EP0351680B1 - Utilisation d'acide p-toluène-sulfonique pour la coloration électrolytique de surfaces d'aluminium obtenues par voie anodique - Google Patents

Utilisation d'acide p-toluène-sulfonique pour la coloration électrolytique de surfaces d'aluminium obtenues par voie anodique Download PDF

Info

Publication number
EP0351680B1
EP0351680B1 EP89112555A EP89112555A EP0351680B1 EP 0351680 B1 EP0351680 B1 EP 0351680B1 EP 89112555 A EP89112555 A EP 89112555A EP 89112555 A EP89112555 A EP 89112555A EP 0351680 B1 EP0351680 B1 EP 0351680B1
Authority
EP
European Patent Office
Prior art keywords
ammonium
alkaline earth
salts
alkali metal
earth metal
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
EP89112555A
Other languages
German (de)
English (en)
Other versions
EP0351680A1 (fr
Inventor
Dieter Dr. Brodalla
Loert Dr. De Riese-Meyer
Jürgen Lindener
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
Priority to AT89112555T priority Critical patent/ATE82022T1/de
Publication of EP0351680A1 publication Critical patent/EP0351680A1/fr
Application granted granted Critical
Publication of EP0351680B1 publication Critical patent/EP0351680B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/14—Producing integrally coloured layers
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/18—After-treatment, e.g. pore-sealing
    • C25D11/20—Electrolytic after-treatment
    • C25D11/22—Electrolytic after-treatment for colouring layers

Definitions

  • the invention relates to the electrolytic coloring of anodically produced surfaces of aluminum and / or aluminum alloys in aqueous electrolytes containing silver salt by means of alternating current and using p-toluenesulfonic acid.
  • Chemical Abstracts 105 (10), Unit 87 431z, discloses the electrolytic coloring of aluminum using an electrolyte containing silver nitrate and sulfuric acid. The coloring process was used for the surface treatment of lamps and aluminum workpieces. It is described that the problems that usually arise from dyeing with organic dyes are solved.
  • JP-A 55-131195 describes the electrolytic coloring of aluminum with a number of metal salts.
  • said electrolytic coloring is carried out.
  • Metal Finishing Abstracts, Vol 23 (1981), No. 1, page 25 F also describes a process for the electrolytic coloring of anodized aluminum, in which an electrolysis bath, the salts of nickel Contains cobalt, tin or copper in the form of sulfate, sulphamate, oxalate, tartrate or phosphate.
  • the bath also contains 5 to 100 g / l p-toluenesulfonate sodium salt or similar compounds and unsaturated compounds, for example formaldehyde, benzylidene acetone, pyridine, quinoline, butynediol, ethylene cyanohydrin, thiourea or azo dyes.
  • the coloring tape contains a silver salt, for example 0.5 g / l silver sulfate and 1 g / l tin sulfate, 20 g / l sulfosalicylic acid, 20 g / l magnesium sulfate and 10 g / l sulfuric acid.
  • a silver salt for example 0.5 g / l silver sulfate and 1 g / l tin sulfate, 20 g / l sulfosalicylic acid, 20 g / l magnesium sulfate and 10 g / l sulfuric acid.
  • the aluminum treated in this way is then immersed in an acidic bath containing, for example, sulfuric acid or nitric acid, or in a neutral bath containing, for example, thiosulfate or thiogluconate. This results in permanent and light-colored layers, for example light-orange colored layers.
  • the invention thus relates to the use of p-toluenesulfonic acid and / or its water-soluble alkali metal, ammonium and / or alkaline earth metal salts for the electrolytic coloring of anodized surfaces of aluminum and / or aluminum alloys, which is characterized in that aqueous electrolyte solutions are used, the 0 , Contain 1 to 10 g / l silver in the form of water-soluble salts, and apply alternating current or alternating current superimposed on direct current.
  • the electrolytic coloring according to the invention also has the decorative effect has the advantage that it can be easily and permanently over-dyed with organic dyes and so, for example, with dyes such as Sanodalblau R from Sandoz AG, Basel, Switzerland, a lightfast green can also be achieved as a combination dyeing.
  • p-toluenesulfonic acid also includes their water-soluble alkali metal salts and / or their water-soluble alkaline earth metal salts.
  • p-toluenesulfonic acid is used in the form of the monohydrate because of its better solubility in water.
  • p-toluenesulfonic acid is used in an amount of 3 to 100 g / l electrolytic solution, while a preferred embodiment of the present invention consists in using 5 to 25 g / l p-toluenesulfonic acid.
  • the electrolytic solution contains the silver in the form of nitrate, acetate and / or sulfate.
  • the electrolyte solution contains 0.3 to 1.2 g / l of silver in the form of water-soluble salts, preferably in the form of nitrate, acetate and / or sulfate.
  • the use of silver sulfate is preferred.
  • a further embodiment of the present invention consists in that the electrolyte solution, if desired, 2.5 to 100 g / l sulfuric acid and / or its alkali metal, ammonium and / or contains alkaline earth metal salts.
  • a particular embodiment of the present invention is that an electrolyte solution is used which contains 2.5 to 25 g / l sulfuric acid.
  • the alkali metal, ammonium and / or alkaline earth metal salts which can be used instead of or together with this are those of sodium, potassium, ammonium, magnesium or mixtures thereof, preferably in the form of the sulfates and / or the acetates.
  • magnesium sulfate together with or instead of the sulfuric acid is particularly preferred.
  • a terminal voltage of 4 to 20 V is set according to the invention.
  • a preferred embodiment of the present invention is to set the terminal voltage in the range from 8 to 16 V.
  • Alternating current or alternating current superimposed with direct current is used.
  • the "alternating current superimposed with direct current” is equivalent to "direct current superimposed with alternating current”.
  • the voltage applied to the bath is defined as the terminal voltage.
  • the generation of gold tones is preferred within the scope of the invention. These preferably result in a voltage range of 8 to 16 V, the treatment times should be shorter the higher the voltage is selected. In this sense, the treatment times are usually in the range of 0.5 to 3 minutes.
  • brown tones result in dyeing times of more than 3 min and higher voltage values, i.e. especially more than 10 V.
  • Voltage values of more than 16 V should generally be avoided with dyeing times of more than 3 minutes, since otherwise the oxide layer may flake off.
  • Electrolyte solutions which contain further cations can also be used within the scope of the invention. Preferred as such are: Cu (II), Ni (II) and Co (II). This results in a wide range of other warm colors.
  • test sheets (dimension 50 mm x 40 mm x 1 mm) made of the material Almg 1 (DIN material no. 3.3315) were used.
  • the sheets were degreased, pickled and pickled using conventional methods.
  • the degreasing was carried out with an alkaline cleaner containing borates, carbonates, phosphates and nonionic surfactants (P3-almeco R 18, Henkel KGaA, Düsseldorf), bath concentration 5% by weight at 70 ° C. in the course of 15 minutes.
  • a mixture (3: 1) of sodium hydroxide and a pickling agent containing alkali, alcohols and salts of inorganic acids (P3-almeco R 46, Henkel KGaA, Duesseldorf) was used.
  • the pickling was carried out using an acidic pickling agent containing salts of inorganic acids and inorganic acids (P3-almeco R 90, Henkel KGaA, Düsseldorf), in a concentration of 15% by weight, at a temperature of 20 ° C. in the course of 3 minutes .
  • P3-almeco R 90 Henkel KGaA, Düsseldorf
  • the subsequent anodization was carried out using the direct current sulfuric acid method; Bath composition: 180 g / l sulfuric acid, 10 g / l aluminum, air injection: 8 m3 / m2h, temperature: 20 ° C, DC voltage 15 V, current density 1.4 A / dm2, anodizing time: 2700 to 3600 sec, depending on the requirements for the production of a constant oxide layer of 20 ⁇ m.
  • the sheets were then rinsed again and subjected to a compression process. At a temperature of about 98 ° C in the course of 60 min. (corresponding to 3 min./ ⁇ m) the compression.
  • a sealing coating inhibitor based on polycarboxylic acids and ammonium acetate was used as a buffer substance (P3-almeco R seal SL, Henkel KGaA, Düsseldorf).

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
  • Electrochemical Coating By Surface Reaction (AREA)
  • Detergent Compositions (AREA)
  • Electrolytic Production Of Metals (AREA)
  • Chemical Treatment Of Metals (AREA)

Claims (11)

1) Utilisation d'acide p-toluène-sulfonique et/ou de ses sels solubles dans l'eau de métal alcalin, ammonium et/ou métal alcalino-terreux pour colorer électrolytiquement des surfaces obtenues anodiquement d'aluminium et/ou d'alliages d'aluminium, caractérisée en ce qu'on met en oeuvre des solutions aqueuses d'électrolyte, qui contiennent 0,1 à 10 g/l d'argent, sous forme de sels solubles dans l'eau, et qu'on utilise du courant alternatif en du courant alternatif superposé à du courant continu.
2) Utilisation selon la revendication 1, caractérisée en ce qu'on utilise de l'acide p-toluène-sulfonique et/ou ses sels solubles dans l'eau de métal alcalin, ammonium et/ou métal alcalino-terreux, à raison de 3 à 100 g/l de solution d'électrolyte.
3) Utilisation selon la revendication 2, caractérisée en ce qu'on utilise de l'acide p-toluène-sulfonique et/ou ses sels solubles dans l'eau de métal alcalin, ammonium et/ou métal alcalino-terreux, à raison de 5 à 25 g/l de solution d'électrolyte.
4) Utilisation selon les revendications 1 à 3, caractérisée en ce qu'on utilise des solutions d'électrolyte qui contiennent de l'argent sous forme de nitrate, acétate et/ou sulfate.
5) Utilisation selon les revendications 1 à 3, caractérisée en ce qu'on utilise des solutions d'électrolyte, qui contiennent de 0,3 à 1,2 g/l d'argent sous forme de sels solubles dans l'eau, de préférence sous forme de nitrate, acétate et/ou sulfate.
6) Utilisation selon les revendications 1 à 5, caractérisée en ce qu'on utilise des solutions d'électrolyte qui contiennent 2,5 à 100 g/l d'acide sulfurique et/ou ses sels de métal alcalin, ammonium et/ou de métal alcalino-terreux.
7) Utilisation selon la revendication 6, caractérisée en ce qu'on utilise des solution d'électrolyte qui contiennent 2,5 à 25 g/l d'acide sulfurique et/ou ses sels de métal alcalin, ammonium et/ou de métal alcalino-terreux.
8) Utilisation selon les revendications 1 à 7, caractérisée en ce qu'on utilise comme sels de métal alcalin, ammonium et/ou de métal alcalino-terreux les sulfates de sodium, potassium, magnésium, ammonium et/ou leurs acétates ainsi que leurs mélanges.
9) Utilisation selon les revendications 1 à 8, caractérisée en ce que les solutions d'électrolyte contiennent d'autres cations de métal de transition de préférence Cu (II), Ni (II) et Co (II).
10) Utilisation selon les revendications 1 à 9, caractérisée en ce qu'on établit une tension aux bornes de 4 à 20 V.
11) Utilisation selon la revendication 10, caractérisée en ce qu'on établit une tension aux bornes comprise entre 8 et 16 V.
EP89112555A 1988-07-19 1989-07-10 Utilisation d'acide p-toluène-sulfonique pour la coloration électrolytique de surfaces d'aluminium obtenues par voie anodique Expired - Lifetime EP0351680B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT89112555T ATE82022T1 (de) 1988-07-19 1989-07-10 Verwendung von p-toluolsulfonsaeure zum elektrolytischen faerben anodisch erzeugter oberflaechen von aluminium.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3824402A DE3824402A1 (de) 1988-07-19 1988-07-19 Verwendung von p-toluolsulfonsaeure zum elektrolytischen faerben anodisch erzeugter oberflaechen von aluminium
DE3824402 1988-07-19

Publications (2)

Publication Number Publication Date
EP0351680A1 EP0351680A1 (fr) 1990-01-24
EP0351680B1 true EP0351680B1 (fr) 1992-11-04

Family

ID=6358983

Family Applications (1)

Application Number Title Priority Date Filing Date
EP89112555A Expired - Lifetime EP0351680B1 (fr) 1988-07-19 1989-07-10 Utilisation d'acide p-toluène-sulfonique pour la coloration électrolytique de surfaces d'aluminium obtenues par voie anodique

Country Status (12)

Country Link
US (1) US4917780A (fr)
EP (1) EP0351680B1 (fr)
JP (1) JPH0273993A (fr)
KR (1) KR900001886A (fr)
AT (1) ATE82022T1 (fr)
AU (1) AU609320B2 (fr)
BR (1) BR8903540A (fr)
DE (2) DE3824402A1 (fr)
ES (1) ES2035994T3 (fr)
GR (1) GR3006151T3 (fr)
NZ (1) NZ229977A (fr)
ZA (1) ZA895471B (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4244021A1 (de) * 1992-12-24 1994-06-30 Henkel Kgaa Verfahren zur elektrolytischen Wechselstromeinfärbung von Aluminiumoberflächen
DE10033434A1 (de) 2000-07-10 2002-01-24 Basf Ag Verfahren zur Herstellung von goldfarbenen Oberflächen von Aluminium oder Aluminium-Legierungen mittels silbersalzhaltigen Formulierungen
CN102808208B (zh) * 2012-08-29 2013-07-24 广东豪美铝业股份有限公司 一种铝材着金色的方法
KR101890681B1 (ko) 2016-12-27 2018-09-28 엘에스산전 주식회사 기중 차단기의 위치표시장치

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5249408B2 (fr) * 1972-11-21 1977-12-17
JPS547267B2 (fr) * 1973-09-21 1979-04-05
US4128460A (en) * 1976-09-13 1978-12-05 Daiwa Kasei Kenkyujo Kabushiki Kaisha Coloring by electrolysis of aluminum or aluminum alloys
FR2380357A1 (fr) * 1977-02-11 1978-09-08 Pechiney Aluminium Procede de coloration electrolytique de l'aluminium et de ses alliages non anodises
US4226680A (en) * 1977-06-06 1980-10-07 Alcan Research And Development Limited Process for electrolytic coloration of anodized aluminium
JPS55131195A (en) * 1979-03-30 1980-10-11 Sumitomo Light Metal Ind Ltd Electrolytic coloring method for aluminum
US4430169A (en) * 1982-03-04 1984-02-07 Woods Jack L Method of producing green coatings on aluminum and aluminum alloys

Also Published As

Publication number Publication date
JPH0273993A (ja) 1990-03-13
AU609320B2 (en) 1991-04-26
US4917780A (en) 1990-04-17
ATE82022T1 (de) 1992-11-15
ES2035994T3 (es) 1993-05-01
KR900001886A (ko) 1990-02-27
BR8903540A (pt) 1990-03-13
NZ229977A (en) 1990-08-28
ZA895471B (en) 1990-03-28
AU3824489A (en) 1990-01-25
GR3006151T3 (fr) 1993-06-21
DE3824402A1 (de) 1990-01-25
EP0351680A1 (fr) 1990-01-24
DE58902601D1 (de) 1992-12-10

Similar Documents

Publication Publication Date Title
DE1446002C3 (de) Verfahren zur Herstellung gleichmäßig gefärbter Oxidschichten auf Aluminium und Aluminiumlegierungen durch anodische Oxydation
EP1301656A1 (fr) Procede de traitement de surfaces de pieces en aluminium ou en alliages d'aluminium a l'aide de formulations contenant de l'acide alcanesulfonique
DE2239255C3 (de) Wäßrige alkalische Losung zum Aufbringen eines korrosions- und wärmebeständigen, beschichtbaren und leicht einf ärbbaren Oxidüberzuges auf ein Substrat aus Aluminium oder einer Aluminiumlegierung
EP0675976B1 (fr) Procede d'encrage electrolytique de surfaces en aluminium a l'aide de courant alternatif
DE1260266B (fr)
DE3334628A1 (de) Oberflaechenbehandlung fuer aluminium oder aluminiumlegierungen
EP0351680B1 (fr) Utilisation d'acide p-toluène-sulfonique pour la coloration électrolytique de surfaces d'aluminium obtenues par voie anodique
DE2633212C3 (de) Verfahren zur Erzeugung einer grün gefärbten Oxidschicht auf Aluminium oder Aluminiumlegierungen
DE3718849A1 (de) Elektrolytisches einfaerben von anodisiertem aluminium
DE2332239A1 (de) Anionische 1:2-chromkomplexverbindung, ihre herstellung und verwendung
DE349227C (de) Verfahren zum Faerben metallischer Flaechen
DE2413149C3 (de) Verfahren zum kathodischen Gleichstrom-Farben von anodischen Oxidschichten auf Aluminium oder Aluminiumlegierungen
DE3522117C2 (fr)
CH682240A5 (fr)
DE1496862C3 (de) Verfahren zum Erzeugen schwarzer Überzüge auf einer Aluminiumlegierung des Typs 6063 durch anodische Oxydation
DE2106388C3 (de) Verfahren zur elektrolytischen Herstellung von blauen Oxidschichten auf Aluminiumlegierungen
AT340219B (de) Verfahren zum erzeugen von kombinationsfarbungen auf einem werkstuck aus aluminium oder aluminiumlegierungen
DE2538622C3 (de) Verfahren zum elektrolytischen Färben von anodisch erzeugten Oxidschichten auf Werkstoffen aus Aluminium oder dessen Legierungen
DE1906225C (de) Bad zur anodischen Herstellung gefärbter Oxidschichten auf Aluminium und Aluminiumlegierungen
DE1963587C (de) Verfahren zur Herstellung von gleichmäßig gefärbten anodischen Oxidüberzügen auf Aluminium oder Aluminiumlegierungen
DE2416027A1 (de) Verfahren zum herstellen eines gefaerbten oxidfilms auf der oberflaeche von aluminium oder einer aluminiumlegierung
DE2550431A1 (de) Verfahren zur herstellung von gefaerbten ueberzuegen durch anodische oxydation auf aluminium oder aluminiumlegierungen
DE2220818A1 (de) Verfahren zur faerbung von aluminium und aluminiumlegierungen
DE2538622A1 (de) Verfahren zum elektrolytischen faerben von anodisch erzeugten oxidschichten auf werkstoffen aus aluminium oder dessen legierungen
DE1913573A1 (de) Elektrolytisches Verfahren zur Erzeugung farbiger Oxidschichten auf Aluminium und Aluminiumlegierungen

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: 19891027

AK Designated contracting states

Kind code of ref document: A1

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

17Q First examination report despatched

Effective date: 19910806

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 FR GB GR IT LI NL SE

REF Corresponds to:

Ref document number: 82022

Country of ref document: AT

Date of ref document: 19921115

Kind code of ref document: T

ET Fr: translation filed
REF Corresponds to:

Ref document number: 58902601

Country of ref document: DE

Date of ref document: 19921210

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: 19920205

REG Reference to a national code

Ref country code: GR

Ref legal event code: FG4A

Free format text: 3006151

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2035994

Country of ref document: ES

Kind code of ref document: T3

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GR

Payment date: 19941129

Year of fee payment: 6

EAL Se: european patent in force in sweden

Ref document number: 89112555.1

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

Ref country code: DE

Payment date: 19950621

Year of fee payment: 7

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

Ref country code: GR

Free format text: THE PATENT HAS BEEN ANNULLED BY A DECISION OF A NATIONAL AUTHORITY

Effective date: 19960131

REG Reference to a national code

Ref country code: GR

Ref legal event code: MM2A

Free format text: 3006151

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

Ref country code: DE

Effective date: 19970402

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

Ref country code: GB

Payment date: 19970701

Year of fee payment: 9

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

Ref country code: FR

Payment date: 19970709

Year of fee payment: 9

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

Ref country code: AT

Payment date: 19970715

Year of fee payment: 9

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

Ref country code: SE

Payment date: 19970716

Year of fee payment: 9

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

Ref country code: ES

Payment date: 19970729

Year of fee payment: 9

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

Ref country code: CH

Payment date: 19970730

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: 19970731

Year of fee payment: 9

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

Ref country code: BE

Payment date: 19970828

Year of fee payment: 9

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: 19980710

Ref country code: AT

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

Effective date: 19980710

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: 19980711

Ref country code: ES

Free format text: LAPSE BECAUSE OF THE APPLICANT RENOUNCES

Effective date: 19980711

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: 19980731

Ref country code: CH

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

Effective date: 19980731

Ref country code: BE

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

Effective date: 19980731

BERE Be: lapsed

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

Effective date: 19980731

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: 19990201

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

Effective date: 19980710

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

EUG Se: european patent has lapsed

Ref document number: 89112555.1

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

Ref country code: FR

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

Effective date: 19990331

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

Effective date: 19990201

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20001009

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;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

Effective date: 20050710