: 19930228

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

Ref country code: FR

Effective date: 19931029

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

Ref country code: DE

Effective date: 19931103

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

EUG Se: european patent has lapsed

Ref document number: 80200097.6

Effective date: 19930912