EP0967301A2 - Solution décapante et activante pour le prétraitement de matériaux composites aluminium-acier avant l'étamage chimique - Google Patents

Solution décapante et activante pour le prétraitement de matériaux composites aluminium-acier avant l'étamage chimique Download PDF

Info

Publication number
EP0967301A2
EP0967301A2 EP99111464A EP99111464A EP0967301A2 EP 0967301 A2 EP0967301 A2 EP 0967301A2 EP 99111464 A EP99111464 A EP 99111464A EP 99111464 A EP99111464 A EP 99111464A EP 0967301 A2 EP0967301 A2 EP 0967301A2
Authority
EP
European Patent Office
Prior art keywords
pickling
aluminum
solutions according
activation
steel composites
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP99111464A
Other languages
German (de)
English (en)
Other versions
EP0967301A3 (fr
EP0967301B1 (fr
Inventor
Jan Eberhardt
Dieter Dr. Guhl
Frank Honselmann
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.)
Evonik Goldschmidt GmbH
Original Assignee
TH Goldschmidt AG
Goldschmidt GmbH
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 TH Goldschmidt AG, Goldschmidt GmbH filed Critical TH Goldschmidt AG
Publication of EP0967301A2 publication Critical patent/EP0967301A2/fr
Publication of EP0967301A3 publication Critical patent/EP0967301A3/fr
Application granted granted Critical
Publication of EP0967301B1 publication Critical patent/EP0967301B1/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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/1803—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces
    • C23C18/1824—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment
    • C23C18/1837—Multistep pretreatment
    • C23C18/1844—Multistep pretreatment with use of organic or inorganic compounds other than metals, first
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • 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
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions

Definitions

  • the invention relates to an aqueous preparation for pickling and activation of aluminum-steel composites before one electroless plating.
  • aluminum-steel composites are plain bearings, bushings, thrust washers, Dry sliding bearings etc. for pumps, motors and gears. After pickling activation, the aluminum and Steel surfaces of the substrate during a subsequent dip tinning even, particularly adhesive tin coatings achieved.
  • EP-A-0 278 752 discloses substrates made of pure aluminum alloys after pretreatment consisting of degreasing and pickling, with acidic tin salt electrolytes in the exchange process to tin.
  • the present invention is therefore concerned with the technical Problem, the pretreatment of the aluminum-steel composite to optimize.
  • the task of present invention therein using the known Dip tinning baths uniform, adhesive tin coatings both on the aluminum as well as on the steel surfaces of the Manufacture substrate.
  • Dilute sulfuric acid is suitable for pickling iron alloys, causes, however, at temperatures of up to 70 ° C and Diving times of a few minutes, no noticeable attack on Aluminum.
  • Hexafluorosilicic acid cleans and activates aluminum alloys, without significantly attacking iron surfaces.
  • the combination of both acids becomes the complex substrate structure made of two alloys with very different chemical and physical properties. Examples of aluminum-steel composites are plain bearings, bushings, thrust washers, Dry sliding bearings etc. for pumps, motors and gears.
  • the acid mixture still have subgroup metal cations, such as B. manganese (II), nickel (II), iron (III) ions, in concentrations of 0.05 to 1 wt .-% are added.
  • manganese (II) ions in a concentration are advantageous of 0.1% by weight at a pickling temperature of 40 ° C. and pickling times of 5 minutes.
  • nitrate and / or nitrite ions proven positive.
  • wetting agents are suitable all surfactants well wetting the substrate, which have a sufficient chemical resistance in the pickling activation electrolyte have.
  • Wetting agents such as they are used in immersion tinning baths which are used in EP-A-0 278 752, for example Polyoxyethylene ether surfactants.
  • the amount of wetting agent is preferably 1 to 20 g / l.
  • the invention thus relates to aqueous pickling activation solutions for the pretreatment of aluminum-steel composites in front of an acidic dip tinning bath, which is characterized are that they are sulfuric acid, hexafluorosilicic acid, Wetting agents, subgroup metal cations and nitrate and / or Contain nitrite ions, in particular consist of them and prepare the substrate surface in such a way that uniform, adhesive tinning is obtained.
  • the Amount of subgroup metal cations, in particular from the Group 1 and 2 and 5 to 8 of the Periodic Table of the Elements is preferably 0.05 to 1% by weight.
  • the amount of nitrite ions is preferably 0.05 to 3% by weight, while the amount of nitrate ions is preferably in the same Area.
  • Another embodiment of the invention includes a method for pickling activation of aluminum-steel composite materials, the is characterized in that pickling activation solutions with the composite at temperatures in the range of 15 to 70 ° C in Contact in the course of 1 to 9 min.
  • test pieces were used as test pieces used. These are half shells made of steel, which on the inside with an aluminum alloy (approx. 80-90% aluminum, alloyed essentially with tin and silicon) are.
  • aluminum alloy approximately 80-90% aluminum, alloyed essentially with tin and silicon
  • the substrates were degreased in a manner known per se and rinsed.
  • the substrates were placed in the solution for 5 minutes submerged.
  • the temperature of the pickling solution was 40 ° C. After The substrates were rinsed for one minute during activation.
  • Examples 1 to 3 and the Comparative Example were placed in a commercially available, acidic, external electroless tinning bath analogous to example 1 to 3 and the comparative example. It was at 30-40 ° C worked.
  • the pickling with the nitric acid pretreatment caused a strong attack on the iron surfaces.
  • the following dip tinning with dip tinning bath 1, 2 or 3 resulted in uneven tin deposits on the substrate surfaces.
  • the iron surface had no closed tin surface.
  • the adhesive strength was checked as above.
  • the adhesive film test showed significant tin detachment from the aluminum surface.
  • the tin layer thickness on the aluminum alloy was 1.8 to 4.2 ⁇ m before the test and only 0.2 to 0.5 ⁇ m after the test.
  • Tinning bath 1 Tinning bath 2 Tinning bath 3 Solution 1 very good tin deposition, excellent adhesion very good tin deposition, excellent adhesion good tin deposition, very good adhesion Solution 2 very good tin deposition, very good adhesion very good tin deposition, very good adhesion good tin deposition, very good adhesion Solution 3 very good tin deposition, very good adhesion very good tin deposition, very good adhesion good tin deposition, very good adhesion Comparative example uneven tin deposition, low adhesive strength uneven tin deposition, low adhesive strength very uneven tin deposition, low adhesive strength very uneven tin deposition, low adhesive strength

Landscapes

  • Chemical & Material Sciences (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
  • Chemically Coating (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
  • Coating With Molten Metal (AREA)
EP99111464A 1998-06-27 1999-06-12 Solution décapante et activante pour le prétraitement de matériaux composites aluminium-acier avant l'étamage chimique Expired - Lifetime EP0967301B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19828811 1998-06-27
DE19828811A DE19828811C1 (de) 1998-06-27 1998-06-27 Beizaktivierungslösung für die Vorbehandlung von Aluminium-Stahl-Verbundwerkstoffen vor einer Tauchverzinnung und Beizaktivierungsverfahren
US09/340,004 US6194369B1 (en) 1998-06-27 1999-06-25 Pickling/activation solution for the pretreatment of aluminum-steel composites prior to dip tinning

Publications (3)

Publication Number Publication Date
EP0967301A2 true EP0967301A2 (fr) 1999-12-29
EP0967301A3 EP0967301A3 (fr) 2000-06-28
EP0967301B1 EP0967301B1 (fr) 2003-11-19

Family

ID=26047094

Family Applications (1)

Application Number Title Priority Date Filing Date
EP99111464A Expired - Lifetime EP0967301B1 (fr) 1998-06-27 1999-06-12 Solution décapante et activante pour le prétraitement de matériaux composites aluminium-acier avant l'étamage chimique

Country Status (7)

Country Link
US (1) US6194369B1 (fr)
EP (1) EP0967301B1 (fr)
AT (1) ATE254678T1 (fr)
CA (1) CA2276475C (fr)
DE (2) DE19828811C1 (fr)
ES (1) ES2210902T3 (fr)
PT (1) PT967301E (fr)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6436816B1 (en) * 1998-07-31 2002-08-20 Industrial Technology Research Institute Method of electroless plating copper on nitride barrier
US8192556B2 (en) 2002-10-15 2012-06-05 Henkel Kgaa Pickling or brightening/passivating solution and process for steel and stainless steel
US10443135B1 (en) 2018-05-11 2019-10-15 Macdermid Enthone Inc. Near neutral pH pickle on multi-metals
CN111676474A (zh) * 2020-06-05 2020-09-18 贵州水钢同鑫晟金属制品有限公司 一种预应力钢绞线低温快速磷化用活化剂及其制备方法
CN113445092B (zh) * 2021-06-29 2022-10-11 钢铁研究总院 一种0Cr15Ni25Ti2MoAlVB不锈钢表面的镀铜方法

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5629751B2 (fr) * 1973-05-22 1981-07-10
US4170525A (en) * 1978-04-28 1979-10-09 Gould Inc. Process for plating a composite structure
US4192722A (en) * 1978-07-25 1980-03-11 Reynolds Metals Company Composition and method for stannate plating of large aluminum parts
IL81530A0 (en) * 1987-02-10 1987-09-16 Techno Chemica Ltd Tin coating immersion solution and coating process using the same
US5227016A (en) * 1992-02-25 1993-07-13 Henkel Corporation Process and composition for desmutting surfaces of aluminum and its alloys
JP3195144B2 (ja) * 1993-11-05 2001-08-06 新日本製鐵株式会社 含Ｃｒ鋼の高能率酸洗方法
IT1276955B1 (it) * 1995-10-18 1997-11-03 Novamax Itb S R L Processo di decapaggio e passivazione di acciaio inossidabile senza impiego di acido nitrico

Also Published As

Publication number Publication date
CA2276475A1 (fr) 1999-12-27
EP0967301A3 (fr) 2000-06-28
PT967301E (pt) 2004-04-30
US6194369B1 (en) 2001-02-27
DE59907772D1 (de) 2003-12-24
ATE254678T1 (de) 2003-12-15
EP0967301B1 (fr) 2003-11-19
ES2210902T3 (es) 2004-07-01
DE19828811C1 (de) 1999-12-09
CA2276475C (fr) 2007-05-22

Similar Documents

Publication Publication Date Title
DE3234558C2 (fr)
DE3118375A1 (de) Verfahren zur phosphatierung von metallen sowie dessen anwendung zur vorbehandlung fuer die elektrotauchlackierung
DE2856682A1 (de) Verfahren zur galvanischen erzeugung einer kupferfolie und dazu geeignetes galvanisierbad
EP0261519B1 (fr) Passivation par revêtement pour des matériaux contenant différents métaux
DE2100021A1 (de) Verfahren zum Aufbringen von Phos phatschichten auf Stahl, Eisen und Zinkoberflachen
DE3821073A1 (de) Verfahren zum galvanischen beschichten von aus aluminium oder aluminiumlegierungen gefertigten gegenstaenden mit einem vorzugsweise loetbaren metallueberzug
EP0155547A1 (fr) Procédé pour la phosphatation au zinc-calcium de surfaces métalliques à basse température de traitement
DE3211759A1 (de) Verfahren zum anodisieren von aluminiumwerkstoffen und aluminierten teilen
DE2932822C2 (de) Phosphat-Überzugslösung und Verfahren zum Erzeugen von Phosphatüberzügen auf Oberflächen von bearbeitetem oder verzinntem Stahl
EP0967301B1 (fr) Solution décapante et activante pour le prétraitement de matériaux composites aluminium-acier avant l'étamage chimique
DE3244715A1 (de) Verfahren zur phosphatierung von metalloberflaechen sowie hierfuer geeignete badloesungen
DE2917019C2 (de) Verfahren zur Metallisierung von Verbundmaterial und dazu geeignete Badzusammensetzung
DE19735314A1 (de) Verfahren zur Vorbehandlung von Bauteilen
DE1297952B (de) Verfahren zur Chromatierung von Zink- oder Aluminiumoberflaechen
EP0183925B1 (fr) Procédé pour décaper les parois des trous aménagés dans les plaques en résine synthétique destinées à la fabrication des circuits imprimés
WO1994008074A1 (fr) Procede de phosphatation de surfaces en acier galvanisees
EP0215041B1 (fr) Procede de phosphatation de surfaces metalliques
DE19740953A1 (de) Verfahren zur Phosphatierung von Stahlband
DE3049417A1 (de) "bad und verfahren zum stromlosen abscheiden von nickelueberzuegen"
EP0459549B1 (fr) Obtention de couches de conversion sur des surfaces en zinc ou en alliage de zinc
EP3728693B1 (fr) Procédé de prétraitement de nettoyage et de protection anticorrosion de composants métalliques
DE3925840A1 (de) Verfahren zur erzeugung von ueberzuegen auf zink
DE4429127C1 (de) Saure Elektrolyte zur Tauchverzinnung von Aluminiumlegierungen
DE3222140C2 (de) Anwendung des Tauch-Verzinkungsverfahrens auf die Herstellung korrosionsgeschützter Aluminiumbauteile und korrosionsgeschütztes Aluminiumbauteil
DE1947003A1 (de) Verfahren zur Erzeugung eines zusammenhaengenden Kupferueberzuges auf Aluminium und dessen Legierungen nach der elektrochemischen Austauschmethode ohne aeussere Stromquelle

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: 19990626

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AT BE CH DE ES FI FR GB IE IT LI NL PT SE

AX Request for extension of the european patent

Free format text: AL;LT;LV;MK;RO;SI

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

Owner name: GOLDSCHMIDT AG

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Kind code of ref document: A3

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

AX Request for extension of the european patent

Free format text: AL;LT;LV;MK;RO;SI

17Q First examination report despatched

Effective date: 20000922

AKX Designation fees paid

Free format text: AT BE CH DE ES FI FR GB IE IT LI NL PT SE

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH DE ES FI FR GB IE IT LI NL PT SE

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REF Corresponds to:

Ref document number: 59907772

Country of ref document: DE

Date of ref document: 20031224

Kind code of ref document: P

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: GERMAN

REG Reference to a national code

Ref country code: SE

Ref legal event code: TRGR

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

Effective date: 20040213

REG Reference to a national code

Ref country code: PT

Ref legal event code: SC4A

Free format text: AVAILABILITY OF NATIONAL TRANSLATION

Effective date: 20040217

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2210902

Country of ref document: ES

Kind code of ref document: T3

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

Effective date: 20040820

REG Reference to a national code

Ref country code: CH

Ref legal event code: PFA

Owner name: GOLDSCHMIDT GMBH

Free format text: GOLDSCHMIDT AG#GOLDSCHMIDTSTRASSE 100#45127 ESSEN (DE) -TRANSFER TO- GOLDSCHMIDT GMBH#GOLDSCHMIDTSTRASSE 100#45127 ESSEN (DE)

REG Reference to a national code

Ref country code: PT

Ref legal event code: PD4A

Free format text: GOLDSCHMIDT DE

Effective date: 20050323

REG Reference to a national code

Ref country code: FR

Ref legal event code: CJ

Ref country code: FR

Ref legal event code: CD

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

Ref country code: ES

Payment date: 20080625

Year of fee payment: 10

Ref country code: CH

Payment date: 20080624

Year of fee payment: 10

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

Ref country code: AT

Payment date: 20080620

Year of fee payment: 10

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

Ref country code: PT

Payment date: 20080603

Year of fee payment: 10

Ref country code: BE

Payment date: 20080623

Year of fee payment: 10

Ref country code: FI

Payment date: 20080625

Year of fee payment: 10

Ref country code: IT

Payment date: 20080625

Year of fee payment: 10

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

Ref country code: SE

Payment date: 20080624

Year of fee payment: 10

Ref country code: NL

Payment date: 20080618

Year of fee payment: 10

Ref country code: IE

Payment date: 20080623

Year of fee payment: 10

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

Ref country code: FR

Payment date: 20080618

Year of fee payment: 10

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

Ref country code: GB

Payment date: 20080624

Year of fee payment: 10

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: 20091214

BERE Be: lapsed

Owner name: *GOLDSCHMIDT G.M.B.H.

Effective date: 20090630

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

Ref country code: FI

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

Effective date: 20090612

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

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

Effective date: 20090612

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

Effective date: 20100101

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20100226

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: 20091214

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

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

Ref country code: LI

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

Effective date: 20090630

Ref country code: IE

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

Effective date: 20090612

Ref country code: FR

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

Effective date: 20090630

Ref country code: CH

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

Effective date: 20090630

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

Ref country code: GB

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

Effective date: 20090612

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: 20090630

Ref country code: AT

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

Effective date: 20090612

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: 20100101

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20090613

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

Ref country code: ES

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

Effective date: 20090613

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

Ref country code: IT

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

Effective date: 20090612

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: 20090613

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

Ref country code: DE

Payment date: 20180831

Year of fee payment: 20

REG Reference to a national code

Ref country code: DE

Ref legal event code: R071

Ref document number: 59907772

Country of ref document: DE