EP0505606B2 - Verfahren zum Beizen und Passivieren von rostfreiem Stahl ohne Verwendung von Salpetersäure - Google Patents

Verfahren zum Beizen und Passivieren von rostfreiem Stahl ohne Verwendung von Salpetersäure Download PDF

Info

Publication number
EP0505606B2
EP0505606B2 EP91113628A EP91113628A EP0505606B2 EP 0505606 B2 EP0505606 B2 EP 0505606B2 EP 91113628 A EP91113628 A EP 91113628A EP 91113628 A EP91113628 A EP 91113628A EP 0505606 B2 EP0505606 B2 EP 0505606B2
Authority
EP
European Patent Office
Prior art keywords
bath
pickling
maintain
acid
stainless 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
EP91113628A
Other languages
English (en)
French (fr)
Other versions
EP0505606A1 (de
EP0505606B1 (de
Inventor
Marco Bianchi
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
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=11359360&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP0505606(B2) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP0505606A1 publication Critical patent/EP0505606A1/de
Publication of EP0505606B1 publication Critical patent/EP0505606B1/de
Application granted granted Critical
Publication of EP0505606B2 publication Critical patent/EP0505606B2/de
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
    • 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
    • C23G1/08—Iron or steel
    • C23G1/086—Iron or steel solutions containing HF
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • 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

Definitions

  • a pickling system which does not involve the use of nitric acid is therefore of considerable industrial interest and various proposals have been advanced in this respect throughout the world, especially during the last ten years.
  • the process is based on the use of a pickling bath containing ferric ions, H 2 SO 4 , HF, H 2 O 2 and conventional additives such as wetting agents, emulsifiers, brighteners and anticorrosives, into which a strong air flow is continuously blown.
  • the operating temperature is generally between 30 and 70°C and preferably between 45 and 55°C.
  • the basic characteristics of the process are as follows:
  • Fe 3+ ion content of the bath on preparing the bath, an Fe 3+ ion quantity of not less than 15 g/l is introduced into the pickling solution in the form of ferric sulphate.
  • the function of this ion is to replace nitric acid as oxidizing agent in the reaction 2Fe 3+ + Fe ---> 3Fe 2+ , favoured by the bath pH conditions.
  • the correct conditions for maximizing the ferric rather than ferrous form for the iron dissolved in the bath must be continuously created.
  • the quantity of hydrogen peroxide consumed must be as small as possible. For this reason it is important to use hydrogen peroxide containing a known stabilizer effective in preventing or at least substantially retarding peroxide decomposition under the operation conditions (temperature up to 70 C, very acid bath pH, iron up to 100 g/l, presence of Ni and Cr ions).
  • a particularly suitable stabilizer is that marketed by Interox (Laporte-Solvay) under the name Interox S 333 or Interox S 333C.
  • the use of suitably stabilized H 2 O 2 in combination with the use of air blown into the bath as complementary oxidation medium has resulted in a process in which the use of H 2 O 2 is economically convenient, this never having been possible with known processes.
  • the pickling bath is prepared with an H 2 O 2 concentration of between 1 and 20 g/l, and preferably 2-5 g/l.
  • the continuous H 2 O 2 feed is regulated on the basis of the type of steel to be pickled, the surface characteristics of the material (or semi-finished product), and the quantity and quality of scale resulting from rolling or annealing. Generally an H 2 O 2 quantity of between 0.3 and 1 g/l of bath per hour of operation is fed.
  • a continuous air flow into the bath is maintained at a rate of at least 3 m 3 /m 3 of bath per hour of operation.
  • This air flow if fed in at a suitable speed, contributes to good bath agitation, this being an important condition for effective pickling as it continuously disturbs the laminar layer in proximity to the surface to be treated, hence ensuring that this surface is always in direct contact with a fresh pickling solution.
  • the blown air also oxidises the ferrous ions in combination with the hydrogen peroxide, so resulting in a considerable reduction in the consumption of this latter.
  • Control of Redox potential it is well known that the behaviour of stainless steel in acid mixtures is characterised by polarization curves which present activity, passivity and transpassivity phases for different potentials, so that the bath must be kept under those conditions in which the material does not corrode, ie the process must be operated at a potential falling within the passivity range, which can be predetermined based on the type of steel.
  • additives for this type of process are used, chosen from non-ionic surfactants acting as wetting agents, emulsifiers, brighteners and acid attack inhibitors. These additives, by mutual synergic action, improve and favour the pickling action. They are used in a total quantity of about 1 g/l of bath.
  • the process according to the invention reduces to a minimum or even prevents sludge formation with consequent further cost saving.
  • This advantage is due inter alia to an appropriate HF concentration during the process and to proper control of the concentration of ferrous ions, which are immediately and adequately oxidized to ferric ions.
  • facility for automatic control the process can be constantly controlled by automatic equipment which on the basis of analytical measurements (free and total acid, free fluoride ion content, bivalent ferrous ion content, Redox potential) meter the quantities of pickling products and stabilized hydrogen peroxide to be fed to achieve correct operating parameters.
  • analytical measurements free and total acid, free fluoride ion content, bivalent ferrous ion content, Redox potential
  • Process versatility the process of the invention is easily adaptable to all industrial stainless steel treatment plants, requiring only modest modification. It is also suitable for treating articles and semifinished products of any type, including wire, rod, strip, plate and tubes, the treatment parameters (temperature, time, concentrations) being able to undergo variation without in any way prejudicing results.
  • the process is suitable for steel of any type: martensitic, ferritic, austenitic.
  • 70 t of steel rod of average diameter 6 mm equivalent to about 5000 m 2 of the following materials: AISI 303, AISI 304 L, AISI 304 K, AISI 304 K2, AISI 316 L, AISI 316 R, AISI 316 Ti and AISI 430, were treated in an industrial tank with a useful bath capacity of 5 m 3 .
  • the initial pickling bath had the following composition:
  • the hydrogen peroxide stabilizer was Interox S 333 of Laporte Interox.
  • the additives consisted of non-ionic surfactants and acid attack inhibitors of known type for pickling baths.
  • the initially measured Redox potential was about 700 mV.
  • H 2 SO 4 was added at intervals to a total of 340 kg, as were HF to a total of 460 kg and additives of the aforesaid type to a total of 25 kg.
  • the bath temperature was maintained between 50 and 60 ° C and the air flow at 30 m 3 /h.
  • the treatment time varied between 40 and 75 minutes according to the type of steel treated, with pickling kinetics similar to if not in various cases better than those of the traditional process based on nitric acid and hydrofluoric acid, which was simultaneously compared in a parallel tank.
  • the Redox potential measured periodically, remained between 350 and 450 mV, hence ensuring optimum surface finish of the material treated.
  • the total iron content was about 100 g/l with an Fe 3+ content of 60 g/l and an Fe 2+ content of 40 g/l.
  • the ratio of the material quantity used to the test tank capacity was equal to that of normal industrial cycles.
  • the temperature was fixed at 50°C and the treatment time varied from 30 to 60 minutes depending on the type of material.
  • the new stainless steel pickling and passivation process characterised by a bath of specific composition, control of the bath during the entire operation, in particular of its Redox potential, and continuous air blowing, represents an optimum solution in terms of the technical result of the treatment, process economy (in particular due to the low H 2 O 2 consumption), and the pollution problem posed by traditional nitric acid processes.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
  • Medicines Containing Material From Animals Or Micro-Organisms (AREA)
  • Detergent Compositions (AREA)

Claims (3)

  1. Verfahren zum Beizen und Passivieren von rostfreiem Stahl, der mit einem Bad bei einer Temperatur von zwischen 30 und 70°C und vorzugsweise zwischen 45 und 55°C in Kontakt gebracht wird, und der die folgende Anfangszusammensetzung hat:
    a) H2SO4 zumindest 150 g/l
    b) Fe3+ zumindest 15 g/l
    c) HF zumindest 40 g/l
    d) H2O2 (umfassend bekannte Stabilisatoren) 1-20 g/l und vorzugsweise 2 bis 5 g/l
    e) Additive vom Typ des nicht-ionischen oberflachenaktiven Mittels (Emulgatoren, Benetzungsmittel, Aufhellmittel) und vom Typ des Säureangriffsinhibitors: etwa 1 g/l insgesamt;
       wobei in das Bad kontinuierlich geführt werden:
    ein Luftfluss von wenigstens 3 m3/h pro m3 Bad, unter Verwendung eines geeigneten Verteilungsgerätes zum Diffundieren des Flusses in die flüssige Masse;
    eine Menge an stabilisiertem H2O2 von zwischen 0,3 und 1 g/l pro Stunde, gesteuert auf der Basis des Redoxpotentials des Bads, das bei ≥ 350 mV gehalten werden muss;
    und gegebenenfalls ausreichende Mengen des Bestandteils e), um dessen Konzentration in dem Bad bei optimalen Gehalten und wobei ausreichende Mengen der Bestandteile a) und c) periodisch zugeführt werden, um ihre Konzentration im Bad bei optimalen Gehalten auf der Grundlage der Badanalyse, d.h. der Werte der freien Säure- und Fluoridionen, zu halten und um den Bad-pH bei weniger als 1 und vorzugsweise zwischen 0 und 0,5 zu halten.
  2. Verfahren nach Anspruch 1,
       dadurch gekennzeichnet, dass
       die Fe3+ -Ionen in das Anfangsbad in der Form von Ferrisulphat eingeführt werden.
  3. Verfahren nach Anspruch 1,
       durchgeführt in Kombination mit der vorherigen teilweisen Entfernung von Oxiden durch ein bekanntes Verfahren.
EP91113628A 1991-03-29 1991-08-14 Verfahren zum Beizen und Passivieren von rostfreiem Stahl ohne Verwendung von Salpetersäure Expired - Lifetime EP0505606B2 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ITMI910879A IT1245594B (it) 1991-03-29 1991-03-29 Processo di decapaggio e di passivazione di acciaio inossidabile senza acido nitrico
ITMI910879 1991-03-29

Publications (3)

Publication Number Publication Date
EP0505606A1 EP0505606A1 (de) 1992-09-30
EP0505606B1 EP0505606B1 (de) 1995-11-02
EP0505606B2 true EP0505606B2 (de) 2003-02-26

Family

ID=11359360

Family Applications (1)

Application Number Title Priority Date Filing Date
EP91113628A Expired - Lifetime EP0505606B2 (de) 1991-03-29 1991-08-14 Verfahren zum Beizen und Passivieren von rostfreiem Stahl ohne Verwendung von Salpetersäure

Country Status (9)

Country Link
EP (1) EP0505606B2 (de)
JP (1) JP2655770B2 (de)
AT (1) ATE129753T1 (de)
DE (2) DE69114265T3 (de)
DK (1) DK0505606T3 (de)
ES (1) ES2082063T5 (de)
FI (1) FI101234B (de)
GR (1) GR3018681T3 (de)
IT (1) IT1245594B (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102012024542A1 (de) * 2012-12-14 2014-06-18 Poligrat Gmbh Thixotropes Beizmittel

Families Citing this family (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IT1255655B (it) * 1992-08-06 1995-11-09 Processo di decapaggio e passivazione di acciaio inossidabile senza impiego di acido nitrico
IT1255855B (it) * 1992-10-12 1995-11-17 Cesare Pedrazzini Processo di decapaggio e di passivazione per lamiere di titanio in nastro, senza impiego di acido nitrico.
DE4237021C1 (de) * 1992-11-02 1994-02-10 Poligrat Gmbh Mittel zum Beizen der Oberfläche von Chromnickelstählen und Chromstählen sowie Verwendung des Mittels
DE4417284C2 (de) * 1993-05-24 1999-03-25 Alfred Schmitz Verfahren zum Beizen von Werkstücken aus hochlegierten Werkstoffen
WO1996009899A1 (en) * 1994-09-26 1996-04-04 E.R. Squibb & Sons, Inc. Stainless steel acid treatment
IT1276954B1 (it) * 1995-10-18 1997-11-03 Novamax Itb S R L Processo di decapaggio e di passivazione di acciaio inossidabile senza impiego di acido nitrico
FR2745301B1 (fr) * 1996-02-27 1998-04-03 Usinor Sacilor Procede de decapage d'une piece en acier et notamment d'une bande de tole en acier inoxydable
FR2772050B1 (fr) * 1997-12-10 1999-12-31 Imphy Sa Procede de decapage d'acier et notamment d'acier inoxydable
DE19755350A1 (de) * 1997-12-12 1999-06-17 Henkel Kgaa Verfahren zum Beizen und Passivieren von Edelstahl
EP0974682A1 (de) * 1998-07-18 2000-01-26 Henkel Kommanditgesellschaft auf Aktien Verfahren zur chemischen Behandlung von Metalloberflächen und dazu geeignete Anlage
IT1302202B1 (it) 1998-09-11 2000-07-31 Henkel Kgaa Processo di decapaggio elettrolitico con soluzioni esenti da acidonitrico.
IT1303814B1 (it) * 1998-12-02 2001-02-23 Henkel Kgaa Apparecchiatura e metodo per controllare processi di decapaggio peracciaio.
DE10157340A1 (de) * 2001-11-22 2003-05-28 Sms Demag Ag Verfahren und Vorrichtung zum Behandeln der Oberflächen eines Metallstrangs, insbesondere zum Beizen eines Stahlbandes
DE10160318A1 (de) 2001-12-07 2003-06-18 Henkel Kgaa Verfahren zum Beizen von martensitischem oder ferritischem Edelstahl
ES2350095T3 (es) 2002-10-15 2011-01-18 HENKEL AG & CO. KGAA Solución y procedimiento de decapado para acero inoxidable.
EP1793016A1 (de) * 2005-12-01 2007-06-06 Elpochem AG Polier- und Entgratungsmittel für Werkstücke aus Kohlenstoffstahl und Verfahren zum chemischen Polieren und Entgraten
KR100936348B1 (ko) * 2007-12-21 2010-01-12 주식회사 포스코 저 크롬계 스테인레스강의 고내식성 표면처리용액 조성물 및 이를 이용한 스테인레스강의 부동태 처리방법
CN102337548B (zh) * 2011-09-14 2012-12-05 西部钛业有限责任公司 一种钛、锆材的无酸雾酸洗方法
GB2499000A (en) 2012-02-02 2013-08-07 Henkel Ag & Co Kgaa Aqueous acidic pickling solution with hydroxylamine accelerators
GB2508827A (en) 2012-12-11 2014-06-18 Henkel Ag & Co Kgaa Aqueous compositions and processes for passivating and brightening stainless steel surfaces
JP6526406B2 (ja) * 2014-12-10 2019-06-05 株式会社Ihi ステンレス鋼部品の不動態化処理方法及びステンレス鋼部品用の不動態化処理液
CN108220937A (zh) * 2018-01-18 2018-06-29 浙江苏泊尔股份有限公司 一种不锈钢工件抗高温变色的处理方法
JP6592624B2 (ja) * 2019-01-15 2019-10-16 株式会社Ihi ステンレス鋼部品の不動態化処理方法及びステンレス鋼部品用の不動態化処理液
EP3951014B1 (de) * 2020-01-09 2024-05-22 Primetals Technologies Japan, Ltd. Verfahren zum beizen von stahlblechen und beizapparat

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS549120A (en) * 1977-06-24 1979-01-23 Tokai Electro Chemical Co Method of controlling acid cleaning liquid for stainless steel
JPS5442850A (en) * 1977-09-10 1979-04-05 Kubota Ltd Method of treating raw sewage
JPS5551514A (en) * 1978-10-12 1980-04-15 Osaka Cement Steel fiber mixing method and its device
JPS568109A (en) * 1979-07-03 1981-01-27 Toshikazu Iwasaki Reflecting telescope
ATE121804T1 (de) * 1985-01-22 1995-05-15 Ugine Sa Verfahren zum säuren beizen von stahlen, insbesondere von rostfreien stahlen.
FR2587369B1 (fr) * 1985-09-19 1993-01-29 Ugine Gueugnon Sa Procede de decapage acide de produits en acier inoxydable

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102012024542A1 (de) * 2012-12-14 2014-06-18 Poligrat Gmbh Thixotropes Beizmittel

Also Published As

Publication number Publication date
FI920580A0 (fi) 1992-02-12
ITMI910879A0 (it) 1991-03-29
ATE129753T1 (de) 1995-11-15
FI101234B (fi) 1998-05-15
EP0505606A1 (de) 1992-09-30
JP2655770B2 (ja) 1997-09-24
JPH04304391A (ja) 1992-10-27
DE69114265D1 (de) 1995-12-07
DE505606T1 (de) 1994-02-03
IT1245594B (it) 1994-09-29
DE69114265T3 (de) 2004-08-05
EP0505606B1 (de) 1995-11-02
DK0505606T3 (da) 1995-12-04
ES2082063T3 (es) 1996-03-16
FI920580A (fi) 1992-09-30
ITMI910879A1 (it) 1992-09-29
GR3018681T3 (en) 1996-04-30
DE69114265T2 (de) 1996-04-18
ES2082063T5 (es) 2003-11-01

Similar Documents

Publication Publication Date Title
EP0505606B2 (de) Verfahren zum Beizen und Passivieren von rostfreiem Stahl ohne Verwendung von Salpetersäure
JP2819378B2 (ja) ステンレス鋼のピックリング法
US5354383A (en) Process for pickling and passivating stainless steel without using nitric acid
US5843240A (en) Process for stainless steel pickling and passivation without using nitric acid
EP0769574B1 (de) Verfahren zum Beizen und Passivieren von rostfreiem Stahl ohne Salpetersäure
US8192556B2 (en) Pickling or brightening/passivating solution and process for steel and stainless steel
US5992196A (en) Process for pickling a piece of steel and in particular a sheet strip of stainless steel
EP1050605B1 (de) Verfahren zum Beizen von rostfreien Stählen ohne Salpetersäure und in Anwesenheit von Chloridionen
JPH0420996B2 (de)
US5690748A (en) Process for the acid pickling of stainless steel products
US7229506B2 (en) Process for pickling martensitic or ferritic stainless steel
CZ213093A3 (en) Method of pickling titanium products or half-finished products
US5332446A (en) Method for continuous pickling of steel materials on a treatment line
JP3216571B2 (ja) 高Ｃｒステンレス鋼の脱スケール用アルカリ溶融塩浴
JPS586980A (ja) 金属の硝酸々洗液

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

Kind code of ref document: A1

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

17P Request for examination filed

Effective date: 19930320

DET De: translation of patent claims
17Q First examination report despatched

Effective date: 19940527

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 DK ES FR GB GR IT LI LU NL SE

REF Corresponds to:

Ref document number: 129753

Country of ref document: AT

Date of ref document: 19951115

Kind code of ref document: T

REG Reference to a national code

Ref country code: DK

Ref legal event code: T3

REF Corresponds to:

Ref document number: 69114265

Country of ref document: DE

Date of ref document: 19951207

ITF It: translation for a ep patent filed
REG Reference to a national code

Ref country code: CH

Ref legal event code: NV

Representative=s name: R. A. EGLI & CO. PATENTANWAELTE

ET Fr: translation filed
REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2082063

Country of ref document: ES

Kind code of ref document: T3

REG Reference to a national code

Ref country code: GR

Ref legal event code: FG4A

Free format text: 3018681

PLBQ Unpublished change to opponent data

Free format text: ORIGINAL CODE: EPIDOS OPPO

PLBI Opposition filed

Free format text: ORIGINAL CODE: 0009260

26 Opposition filed

Opponent name: CONDOROIL IMPIANTI S.R.L.

Effective date: 19960514

PLBI Opposition filed

Free format text: ORIGINAL CODE: 0009260

REG Reference to a national code

Ref country code: CH

Ref legal event code: PUE

Owner name: ITB S.R.L. TRANSFER- NOVAMAX ITB S.R.L.

PLBQ Unpublished change to opponent data

Free format text: ORIGINAL CODE: EPIDOS OPPO

PLBQ Unpublished change to opponent data

Free format text: ORIGINAL CODE: EPIDOS OPPO

PLBI Opposition filed

Free format text: ORIGINAL CODE: 0009260

REG Reference to a national code

Ref country code: GB

Ref legal event code: 732E

PLBQ Unpublished change to opponent data

Free format text: ORIGINAL CODE: EPIDOS OPPO

PLAB Opposition data, opponent's data or that of the opponent's representative modified

Free format text: ORIGINAL CODE: 0009299OPPO

NLR1 Nl: opposition has been filed with the epo

Opponent name: CONDOROIL IMPIANTI S.R.L.

NLS Nl: assignments of ep-patents

Owner name: NOVAMAX ITB S.R.L

PLBF Reply of patent proprietor to notice(s) of opposition

Free format text: ORIGINAL CODE: EPIDOS OBSO

26 Opposition filed

Opponent name: CONDOROIL IMPIANTI S.R.L.

Effective date: 19960514

Opponent name: EKA CHEMICALS AB PATENT DEPARTMENT

Effective date: 19960629

26 Opposition filed

Opponent name: USINOR SACILOR S.A.

Effective date: 19960801

Opponent name: SOLVAY INTEROX LTD.

Effective date: 19960802

Opponent name: EKA CHEMICALS AB PATENT DEPARTMENT

Effective date: 19960629

Opponent name: CONDOROIL IMPIANTI S.R.L.

Effective date: 19960514

R26 Opposition filed (corrected)

Opponent name: CONDOROIL IMPIANTI S.R.L. * 960629 EKA CHEMICALS A

Effective date: 19960514

NLR1 Nl: opposition has been filed with the epo

Opponent name: CONDOROIL IMPIANTI S.R.L.

Opponent name: USINOR SACILOR S.A.

Opponent name: SOLVAY INTEROX LTD.

Opponent name: EKA CHEMICALS AB PATENT DEPARTMENT

REG Reference to a national code

Ref country code: FR

Ref legal event code: CA

Ref country code: FR

Ref legal event code: CD

Ref country code: FR

Ref legal event code: TP

NLR1 Nl: opposition has been filed with the epo

Opponent name: EKA CHEMICALS AB PATENT DEPARTMENT

Opponent name: SOLVAY INTEROX LTD.

Opponent name: USINOR SACILOR S.A.

Opponent name: CONDOROIL IMPIANTI S.R.L.

BECA Be: change of holder's address

Free format text: 960702 *NOVAMAX ITB S.R.L.:VIA BOSCHETTI 6, MILAN

BECN Be: change of holder's name

Effective date: 19960702

PLBF Reply of patent proprietor to notice(s) of opposition

Free format text: ORIGINAL CODE: EPIDOS OBSO

PLBF Reply of patent proprietor to notice(s) of opposition

Free format text: ORIGINAL CODE: EPIDOS OBSO

PLBF Reply of patent proprietor to notice(s) of opposition

Free format text: ORIGINAL CODE: EPIDOS OBSO

PLBF Reply of patent proprietor to notice(s) of opposition

Free format text: ORIGINAL CODE: EPIDOS OBSO

PLBF Reply of patent proprietor to notice(s) of opposition

Free format text: ORIGINAL CODE: EPIDOS OBSO

PLBQ Unpublished change to opponent data

Free format text: ORIGINAL CODE: EPIDOS OPPO

PLAB Opposition data, opponent's data or that of the opponent's representative modified

Free format text: ORIGINAL CODE: 0009299OPPO

R26 Opposition filed (corrected)

Opponent name: CONDOROIL IMPIANTI S.R.L. * 960629 EKA CHEMICALS A

Effective date: 19960514

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

Ref country code: DK

Payment date: 19980813

Year of fee payment: 8

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

Ref country code: LU

Payment date: 19980819

Year of fee payment: 8

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

Ref country code: NL

Payment date: 19980827

Year of fee payment: 8

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

Ref country code: GR

Payment date: 19980831

Year of fee payment: 8

NLR1 Nl: opposition has been filed with the epo

Opponent name: CONDOROIL IMPIANTI S.R.L.

Opponent name: USINOR SACILOR S.A.

Opponent name: SOLVAY INTEROX LTD.

Opponent name: EKA CHEMICALS AB PATENT DEPARTMENT

PLBQ Unpublished change to opponent data

Free format text: ORIGINAL CODE: EPIDOS OPPO

PLAB Opposition data, opponent's data or that of the opponent's representative modified

Free format text: ORIGINAL CODE: 0009299OPPO

RDAH Patent revoked

Free format text: ORIGINAL CODE: EPIDOS REVO

R26 Opposition filed (corrected)

Opponent name: CONDOROIL IMPIANTI S.R.L. * 960629 EKA CHEMICALS A

Effective date: 19960514

RAP2 Party data changed (patent owner data changed or rights of a patent transferred)

Owner name: HENKEL KGAA

NLR1 Nl: opposition has been filed with the epo

Opponent name: USINOR SACILOR S.A.

Opponent name: EKA CHEMICALS AB PATENT DEPARTMENT

Opponent name: CONDOROIL IMPIANTI S.R.L.

Opponent name: SOLVAY INTEROX LTD.

APAC Appeal dossier modified

Free format text: ORIGINAL CODE: EPIDOS NOAPO

APAC Appeal dossier modified

Free format text: ORIGINAL CODE: EPIDOS NOAPO

APAE Appeal reference modified

Free format text: ORIGINAL CODE: EPIDOS REFNO

NLT2 Nl: modifications (of names), taken from the european patent patent bulletin

Owner name: HENKEL KGAA

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

Ref country code: LU

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

Effective date: 19990814

Ref country code: DK

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

Effective date: 19990814

APAC Appeal dossier modified

Free format text: ORIGINAL CODE: EPIDOS NOAPO

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

Ref country code: GR

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

Effective date: 19990831

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: 20000301

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

Effective date: 20000301

REG Reference to a national code

Ref country code: DK

Ref legal event code: EBP

REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

APAC Appeal dossier modified

Free format text: ORIGINAL CODE: EPIDOS NOAPO

PLAW Interlocutory decision in opposition

Free format text: ORIGINAL CODE: EPIDOS IDOP

PUAH Patent maintained in amended form

Free format text: ORIGINAL CODE: 0009272

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

Free format text: STATUS: PATENT MAINTAINED AS AMENDED

27A Patent maintained in amended form

Effective date: 20030226

AK Designated contracting states

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

REG Reference to a national code

Ref country code: CH

Ref legal event code: AEN

Free format text: AUFRECHTERHALTUNG DES PATENTES IN GEAENDERTER FORM

REG Reference to a national code

Ref country code: SE

Ref legal event code: RPEO

REG Reference to a national code

Ref country code: CH

Ref legal event code: PUE

Owner name: HENKEL KGAA

Free format text: NOVAMAX ITB S.R.L.#VIA BOSCHETTI N.6#MILANO (IT) -TRANSFER TO- HENKEL KGAA#HENKELSTRASSE 67#40589 DUESSELDORF (DE)

ET3 Fr: translation filed ** decision concerning opposition
REG Reference to a national code

Ref country code: ES

Ref legal event code: DC2A

Date of ref document: 20030523

Kind code of ref document: T5

APAH Appeal reference modified

Free format text: ORIGINAL CODE: EPIDOSCREFNO

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

Ref country code: CH

Payment date: 20070815

Year of fee payment: 17

Ref country code: AT

Payment date: 20070813

Year of fee payment: 17

PLAB Opposition data, opponent's data or that of the opponent's representative modified

Free format text: ORIGINAL CODE: 0009299OPPO

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

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

Ref country code: AT

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

Effective date: 20080814

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: 20080831

Ref country code: CH

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

Effective date: 20080831

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

Ref country code: ES

Payment date: 20100915

Year of fee payment: 20

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

Ref country code: IT

Payment date: 20100818

Year of fee payment: 20

Ref country code: SE

Payment date: 20100812

Year of fee payment: 20

Ref country code: FR

Payment date: 20100824

Year of fee payment: 20

Ref country code: DE

Payment date: 20100812

Year of fee payment: 20

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

Ref country code: GB

Payment date: 20100811

Year of fee payment: 20

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

Ref country code: BE

Payment date: 20100818

Year of fee payment: 20

REG Reference to a national code

Ref country code: DE

Ref legal event code: R071

Ref document number: 69114265

Country of ref document: DE

REG Reference to a national code

Ref country code: DE

Ref legal event code: R071

Ref document number: 69114265

Country of ref document: DE

BE20 Be: patent expired

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

Effective date: 20110814

REG Reference to a national code

Ref country code: GB

Ref legal event code: PE20

Expiry date: 20110813

REG Reference to a national code

Ref country code: SE

Ref legal event code: EUG

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

Ref country code: GB

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 20110813

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20120206

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

Ref country code: ES

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 20110815

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

Ref country code: DE

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 20110815