EP1046703B1 - Reinigungs- oder Trocknungszusammensetzungen auf Basis von Pentafluorbutan, Methylenchlorid, Methanol und Decafluorpentan - Google Patents

Reinigungs- oder Trocknungszusammensetzungen auf Basis von Pentafluorbutan, Methylenchlorid, Methanol und Decafluorpentan Download PDF

Info

Publication number
EP1046703B1
EP1046703B1 EP00400777A EP00400777A EP1046703B1 EP 1046703 B1 EP1046703 B1 EP 1046703B1 EP 00400777 A EP00400777 A EP 00400777A EP 00400777 A EP00400777 A EP 00400777A EP 1046703 B1 EP1046703 B1 EP 1046703B1
Authority
EP
European Patent Office
Prior art keywords
cleaning
methanol
azeotropic
pentafluorobutane
decafluoropentane
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
EP00400777A
Other languages
English (en)
French (fr)
Other versions
EP1046703A1 (de
Inventor
Pascal Michaud
Jean-Jacques Martin
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
Atofina 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 Atofina SA filed Critical Atofina SA
Publication of EP1046703A1 publication Critical patent/EP1046703A1/de
Application granted granted Critical
Publication of EP1046703B1 publication Critical patent/EP1046703B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • 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
    • C11D7/5036—Azeotropic mixtures containing halogenated solvents
    • C11D7/5068—Mixtures of halogenated and non-halogenated solvents
    • C11D7/5077—Mixtures of only oxygen-containing solvents
    • C11D7/5081—Mixtures of only oxygen-containing solvents the oxygen-containing solvents being alcohols only

Definitions

  • the present invention relates to the field of fluorinated hydrocarbons and more particularly for the subject of new compositions which can be used for cleaning or drying solid surfaces.
  • 1,1,2-Trichloro-1,2,2-trifluoroethane (known in the trade under the designation F113) has been widely used in industry for cleaning and degreasing very diverse solid surfaces (metal parts, glasses, plastics, composites), for which an absence - or at least a residual content as low as possible - in impurities, especially organic in nature, is required.
  • the F 113 was suitable particularly well for this use because of its non-aggressive nature towards used materials.
  • This product has been used in particular in the field of manufacturing printed circuits, to remove residues from substances used to improve the quality of welds (designated by the term weld flux). This operation elimination is designated in the art by the term "defluxing".
  • F113 to degreasing parts heavy metal and cleaning of high quality and large mechanical parts precision such as, for example, gyroscopes and military, aerospace or medical.
  • the F113 is most often associated with other organic solvents (eg methanol), to improve its cleaning capacity.
  • azeotropic or quasi-azeotropic mixtures a mixture of compounds generally miscible chemicals which under certain specific conditions of proportions, temperature and pressure, tip at substantially constant temperature while retaining substantially the same composition.
  • quasi-azeotropic mixture When heated to reflux, such quasi-azeotropic mixture is in equilibrium with a vapor phase whose composition is substantially the same as that of the liquid phase.
  • Such azeotropic behavior or almost azeotropic is desirable to ensure satisfactory operation of machines in which the abovementioned cleaning operations are carried out, and in particular for recycling the cleaning fluid by distillation.
  • the F113 is also used in the fields, in particular in optics, for which are required to have water-free surfaces, i.e. surfaces where water is only present in traces undetectable by the measurement method (method Karl Fisher).
  • F113 is used in drying operations (or dewetting) of said surfaces, in combination with surfactants hydrophobic.
  • compositions based on F113 are now prohibited since the F113 is one of the chlorofluorocarbons (CFCs) suspected of attacking or degrading ozone stratospheric.
  • CFCs chlorofluorocarbons
  • F113 can be replaced by 1,1-dichloro-1-fluoroethane (known as F141b), but the use of this substitute is already regulated because, although weak, its destructive effect on ozone is not zero.
  • F141b 1,1-dichloro-1-fluoroethane
  • Application EP 0512885 describes a composition comprising from 93 to 99% by weight of 1,1,1,3,3-pentafluorobutane and from 1 to 7% of methanol, usable as substitute for F113.
  • 1,1,1,3,3-pentafluorobutane also known in the art as denomination of F365mfc, has no destructive effect with respect to ozone.
  • EP 0856578 describes a composition comprising from 10 to 90% in weight of 1,1,1,2,3,4,4,5,5,5,5-decafluoropentane, 10 to 90% of dichloromethane, and 0 10% methanol, also usable as a substitute for F113.
  • 1,1,1,2,3,4,4,5,5,5-decafluoropentane known in the art under the name of 43-10mee is also devoid of destructive effect with respect to ozone.
  • the object of the invention is to propose other compositions capable of being used as a substitute for F113 or F141b, and devoid of any destructive effect on it of ozone.
  • compositions according to the invention make it possible to obtain very good results for cleaning and degreasing of solid surfaces, as well as in drying and dewetting of surfaces.
  • these compositions do not have a point flash under standard determination conditions (ASTM D 3828) and allow therefore to work safely.
  • compositions according to the invention can be easily prepared by simple mixing of the constituents.
  • the 43-10 mee is commercially available; 365mfc can be prepared by at least one of the following methods: Zh. Org. Khim. 1980, 1401-1408 and 1982, 946 and 1168 ;. Zh. Org. Khim. 1988, 1558. J. Chem. Soc Perk. I, 1980, 2258; J Chem. Soc Perk. Trans, 2. 1983, 1713; J. Chem. Soc. C Perk. Trans, 2.198, 1713: J. Chem. Soc. C 1969, 1739: Chem. Soc. 1949, 2860: Zh. Anal. Khim, 1981 36 (6), 1125; J. Fluorite Chem.
  • cleaning compositions based on 365 mfc, dichloromethane, methanol and 43-10 mee can, if desired, be protected against attack chemicals resulting from their contact with water (hydrolysis), with light metals (constituting the solid surfaces to be cleaned), and / or against radical attacks likely to occur in cleaning processes, adding a usual stabilizer such as, for example, nitroalkanes (especially nitromethane, nitroethane, nitropropane), acetals (dimethoxymethane) or ethers (1,4-dioxane, 1,3-dioxolane).
  • a usual stabilizer such as, for example, nitroalkanes (especially nitromethane, nitroethane, nitropropane), acetals (dimethoxymethane) or ethers (1,4-dioxane, 1,3-dioxolane).
  • the proportion of stabilizer can range from 0.01 to 5% relative to the total weight of the composition.
  • compositions according to the invention other solvents such as alcohols, ketones, ethers, acetals, esters, hydrocarbons, solvents chlorinated, brominated, iodinated, sulfones, or water, in the presence of surfactants (anionics, non-ionic or cationic) fluorinated, silicone or not, in order to obtain properties specific, especially in dry cleaning.
  • solvents such as alcohols, ketones, ethers, acetals, esters, hydrocarbons, solvents chlorinated, brominated, iodinated, sulfones, or water
  • surfactants anionics, non-ionic or cationic fluorinated, silicone or not
  • compositions according to the invention can be used in the same applications and be implemented in the same manner as the compositions prior to F113 or F141b. They are therefore particularly suitable for use for cleaning and degreasing solid surfaces, preferably for defluxing of printed circuits, as well as for surface drying operations.
  • a surfactant hydrophobic soluble in the composition, in order to further improve the elimination of water from surfaces to be treated, until 100% elimination is achieved.
  • the composition generally comprises from 92 to 99.5% of the quaternary azeotropic composition, and 0.05 to 8% surfactant.
  • compositions according to the invention one can cite in particular the implementation in devices adapted to the cleaning and / or drying of surfaces, as well as by aerosol.
  • compositions according to the invention can be packaged with, as propellant, 134a (or 227e of formula CF 3 CHF-CF 3 ), and their mixture with 152a and / or DME (Dimethylether) to offer additional cleaning possibilities, especially at room temperature.
  • the compositions according to the invention thus conditioned do not have a flame length, according to standard 609F of the European Aerosol Federation (Brussels, Belgium) (Determination of the ignition distance of a spray or a jet emitted at from an aerosol container).
  • compositions can also be used as a blowing agent for polyurethane foams, as a dry cleaning agent for textiles, and as a fluid refrigerant.
  • 50 g of 43-10 are introduced into the distiller of a distillation column (30 trays) mee and 100 g of 365mfc, 50 g of methanol and 100 g of dichloromethane. The mixture is then heated at reflux for an hour to bring the system to balance.
  • a fraction of approximately 20 g is withdrawn, which is analyzed by chromatography in gas phase.
  • the above azeotropic composition can be stabilized with 0.5% of dimethoxymethane.
  • test circuits conforming to the IPC-B-25 standard. described in the IPC (Institute for Interconnecting and Packaging Electronic Circuits; Lincolnwood, IL, USA). These circuits are coated with flux rosin-based solder (product marketed by ALPHAMETAL under the name flow R8F) and annealed in an oven at 220 ° C for 30 seconds.
  • flux rosin-based solder product marketed by ALPHAMETAL under the name flow R8F
  • these circuits are cleaned using the azeotropic composition of Example 1, in a small ultrasonic machine for 3 minutes by immersion in the liquid phase and 3 minutes in the vapor phase.
  • the cleaning is evaluated according to the standardized procedure IPC 2.3.26 (described also in the manual cited above) using a precision conductivity meter.
  • a 5x3 cm stainless steel grid is soaked in water for a few seconds.
  • the water retention capacity of this grid is measured by soaking the grid in absolute ethyl alcohol, then assay by the Karl Fisher method implemented with this alcoholic solution.
  • This grid is then immersed for 30 seconds in the composition of drying thus prepared, by stirring manually. We remove the grid from this composition, and the residual water is assayed using the Karl Fischer method, as described above.
  • the amount of water called the elimination rate (expressed as a percentage) residual after drying divided by the water retention capacity of the grid (corrected for the water content of the absolute ethyl alcohol used).

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)

Claims (5)

  1. Azeotrope oder quasi-azeotrope Zusammensetzungen, enthaltend:
    45 bis 65% 1,1,1,3,3-Pentafluorbutan, vorzugsweise 50 bis 60%,
    30 bis 50% Dichlormethan, vorzugsweise 35 bis 45%,
    1 bis 10% Methanol, vorzugsweise 2 bis 5%, und
    0,1 bis 2% 1,1,1,2,3,4,4,5,5,5-Decafluorpentan, vorzugsweise 0,2 bis 1%.
  2. Zusammensetzung nach Anspruch 1 in Form eines Azeotrops mit einem Siedepunkt von 31,9°C bei Normaldruck.
  3. Zusammensetzungen nach Anspruch 1 oder 2, die außerdem auch noch einen Stabilisator enthalten, vorzugsweise Dimethoxymethan.
  4. Zusammensetzungen nach einem der Ansprüche 1 bis 3, die außerdem auch noch ein lösliches hydrophobes Tensid enthalten, vorzugsweise ein Diamid der Formel: R-CO-NR-(CH2)n-NH-CO-R worin R für einen Alkylrest mit 14 bis 22 Kohlenstoffatomen und vorzugsweise 16 bis 20 Kohlenstoffatomen steht und n für eine ganze Zahl zwischen 1 und 5 einschließlich steht und vorzugsweise gleich 3 ist.
  5. Verwendung der Zusammensetzungen nach einem der Ansprüche 1 bis 6 zum Reinigen oder Entfetten von festen Oberflächen, vorzugsweise zum Entfernen von Flußmittelresten von Leiterplatten, sowie für Oberflächentrocknungsoperationen.
EP00400777A 1999-04-22 2000-03-21 Reinigungs- oder Trocknungszusammensetzungen auf Basis von Pentafluorbutan, Methylenchlorid, Methanol und Decafluorpentan Expired - Lifetime EP1046703B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR9905130A FR2792647B1 (fr) 1999-04-22 1999-04-22 COMPOSITIONS DE NETTOYAGE OU DE SECHAGE A BASE DE F365 mfc, CH2CL2, CH3OH ET 43-10mee
FR9905130 1999-04-22

Publications (2)

Publication Number Publication Date
EP1046703A1 EP1046703A1 (de) 2000-10-25
EP1046703B1 true EP1046703B1 (de) 2003-10-15

Family

ID=9544753

Family Applications (1)

Application Number Title Priority Date Filing Date
EP00400777A Expired - Lifetime EP1046703B1 (de) 1999-04-22 2000-03-21 Reinigungs- oder Trocknungszusammensetzungen auf Basis von Pentafluorbutan, Methylenchlorid, Methanol und Decafluorpentan

Country Status (8)

Country Link
US (1) US6291416B1 (de)
EP (1) EP1046703B1 (de)
JP (1) JP2000328095A (de)
AU (1) AU764299B2 (de)
CA (1) CA2305019A1 (de)
DE (1) DE60005881T2 (de)
ES (1) ES2208232T3 (de)
FR (1) FR2792647B1 (de)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7091170B2 (en) * 2001-02-14 2006-08-15 Kaneko Chemical Co., Ltd. Solvent composition for washing
US6979668B2 (en) * 2002-12-16 2005-12-27 Generex Pharmaceuticals Incorporated Cleaning compound for and method of cleaning valves and actuators of metered dose dispensers containing pharmaceutical compositions
AU2003300937B2 (en) * 2002-12-17 2008-05-29 Honeywell International, Inc. Compositions and methods for cleaning contaminated articles
JP3640661B1 (ja) * 2004-03-09 2005-04-20 株式会社カネコ化学 ペンタフルオロブタン組成物
FR2874383B1 (fr) * 2004-08-18 2006-10-13 Arkema Sa Composition a base de 1,1,1,3,3 - pentafluorobutane, utilisable dans des applications de depot, nettoyage, degraissage et sechage
JP3955878B1 (ja) 2006-06-28 2007-08-08 株式会社カネコ化学 ペンタフルオロブタン組成物
US7540973B2 (en) 2006-12-12 2009-06-02 E. I. Du Pont De Nemours And Company Azeotrope-like mixtures comprising heptafluorocyclopentane

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2676067B1 (fr) * 1991-05-02 1993-07-23 Atochem Composition a base de 1,1,1,3,3-pentafluorobutane et de methanol, pour le nettoyage et/ou le sechage de surfaces solides.
FR2676066B1 (fr) * 1991-05-02 1993-07-23 Atochem Composition a base de 1,1-dichloro-1-fluoroethane, de 1,1,1,3,3-pentafluorobutane et de methanol, pour le nettoyage et/ou le sechage de surfaces solides.
FR2694942B1 (fr) * 1992-08-21 1994-10-14 Atochem Elf Sa Composition à base de 1,1,1,3,3-pentafluorobutane et de chlorure de méthylène, pour le nettoyage et/ou le séchage de surfaces solides.
FR2694943B1 (fr) * 1992-08-21 1994-10-14 Atochem Elf Sa Composition à base de 1,1,1,3,3-pentafluorobutane, de chlorure de méthylène et de méthanol, pour le nettoyage et/ou le séchage de surfaces solides.
FR2732356B1 (fr) * 1995-03-31 1997-05-30 Solvay Compositions comprenant un hydrofluorocarbure et procede d'elimination d'eau d'une surface solide
US5759986A (en) * 1997-03-03 1998-06-02 Merchant; Abid Nazarali Decafluoropentane compositions
FR2757871B1 (fr) * 1996-12-27 1999-03-26 Aerospatiale Composition hydrofuge comprenant un agent hydrophobe et un solvant, application a l'elimination de l'eau de surface notamment de pare-brise de vehicules ou d'aeronefs
FR2766836B1 (fr) * 1997-07-31 1999-09-24 Atochem Elf Sa Melange quasi azeotropique a base de 1,1,1,3,3- pentafluorobutane, de chlorure de methylene et de methanol pour le traitement de surfaces solides
WO1999035210A1 (en) * 1998-01-02 1999-07-15 E.I. Du Pont De Nemours And Company Decafluoropentane compositions
US6103684A (en) * 1998-06-25 2000-08-15 Alliedsignal Inc. Compositions of 1-bromopropane and an organic solvent
FR2781499B1 (fr) * 1998-07-24 2000-09-08 Atochem Elf Sa Compositions de nettoyage ou de sechage a base de 1,1,1,2,3,4,4,5,5, 5 - decafluoropentane
US6951835B1 (en) * 1999-03-22 2005-10-04 E.I. Du Pont De Nemours And Company Azeotrope-like compositions of 1,1,1,3,3-pentafluorobutane

Also Published As

Publication number Publication date
DE60005881T2 (de) 2004-08-19
JP2000328095A (ja) 2000-11-28
FR2792647A1 (fr) 2000-10-27
FR2792647B1 (fr) 2001-06-08
AU2894400A (en) 2000-10-26
US6291416B1 (en) 2001-09-18
AU764299B2 (en) 2003-08-14
DE60005881D1 (de) 2003-11-20
CA2305019A1 (fr) 2000-10-22
ES2208232T3 (es) 2004-06-16
EP1046703A1 (de) 2000-10-25

Similar Documents

Publication Publication Date Title
CA2354566C (fr) Compositions comprenant du 1,1,1,3,3-pentafluorobutane et utilisation de ces compositions
EP0443911B1 (de) Anwendung von Perfluoralkyl-Ethylenen als Reinigungs- oder Trocknungsmittel
JP5518878B2 (ja) 洗浄組成物
BE1011609A3 (fr) Compositions comprenant du perfluorobutyl methyl ether et utilisation de ces compositions.
EP0512884B1 (de) Zusammensetzung auf Basis von 1,1-Dichlor-1-fluorethan, 1,1,1,3,3-Pentafluorbutan und Methanol für die Reinigung und/oder Trocknung von harten Oberflächen
EP0974642B1 (de) Reinigungs- und Trocknungsmittel auf Basis von 1,1,1,2,3,4,4,5,5,5-Decafluorpentan und 1,1,1,3,3-pentafluorbutan
EP1046703B1 (de) Reinigungs- oder Trocknungszusammensetzungen auf Basis von Pentafluorbutan, Methylenchlorid, Methanol und Decafluorpentan
FR2731436A1 (fr) Utilisation d'hydrofluoroalcenes comme agents de nettoyage, et compositions utilisables a cet effet
EP0894851A1 (de) Quasi-azeotrope Mischungen auf Basis von 1,1,1,3,3,-Pentafluorobutan, Methylene Chloride und Methanol zur Behandlung von festen Oberflächen
EP0856578B1 (de) Reinigungs- oder Trocknungsmittel enthaltend 1,1,1,2,3,4,4,5,5,5-Decafluoropentan
FR2792648A1 (fr) COMPOSITIONS DE NETTOYAGE OU DE SECHAGE A BASE DE 43-10mee ET DE TRICHLORETHYLENE
FR2929956A1 (fr) Composition de nettoyage
FR2792649A1 (fr) COMPOSITIONS DE NETTOYAGE OU DE SECHAGE A BASE DE 43-10mee, DE CH2CL2, DE CYCLOPENTANE ET DE CH3OH
EP0456551A1 (de) 1,1,1,2,2-Pentafluor-3,3-Dichlor-Propan und Methyl Ter-Butyl-Aether enthaltende Reinigungsmittelzusammensetzung
WO2003025109A1 (fr) Compositions de nettoyage ou de sechage a base de n-perfluorobutyl-ethylene et de hfc 365mfc
EP0525266B1 (de) Zusammensetzung auf der Basis von N-Perfluorbutylethylen zum Reinigen von festen Oberflächen
EP0441663A1 (de) Reinigungsmittel auf der Grundlage von 1,1-Dichlor-1-Fluorethan und Methylformiat
US20230399591A1 (en) Cleaning solvent blends of low global warming potential exhibiting azeotrope-like behavior and their use
FR2740469A1 (fr) Compositions de nettoyage a base de 1,1,1,2,2,4,4,- heptafluorobutane et d'alcools
EP0441664A1 (de) Reinigungsmittel auf Basis von 1,1-Dichlor-1-Fluorethan, Methylformiat und Methanol
FR2656327A1 (fr) Composition nettoyage a base de 1,1-dichloro-2,2,2-trifluoroethane et de formiate de methyle.
FR2766837A1 (fr) Compositions azeotropiques a base de (n.perfluorohexyl) ethylene pour le traitement de surfaces solides
FR2656328A1 (fr) Composition nettoyante a base de 1,1-dichloro-2,2,2-trifluoroethane, de formiate de methyle et de methanol.

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: 20000404

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): DE ES FR GB IT

AX Request for extension of the european patent

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

AKX Designation fees paid

Free format text: DE ES FR GB IT

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): DE ES FR GB IT

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REF Corresponds to:

Ref document number: 60005881

Country of ref document: DE

Date of ref document: 20031120

Kind code of ref document: P

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

Effective date: 20031224

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

Ref country code: FR

Payment date: 20040309

Year of fee payment: 5

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

Ref country code: GB

Payment date: 20040317

Year of fee payment: 5

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

Ref country code: ES

Payment date: 20040318

Year of fee payment: 5

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

Ref country code: DE

Payment date: 20040401

Year of fee payment: 5

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2208232

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

Effective date: 20040716

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: 20050321

Ref country code: GB

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

Effective date: 20050321

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: 20050322

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 NON-PAYMENT OF DUE FEES

Effective date: 20051001

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

Effective date: 20050321

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: 20051130

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20051130

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20050322