EP0571246A1 - Verfahren zur Entfettung einer Vielzahl von Objekten - Google Patents

Verfahren zur Entfettung einer Vielzahl von Objekten Download PDF

Info

Publication number
EP0571246A1
EP0571246A1 EP93401217A EP93401217A EP0571246A1 EP 0571246 A1 EP0571246 A1 EP 0571246A1 EP 93401217 A EP93401217 A EP 93401217A EP 93401217 A EP93401217 A EP 93401217A EP 0571246 A1 EP0571246 A1 EP 0571246A1
Authority
EP
European Patent Office
Prior art keywords
degreasing
liquid
phase
degreasing liquid
fatty substance
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
EP93401217A
Other languages
English (en)
French (fr)
Other versions
EP0571246B1 (de
Inventor
Jean-Pierre Lallier
Daniel Bignon
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.)
Arkema France SA
Original Assignee
Elf Atochem 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 Elf Atochem SA filed Critical Elf Atochem SA
Publication of EP0571246A1 publication Critical patent/EP0571246A1/de
Application granted granted Critical
Publication of EP0571246B1 publication Critical patent/EP0571246B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

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
    • C23G5/00—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents
    • C23G5/02—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using organic solvents
    • C23G5/032—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using organic solvents containing oxygen-containing compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B08—CLEANING
    • B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
    • B08B3/00—Cleaning by methods involving the use or presence of liquid or steam
    • B08B3/04—Cleaning involving contact with liquid
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B08—CLEANING
    • B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
    • B08B7/00—Cleaning by methods not provided for in a single other subclass or a single group in this subclass
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B08—CLEANING
    • B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
    • B08B7/00—Cleaning by methods not provided for in a single other subclass or a single group in this subclass
    • B08B7/0014—Cleaning by methods not provided for in a single other subclass or a single group in this subclass by incorporation in a layer which is removed with the contaminants
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/26—Organic compounds containing oxygen
    • C11D7/261—Alcohols; Phenols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/26—Organic compounds containing oxygen
    • C11D7/264—Aldehydes; Ketones; Acetals or ketals
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/50—Solvents
    • C11D7/5004—Organic solvents
    • C11D7/5022—Organic solvents containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/40—Specific cleaning or washing processes
    • C11D2111/46—Specific cleaning or washing processes applying energy, e.g. irradiation

Definitions

  • the present invention relates to the technical field of the treatment of surfaces of manufactured objects, and, more specifically, to the industrial degreasing of a plurality of objects.
  • degreasing is to remove from the surface of an object all the fatty products and the various soiling it contains, so that this surface, made clean, regains the intrinsic physicochemical properties of the matter which forms it.
  • This material is generally a metal or a metal alloy, in particular based on copper, iron, aluminum, zinc or even a precious metal such as gold or platinum. It can also be a mineral glass, a ceramic or a plastic.
  • degreasing operations are an essential step in all production processes and lead to improved product quality and reliability.
  • residues from degreasing with chlorinated solvents mainly contain oils and greases.
  • the level of chlorinated solvent in these residues can be lowered by distillation.
  • the highly concentrated final residue must be disposed of in accordance with current legislation - (see reference: Handling of residues and waste of chlorinated solvents Chimie et Industrie, (1988), 522-525.
  • aqueous processes In terms of energy, aqueous processes generally require more energy than processes operating with chlorinated solvents mainly when a drying step is required. If this step can be avoided, the energy consumption of aqueous processes may be lower.
  • the energy considered above covers the production of the chemical substances used, cleaning proper as well as recycling and disposal of waste.
  • the object of the present invention is to find an industrial degreasing process which does not have the drawbacks of the two processes mentioned above, in particular as regards the possible impact on the environment.
  • step a / the layer of fatty substance is covered with the degreasing liquid by any suitable means and in particular by spraying with a jet or spray or else by immersion of the surface of the object in the degreasing liquid.
  • pressurized jet also causes a mechanical action facilitating the release of the layer of fatty substance covering the surface of the object.
  • the degreasing liquid being chosen in such a way that it is practically immiscible or only partially miscible with the fatty substance, there is no phenomenon of total dilution of the fatty substance by a solvent as is the case for example with chlorinated solvents.
  • the fatty substance is collected practically undiluted or very little diluted, which corresponds to a collection of the different layers of the fatty substances of the objects subjected to the process according to the invention.
  • the degreasing liquid, forming a second phase distinct from that forming the combined fatty substance, is recycled with an excellent recovery yield.
  • this liquid contains dissolved at equilibrium only a small percentage by weight of fatty substance. There is therefore no significant pollution of the degreasing liquid by the fatty substance.
  • the degreasing liquid may not contain a surfactant.
  • this has the advantage of simplifying the formulation of this same liquid.
  • the degreasing liquid does not contain an organic halogen atom.
  • organic halogen is meant a halogen entering the chemical formula of an organic compound.
  • the degreasing liquid comprises benzyl alcohol.
  • the degreasing liquid comprises diacetone alcohol.
  • the liquid can be pure diacetone alcohol or contain additives, in particular a small amount in percentage by weight of methanol or water relative to the total weight of the liquid or alternatively mono- and / or di-methyl phosphoric esters.
  • the degreasing liquid has an adhesion tension equal to or greater than 30 x 10 ⁇ 3 N / m; this adhesion tension is in fact generally greater than that of a fatty substance on a metal surface.
  • the fatty substances capable of being treated by the process can be of any kind, in particular of animal, vegetable, mineral or even synthetic origin.
  • each object is chosen so that its surface has hydrophilic polar groups. This facilitates the departure of the layer of fatty substances having a marked lipophilic character.
  • the surface to be cleaned is metallic, but it can also be made of mineral glass or ceramic, or even an organic polymer.
  • step a / the degreasing liquid can be maintained at a temperature close to room temperature, for example in a range between 15 ° C and 40 ° C.
  • step c / it is possible in step c /, to facilitate the separation of the two phases, to provide cooling of the suspension to further reduce, if necessary, the very low solubility of the fatty substance in the degreasing liquid and the very poor solubility of the degreasing liquid in the fatty substance.
  • the degreasing liquid is chosen so that it can be evaporated at a temperature less than or equal to 100 ° C. under normal pressure. This allows that after step b /, the thin layer of said liquid is evaporated covering the surface of the object.
  • the degreasing liquid is chosen to be miscible with an evaporable solvent at a temperature less than or equal to 100 ° C. under normal pressure.
  • diacetone alcohol (DA) or 4-hydroxy-4-methyl pentanone-2 which is, in the process according to the invention, one of the preferred degreasing liquids, is miscible with alcohols, esters and water.
  • diacetone alcohol has a very low vapor pressure (133 Pa at 20 ° C), 100 times lower than that of the chlorinated solvent T 111, a flash point of + 62 ° C (in closed cup), a good stability in neutral medium, at room temperature and in the presence of metals.
  • the evaporable solvent is chosen from water, acetone, methanol, ethanol or one of their mixtures.
  • step b / the surface of the object covered with a thin layer of degreasing liquid is washed with the evaporable solvent, which has the effect of eliminating this layer of liquid and temporarily replacing it with a layer of solvent.
  • the surface is then dried which gives a surface without fatty substance.
  • a second phase is obtained essentially comprising degreasing liquid.
  • the fatty substance even if it is practically immiscible with this liquid, can dissolve therein very slightly.
  • This purification can also be done by rectification.
  • Step c / can be carried out by decantation. Two distinct phases are then obtained, one of these phases covering the other, the assembly being contained in a suitable container.
  • the degreasing of each object could be carried out by immersion of each object in the second phase passing through the first then extracting each object in the opposite direction, passing last through the first phase based on fatty substances. Indeed, the fatty substance rolls or slides on the thin layer of degreasing liquid covering the surface of the object.
  • a NM 22S stainless steel plate coated with petroleum jelly oil (fully aliphatic oil) is quenched for 15 min. in the solvent tested at room temperature and without using ultrasound.
  • the plate is quickly rinsed with methanol (this alcohol is a bad degreaser), then dried at room temperature.
  • Ten drops of water are distributed on the two sides of the plate, which gives a total of 20 contact angle measurements determined with the goniometer (This angle is determined according to "Testing Surfaces for Cleanliness, WC Jones, Metal Finishing, October 1985 , p. 13 ").
  • the degreasing performance is evaluated by calculating the average.
  • the standard deviation of the measurements gives a idea of the homogeneity of degreasing.
  • This static procedure by simple soaking without using ultrasound has the advantage of only evaluating the suitability of a determined solvent.
  • the use of ultrasound, agitation, sprinkling, a rise in temperature are all factors that increase the effectiveness of degreasing.
  • a mixture of polar and non-polar oils was used to replace the above petroleum jelly oil.
  • the mixture consists of 50% by volume of vaseline oil, 25% of ELF Aleda EE 40 oil (phosphochlorinated mineral oil), 25% by volume of Etirelf BFE 53 oil (completely chlorine-free oil).
  • adhesion tensions were determined at 20 ° C, for petroleum jelly oil and the various solvents indicated in the examples below, and are expressed in milli-Newton per meter.
  • Diacetone alcohol performs better than T 111 at boiling point or T 111 in the vapor phase, which is particularly remarkable since DA is used at room temperature.
  • the diacetone alcohol additive with 3% (w / w) of methanol and used at room temperature is as effective as a boiling T 111 boiling cycle, T 111 soaking cycle at room temperature, T 111 rinsing in the vapor phase. This cycle is commonly used in degreasing machines. It is also much more efficient than just one of the 3 operations.
  • Diacetone alcohol even without methanol additive, is more effective than degreasers based on 2-methoxy-propanol-1.
  • the NM 22S stainless steel plates were coated with an oil chosen from three different oils, then degreased with a liquid composition comprising, in percentages by weight, 89% of DA, 10% of water and 1% of a mixture 50/50 by weight of mono- and di-methyl ester of phosphoric acid, neutralized with triethanolamine.
  • This example describes, with reference to the single figure, a prototype of a degreasing machine 1 with two baths using diacetone alcohol (DA). The degreasing evaluation tests are carried out according to the second procedure.
  • DA diacetone alcohol
  • This machine 1 comprises a first tank 2 partially filled with the first bath which is in the form of a first oil phase 6 covering a second phase 5 essentially comprising diacetonalcohol (DA).
  • DA diacetonalcohol
  • the supernatant phase 6 overflows into the decanter 4 by forming an oil column 7 whose height in the decanter increases during the successive cleaning of the objects.
  • This column of oil 7 floats above a layer 8 of DA coming from the overflow of the tank 2 or from the finish of the settling of the phases 5, 6.
  • This pipe and its pump make it possible to recycle the layer 8 of DA in the second phase 5 of the tank 2 or to direct the oil from column 7 to a pipe 12 for recovering the oil for its subsequent treatment as waste.
  • This machine 1 also includes a second tank 3 partially filled with a bath 13 of DA which receives the objects or parts to be degreased only after their successive passage in phases 5 and 6 of the first tank 2.
  • the degreasing path, by immersion of the objects, is shown by the dotted line 14 for an object 15.
  • the first bath removes most of the oil. This settles on the surface of the DA and is found in the upper phase of the settling tank 4. A good part of the pollution of the first bath is thus eliminated. However, some polar oils are soluble in DA. To have a very good degreasing, the installation is completed by the second bath 13 of clean DA which is used for finishing the degreasing and whose service life is very high.
  • This degreasing process at room temperature is therefore particularly effective. In addition, it causes very slow pollution of the degreasing baths. In extreme pollution conditions, it is still effective.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Detergent Compositions (AREA)
  • Physical Or Chemical Processes And Apparatus (AREA)
  • Control Of Vending Devices And Auxiliary Devices For Vending Devices (AREA)
  • Management, Administration, Business Operations System, And Electronic Commerce (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
EP93401217A 1992-05-18 1993-05-13 Verfahren zur Entfettung einer Vielzahl von Objekten Expired - Lifetime EP0571246B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR9205983A FR2691168B1 (fr) 1992-05-18 1992-05-18 Procédé de dégraissage d'une pluralité d'objets.
FR9205983 1992-05-18

Publications (2)

Publication Number Publication Date
EP0571246A1 true EP0571246A1 (de) 1993-11-24
EP0571246B1 EP0571246B1 (de) 1995-06-28

Family

ID=9429869

Family Applications (1)

Application Number Title Priority Date Filing Date
EP93401217A Expired - Lifetime EP0571246B1 (de) 1992-05-18 1993-05-13 Verfahren zur Entfettung einer Vielzahl von Objekten

Country Status (7)

Country Link
EP (1) EP0571246B1 (de)
AT (1) ATE124302T1 (de)
DE (1) DE69300217T2 (de)
ES (1) ES2075767T3 (de)
FI (1) FI100999B (de)
FR (1) FR2691168B1 (de)
NO (1) NO307573B1 (de)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0662529A1 (de) * 1994-01-11 1995-07-12 Mitsubishi Chemical Corporation Entfettungsmittel und Verfahren zur Reinigung von Öl-verschützten Gegenständen
CN120753370A (zh) * 2025-09-09 2025-10-10 内蒙古农业大学 羊皮可食化加工方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10050315C2 (de) * 2000-10-10 2003-08-21 Uhde Gmbh Verfahren zur Auflösung von Salzen in 1,2-Dichlorethan mittels Ultraschall und Vorrichtung zur Durchführung des Verfahrens

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2104104A (en) * 1981-08-14 1983-03-02 Protective Finishing Group Lim Cleaning of chemically treated articles
FR2531805A1 (fr) * 1981-02-19 1984-02-17 Videocolor Sa Procede pour enlever de minces feuilles et des restes de feuilles de supports d'ecran de tubes a rayons cathodiques
EP0360866A1 (de) * 1988-03-29 1990-04-04 Institut Khimii Nefti Sibirskogo Otdelenia Akademii Nauk Sssr Vorrichtung und verfahren zur reinigung von stücken

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2531805A1 (fr) * 1981-02-19 1984-02-17 Videocolor Sa Procede pour enlever de minces feuilles et des restes de feuilles de supports d'ecran de tubes a rayons cathodiques
GB2104104A (en) * 1981-08-14 1983-03-02 Protective Finishing Group Lim Cleaning of chemically treated articles
EP0360866A1 (de) * 1988-03-29 1990-04-04 Institut Khimii Nefti Sibirskogo Otdelenia Akademii Nauk Sssr Vorrichtung und verfahren zur reinigung von stücken

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0662529A1 (de) * 1994-01-11 1995-07-12 Mitsubishi Chemical Corporation Entfettungsmittel und Verfahren zur Reinigung von Öl-verschützten Gegenständen
US5674827A (en) * 1994-01-11 1997-10-07 Mitsubishi Chemical Corporation Degreasing cleaner and method for cleaning oil-deposited material
CN120753370A (zh) * 2025-09-09 2025-10-10 内蒙古农业大学 羊皮可食化加工方法

Also Published As

Publication number Publication date
FR2691168A1 (fr) 1993-11-19
FI932234A0 (fi) 1993-05-17
ES2075767T3 (es) 1995-10-01
DE69300217T2 (de) 1995-12-21
ATE124302T1 (de) 1995-07-15
FI100999B (fi) 1998-03-31
EP0571246B1 (de) 1995-06-28
NO931761D0 (no) 1993-05-14
FR2691168B1 (fr) 1995-01-20
DE69300217D1 (de) 1995-08-03
NO931761L (no) 1993-11-19
FI932234L (fi) 1993-11-19
NO307573B1 (no) 2000-04-25

Similar Documents

Publication Publication Date Title
CA1199756A (fr) Composition pour le demouillage des surfaces
CA2711205C (fr) Utilisation d'acide alcane sulfonique pour elimination de la rouille
FR2528323A1 (fr) Composition de dispersant
CA2096713C (fr) Compositions pour le demouillage ou le degraissage de surfaces solides
EP0571246B1 (de) Verfahren zur Entfettung einer Vielzahl von Objekten
EP0360866B1 (de) Vorrichtung und verfahren zur reinigung von stücken
CA2228785C (fr) Compositions pour le sechage de surfaces solides
CN111971374A (zh) 用于除去污染物的组合物
EP4021608A1 (de) Zusammensetzung zur trennung eines öl-wasser-gemisches
CA1118744A (fr) Procede de nettoyage de surfaces polluees par des hydrocarbures, graisses, huiles et matiere analogues et composition utilisable a cet effet
FR2737499A1 (fr) Composition nettoyante a base d'un compose hydrocarbone aliphatique comprenant au moins un substituant aromatique
EP1322742B1 (de) Verfahren und vorrichtung zum entfetten
EP0887395B1 (de) Zusammensetzung zum Trocknen von Feststoffen durch Versetzung von Wasser und Verfahren
FR2672060A1 (fr) Compositions aqueuses contenant notamment des produits d'addition d'oxydes d'alkylenes sur des alcools gras et leur procede d'utilisation pour le degraissage de metaux.
EP0821724B1 (de) Cycloalkane enthaltendes reinigungsmittel
CH696440A5 (fr) Procédé de dégraissage, lavage et séchage de pièces mécaniques utilisant des hydrocarbures non halogénés puis des solvants lessiviels dans une installation monocuve sous vide
FR2745560A1 (fr) Procede et installation pour la reduction de la dco dans les bains de rincage comportant des solvants organiques
EP0666897B1 (de) Verfahren und zusammensetzung zur entfettung der oberfläche eines gegenstandes
EA041430B1 (ru) Композиция для удаления загрязнений
EP0155208A1 (de) Oberflächenaktive Zusammensetzungen, besonders verwendbar zum Dispergieren eines Ölfilms auf einer Wasserfläche
CH616153A5 (en) Process for the manufacture of diphthaloyl peroxide
CH146799A (fr) Procédé pour le nettoyage de routes, de surfaces pavées, etc.
FR2736655A1 (fr) Procede et installation pour le decapage chimique de peintures comportees par des substrats notamment a base d'al, de zn, de mg et de leurs alliages
BE859618A (fr) Procede pour la separation des acides paraffine sulfoniques contenus dans une solution sulfonique brute
BE365572A (de)

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: 19930517

AK Designated contracting states

Kind code of ref document: A1

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

17Q First examination report despatched

Effective date: 19940923

ITF It: translation for a ep patent filed
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 IE IT LI LU NL PT SE

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 FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 19950628

Ref country code: DK

Effective date: 19950628

REF Corresponds to:

Ref document number: 124302

Country of ref document: AT

Date of ref document: 19950715

Kind code of ref document: T

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: 64339

REF Corresponds to:

Ref document number: 69300217

Country of ref document: DE

Date of ref document: 19950803

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

Ref country code: SE

Effective date: 19950928

Ref country code: PT

Effective date: 19950928

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2075767

Country of ref document: ES

Kind code of ref document: T3

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

Effective date: 19950907

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
REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

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

Ref country code: NL

Payment date: 20040505

Year of fee payment: 12

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

Ref country code: FR

Payment date: 20040510

Year of fee payment: 12

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

Ref country code: AT

Payment date: 20040512

Year of fee payment: 12

Ref country code: LU

Payment date: 20040512

Year of fee payment: 12

Ref country code: IE

Payment date: 20040512

Year of fee payment: 12

Ref country code: GB

Payment date: 20040512

Year of fee payment: 12

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

Ref country code: CH

Payment date: 20040517

Year of fee payment: 12

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

Ref country code: ES

Payment date: 20040518

Year of fee payment: 12

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

Ref country code: DE

Payment date: 20040520

Year of fee payment: 12

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

Ref country code: BE

Payment date: 20040715

Year of fee payment: 12

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: 20050513

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: 20050513

Ref country code: IE

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

Effective date: 20050513

Ref country code: GB

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

Effective date: 20050513

Ref country code: AT

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

Effective date: 20050513

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: 20050514

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: 20050531

Ref country code: CH

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

Effective date: 20050531

Ref country code: BE

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

Effective date: 20050531

BERE Be: lapsed

Owner name: S.A. *ELF ATOCHEM

Effective date: 20050531

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: 20051201

Ref country code: DE

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

Effective date: 20051201

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: 20050513

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: 20060131

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

Effective date: 20051201

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20060131

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20050514

BERE Be: lapsed

Owner name: S.A. *ELF ATOCHEM

Effective date: 20050531