EP0409502B1 - Wäscheweichmacher - Google Patents

Wäscheweichmacher Download PDF

Info

Publication number
EP0409502B1
EP0409502B1 EP90307691A EP90307691A EP0409502B1 EP 0409502 B1 EP0409502 B1 EP 0409502B1 EP 90307691 A EP90307691 A EP 90307691A EP 90307691 A EP90307691 A EP 90307691A EP 0409502 B1 EP0409502 B1 EP 0409502B1
Authority
EP
European Patent Office
Prior art keywords
fabric softening
quaternary ammonium
fatty acid
softening composition
materials
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
EP90307691A
Other languages
English (en)
French (fr)
Other versions
EP0409502A3 (en
EP0409502A2 (de
Inventor
Sabine Dagmer Tandela
Brian William Topping
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.)
Unilever PLC
Unilever NV
Original Assignee
Unilever PLC
Unilever NV
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 Unilever PLC, Unilever NV filed Critical Unilever PLC
Publication of EP0409502A2 publication Critical patent/EP0409502A2/de
Publication of EP0409502A3 publication Critical patent/EP0409502A3/en
Application granted granted Critical
Publication of EP0409502B1 publication Critical patent/EP0409502B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38Cationic compounds
    • C11D1/62Quaternary ammonium compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/20Organic compounds containing oxygen
    • C11D3/2075Carboxylic acids-salts thereof
    • C11D3/2079Monocarboxylic acids-salts thereof

Definitions

  • the present invention relates to a fabric softening composition and to a method for its preparation. Specifically, the present invention relates to a fabric softening composition for use in the rinse step of a fabric washing process.
  • EP-A-0,240,727 (Henkel) describes a softening composition including a quaternary ammonium compound having two 2-acyloxyalkyl groups, together with an alkali metal soap or the corresponding fatty acid.
  • the quaternary ammonium compounds which it specifically discloses do not include the softening materials used in the present invention.
  • EP-A-0,302,567 (Procter and Gamble) describes a method for preparing a fabric softener by combining a C1-C4 monohydric alcohol with a quaternary ammonium compound including two ester groups. Again, the quaternary ammonium compound is not of the type used in the present invention.
  • the document refers to the possibility of adding a fatty acid to the softening composition, as a viscosity control agent.
  • EP-A-0,122,141 (Unilever) relates to a softening composition including a water-insoluble cationic softener and a nonionic material which may be a C8-C24 fatty acid.
  • the cationic softeners referred to do not include those used in the present invention.
  • GB-A-2,039,556 (Unilever) describes a softening composition which includes a quaternary ammonium softener (substituted only with alkyl or alkenyl groups) and a C8-C24 carboxylic acid.
  • the present invention relates to a fabric softening composition
  • a fabric softening composition comprising:
  • Preferred materials of this class and their method of preparation are, for example, described in US 4 137 180 (LEVER BROTHERS).
  • these materials comprise small amounts of the corresponding monoester as described in US 4 137 180 for example 1-tallowoxy, 2-hydroxy trimethyl ammonium propane chloride.
  • the level of ester-linked quaternary ammonium compounds is at least 1% by weight of the composition, more preferably more than 3% by weight of the composition; especially interesting are compositions of high active level, e.g. which comprise more than 8% of the ester-linked quaternary ammonium compound.
  • the level of ester-linked quaternary ammonium compounds preferably is less than 70% by weight of the composition, more preferably less than 50%, typically from 3 to 30% by weight of the composition.
  • the fatty acid material or salt thereof can be any mono-, di- or tri-carboxylic acid comprising an alkyl or alkenyl chain having from 8 to 28 carbon atoms or salts thereof.
  • Preferred fatty acid materials or their salts may be represented by the formula: R1COOR2 wherein R1 is a straight or branched alkyl or alkenyl chain having from 8 to 28 carbon atoms, and wherein R2 is hydrogen or a cation.
  • Preferred cations are alkali metal ions or alkali earth metal ions; more preferred are sodium, potassium or calcium.
  • a non-saponified fatty acid material is particularly preferred.
  • the level of fatty acid material is more than 0.1% by weight of the composition, more preferably more than 0.2%; especially preferred are concentrated systems comprising more than 0.5% of fatty acid material.
  • the level of fatty acid material will usually not exceed 50% by weight of the composition, more preferably the level of fatty acid material is less than 30%, typically from 0.5 to 10% by weight of the composition.
  • the weight ratio of ester-linked quaternary ammonium materials to fatty acid materials is preferably from 10:1 to 1:10, more preferably from 8:1 to 1:1, especially preferably from 7:1 to 3:1.
  • compositions of the invention preferably have a pH of more than 2.0.
  • the pH is preferably less than 5.0 to prevent saponification of the fatty acids.
  • the pH is 5.0 or more, more preferably between 5.0 and 8.0.
  • compositions of the invention may, in addition to the above described two ingredients, also comprise other active ingredients such as further fabric conditioning materials.
  • compositions of the invention do not comprise large amounts of conventional non-ester-linked quaternary ammonium comounds, more preferably the compositions of the invention are substantially free of these quaternary ammonium compounds.
  • Suitable conditioning materials for inclusion in compositions of the invention comprise nonionic materials.
  • Suitable nonionic fabric softening agents include glycerol esters, such as glycerol monostearate, fatty alcohols, such as stearyl alcohol, alkoxylated fatty alcohols, C9-C24 fatty acids and lanolin and derivatives thereof.
  • Suitable materials are disclosed in European Patent Applications 88 520 (Unilever PLC/NV - Case C1325), 122 141 (Unilever PLC/NC - Case C1363) and 79 746 (Procter & Gamble).
  • softening materials which may be incorporated in a composition of the invention are amines, such as, for instance, described in EP 89200545.5, or biodegradable amphoteric softening materials such as, for instance, described in EP 89200113.2.
  • the amount of softening materials other than the above mentioned ester-linked materials and fatty acid materials is relatively low, i.e. the weight ratio of other softener materials to the total of the two essential softener components is preferably less than 2:1; more preferably less than 1:1, most preferably less than 0.5:1.
  • the composition can also contain one or more optional ingredients selected from non-aqueous solvents such as C1-C4 alkanols and polyhydric alcohols, pH buffering agents such as strong or weak acids, e.g. HCl, H2SO4, phosphoric, benzoic or citric acids, rewetting agents, viscosity modifiers such as electrolytes, for example calcium chloride, anti-gelling agents, perfumes, perfume carriers, fluorescers, colourants, hydrotropes, anti-foaming agents, anti-redeposition agents, enzymes, optical brightening agents, opacifiers, stabilizers such as guar gum and polyethylene glycol, emulsifiers, anti-shrinking agents, anti-wrinkle agents, fabric crisping agents, anti-spotting agents, soil-release agents, germicides, linear or branched silicones, fungicides, anti-oxidants, anti-corrosion agents, preservatives such as Bronopol (Trade Mark), a commercially available form
  • These optional ingredients are preferably present at levels up to 5% by weight of the composition.
  • the liquid compositions according to the invention may be prepared by a variety of methods.
  • One suitable method is to form a molten mixture of the ester-linked quaternary ammonium materials and the fatty acid materials, optionally in combination with other softening materials, and adding this premix to water with stirring to form a dispersion and thereafter adding any other optional ingredients.
  • the fabric conditioning composition of the invention may be added to a large volume of water to form a liquor with which the fabrics to be treated are contacted.
  • the total concentration of the ester-linked quaternary ammonium compound and the fatty acid compound in this liquor will be between about 30 ppm and 1000 ppm.
  • the weight ratio of the fabrics to the liquor will generally be between 1:1 and 1:20.
  • composition D is a commercially available fabric conditioner (COCCOLINO CONCENTRATE).
  • COCCOLINO CONCENTRATE a commercially available fabric conditioner
  • compositions of 0.89 were requried for a 95% significance.
  • composition F compared to compositions D and E.
  • ester-linked quaternary ammonium materials suitable for use in compositions according to the invention are more biodegradable than quaternary ammonium materials which are more generally 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)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Claims (6)

  1. Textilweichmachendes Mittel, umfassend:
    (i) ein quaternäres Ammoniummaterial, das eine Verbindung mit zwei C₁₂₋₂₈-Alkyl- oder -Alkenylgruppen umfaßt, welche an das Molekül über eine Esterbindung gebunden sind, wobei die Verbindung die Formel aufweist:
    Figure imgb0003
       worin jede der Gruppen R₁ unabhängig voneinander ausgewählt ist aus C₁₋₄-Alkyl-, Alkenyl- oder Hydroxyalkylgruppen; jede Gruppe R₂ unabhängig ausgewählt ist aus C₈₋₂₈-Alkyl- oder -Alkenylgruppen und n eine ganze Zahl von 0 bis 5 ist, und
    (ii) ein C₈₋₂₈-Fettsäurematerial oder Salz davon.
  2. Textilweichmachendes Mittel nach Anspruch 1, das eine Flüssigkeit darstellt und eine wässerige Grundlage umfaßt.
  3. Textilweichmachendes Mittel nach Anspruch 1 oder Anspruch 2, mit einem pH-Wert von 2,0 bis 5,0.
  4. Textilweichmachendes Mittel nach einem der vorangehenden Ansprüche, wobei das Fettsäurematerial nicht verseift ist.
  5. Textilweichmachendes Mittel nach einem der vorangehenden Ansprüche, wobei das Gewichtsverhältnis des quaternären Ammoniummaterials (i) zu dem Fettsäurematerial (ii) 10:1 bis 1:10 beträgt.
  6. Textilweichmachendes Mittel nach einem der vorangehenden Ansprüche, wobei das quaternäre Ammoniummaterial 1,2-Ditalgoxytrimethylammoniumpropanchlorid umfaßt.
EP90307691A 1989-07-17 1990-07-13 Wäscheweichmacher Expired - Lifetime EP0409502B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB8916306 1989-07-17
GB898916306A GB8916306D0 (en) 1989-07-17 1989-07-17 Fabric softening composition

Publications (3)

Publication Number Publication Date
EP0409502A2 EP0409502A2 (de) 1991-01-23
EP0409502A3 EP0409502A3 (en) 1991-11-13
EP0409502B1 true EP0409502B1 (de) 1995-11-15

Family

ID=10660145

Family Applications (1)

Application Number Title Priority Date Filing Date
EP90307691A Expired - Lifetime EP0409502B1 (de) 1989-07-17 1990-07-13 Wäscheweichmacher

Country Status (9)

Country Link
EP (1) EP0409502B1 (de)
JP (1) JP2611036B2 (de)
AU (1) AU640152B2 (de)
BR (1) BR9003453A (de)
CA (1) CA2021322C (de)
DE (1) DE69023561T2 (de)
ES (1) ES2080119T3 (de)
GB (1) GB8916306D0 (de)
ZA (1) ZA905607B (de)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003018534A1 (en) 2001-08-23 2003-03-06 Akzo Nobel Nv A nitrogen-containing ortho ester-based surfactant, its preparation and use
US6897194B2 (en) 2000-02-08 2005-05-24 Unilever Home & Personal Care Usa Division Of Conopco, Inc. Fabric conditioning compositions

Families Citing this family (29)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1992008837A2 (en) * 1990-11-16 1992-05-29 Akzo N.V. Biodegradable fabric softeners
GB9115255D0 (en) * 1991-07-15 1991-08-28 Unilever Plc Fabric softening composition
GB9114540D0 (en) * 1991-07-05 1991-08-21 Unilever Plc Fabric softening composition
WO1993017085A1 (en) * 1992-02-20 1993-09-02 Akzo Nobel N.V. Biodegradable fabric softeners
CA2131306C (en) * 1992-03-16 1998-02-10 Alice Marie Vogel Fabric softening compositions containing mixtures of softener material and highly ethoxylated curd dispersant
GB9208652D0 (en) * 1992-04-22 1992-06-10 Unilever Plc Hair care composition
GB9209170D0 (en) * 1992-04-28 1992-06-10 Unilever Plc Rinse conditioner
ATE181956T1 (de) * 1992-05-12 1999-07-15 Procter & Gamble Konzentrierte flüssige gewebeweichmacherzusammensetzungen mit biologisch abbaubaren gewebeweichmachern
EP0644925B1 (de) * 1992-06-10 1997-03-19 The Procter & Gamble Company Stabile, biologisch abbaubare gewebeweichmacherzusammensetzungen
GB9218342D0 (en) * 1992-08-28 1992-10-14 Unilever Plc Use of fabric softening composition
US5543067A (en) * 1992-10-27 1996-08-06 The Procter & Gamble Company Waterless self-emulsiviable biodegradable chemical softening composition useful in fibrous cellulosic materials
EP0687291B2 (de) * 1993-03-01 2005-08-24 The Procter & Gamble Company Konzentrierte biologisch abbaubare weichspülerzusammensetzungen auf der basis von quartären ammoniumverbindungen
EP0637625A1 (de) * 1993-08-02 1995-02-08 The Procter & Gamble Company Emulsionssuperkonzentrate mit Textilweichmachern
US5750491A (en) * 1993-08-02 1998-05-12 The Procter & Gamble Company Super concentrate emulsions with fabric actives
WO1995031524A2 (en) * 1994-05-18 1995-11-23 The Procter & Gamble Company Concentrated biodegradable fabric softener compositions
US5463094A (en) * 1994-05-23 1995-10-31 Hoechst Celanese Corporation Solvent free quaternization of tertiary amines with dimethylsulfate
WO1996003481A1 (en) * 1994-07-26 1996-02-08 The Procter & Gamble Company Rinse added fabric softener compositions containing antioxidants for sun-fade protection for fabrics
US5552137A (en) * 1994-08-05 1996-09-03 Witco Corporation Biodegradable quaternary hair conditioners
US5503756A (en) * 1994-09-20 1996-04-02 The Procter & Gamble Company Dryer-activated fabric conditioning compositions containing unsaturated fatty acid
US5460736A (en) * 1994-10-07 1995-10-24 The Procter & Gamble Company Fabric softening composition containing chlorine scavengers
US5505866A (en) * 1994-10-07 1996-04-09 The Procter & Gamble Company Solid particulate fabric softener composition containing biodegradable cationic ester fabric softener active and acidic pH modifier
US5474690A (en) * 1994-11-14 1995-12-12 The Procter & Gamble Company Concentrated biodegradable quaternary ammonium fabric softener compositions containing intermediate iodine value fatty acid chains
GB9517432D0 (en) * 1995-08-25 1995-10-25 Unilever Plc Fabric softening composition
EP0760243B1 (de) * 1995-08-31 2006-03-29 The Procter & Gamble Company Verwendung von Allylalkohol als ein Mittel zur Verminderung von schlechten Gerüchen
US6022845A (en) * 1995-11-03 2000-02-08 The Procter & Gamble Co. Stable high perfume, low active fabric softener compositions
GB2301843A (en) * 1996-05-10 1996-12-18 Unilever Plc Stable fabric conditioning composition
US6083899A (en) * 1996-09-19 2000-07-04 The Procter & Gamble Company Fabric softeners having increased performance
GB0121806D0 (en) 2001-09-10 2001-10-31 Unilever Plc A method of reducing the viscosity of fabric conditioning compositions
GB0121807D0 (en) 2001-09-10 2001-10-31 Unilever Plc Fabric conditioning compositions

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1567947A (en) * 1976-07-02 1980-05-21 Unilever Ltd Esters of quaternised amino-alcohols for treating fabrics
FR2440433A1 (fr) * 1978-11-03 1980-05-30 Unilever Nv Composition d'assouplissement des etoffes et procede pour la preparer
JPS6039791B2 (ja) * 1981-07-10 1985-09-07 ライオン株式会社 柔軟剤組成物
JPS628427A (ja) * 1985-07-04 1987-01-16 Mitsubishi Electric Corp 防眩形陰極線管の製造方法
DE3608093A1 (de) * 1986-03-12 1987-09-17 Henkel Kgaa Konfektioniertes textilweichmacher-konzentrat
JPS6361426A (ja) * 1986-08-22 1988-03-17 Csk Corp 光記録媒体のデ−タ追記方式
US4789491A (en) * 1987-08-07 1988-12-06 The Procter & Gamble Company Method for preparing biodegradable fabric softening compositions
DE3818061A1 (de) * 1988-05-27 1989-12-07 Henkel Kgaa Fluessiges, waessriges waeschenachbehandlungsmittel
GB8914054D0 (en) * 1989-06-19 1989-08-09 Unilever Plc Fabric softening composition
GB8916307D0 (en) * 1989-07-17 1989-08-31 Unilever Plc Fabric softening composition

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6897194B2 (en) 2000-02-08 2005-05-24 Unilever Home & Personal Care Usa Division Of Conopco, Inc. Fabric conditioning compositions
WO2003018534A1 (en) 2001-08-23 2003-03-06 Akzo Nobel Nv A nitrogen-containing ortho ester-based surfactant, its preparation and use
US7288510B2 (en) 2001-08-23 2007-10-30 Akzo Nobel N.V. Nitrogen-containing ortho ester-based surfactant, its preparation and use

Also Published As

Publication number Publication date
AU5900790A (en) 1991-01-17
CA2021322A1 (en) 1991-01-18
DE69023561D1 (de) 1995-12-21
DE69023561T2 (de) 1996-04-18
BR9003453A (pt) 1991-08-27
ES2080119T3 (es) 1996-02-01
ZA905607B (en) 1992-03-25
EP0409502A3 (en) 1991-11-13
AU640152B2 (en) 1993-08-19
JP2611036B2 (ja) 1997-05-21
GB8916306D0 (en) 1989-08-31
JPH03113077A (ja) 1991-05-14
EP0409502A2 (de) 1991-01-23
CA2021322C (en) 2000-10-31

Similar Documents

Publication Publication Date Title
EP0409502B1 (de) Wäscheweichmacher
EP0409504B1 (de) Wäschweichmacher
EP0326213B1 (de) Textilbehandlungszubereitung und deren Herstellung
JP3902783B2 (ja) 濃縮生分解性四級アンモニウム布帛柔軟剤組成物、および中間ヨウ素価不飽和脂肪酸鎖を含む化合物
EP0507478B1 (de) Wäscheweichmacherzusammensetzung
JPH10508622A (ja) 中間ヨウ素価脂肪酸鎖を含有する濃縮生分解性第四級アンモニウム布帛柔軟剤組成物
JP2001524616A (ja) 高含有量の電解質および所望により相安定剤を含む、透明または半透明の水性布地柔軟化組成物
US6878684B2 (en) Fabric conditioning composition
EP0280550A2 (de) Weichmacherzusammensetzung für Textilien
EP0746603B1 (de) Gewebeweichmacherzusammensetzung
EP0332270B1 (de) Wäscheweichmacherzusammensetzung
US5077119A (en) Fabric conditioning
EP0530959B1 (de) Weichspülerzusammensetzungen auf der Basis einer Pentaerythritverbindung und Dispergiermittel für eine solche Verbindung
EP0107479B1 (de) Textilweichmacherzusammensetzung
EP0159921A2 (de) Wässrige Textilweichmacherzusammensetzung
EP0125031B1 (de) Flüssige Gewebeweichmacher-Zusammensetzung
EP0409503B1 (de) Wäscheweichmacher
EP0681604B1 (de) Textilweichmacherzusammensetzung
EP0387064A2 (de) Wäscheweichmachen
CA2399441C (en) Fabric conditioning compositions
EP0159922A2 (de) Wässrige Textilweichmacherzusammensetzung

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: A2

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

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Kind code of ref document: A3

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

17P Request for examination filed

Effective date: 19920110

RAP3 Party data changed (applicant data changed or rights of an application transferred)

Owner name: UNILEVER N.V.

Owner name: UNILEVER PLC

17Q First examination report despatched

Effective date: 19930730

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

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

REF Corresponds to:

Ref document number: 69023561

Country of ref document: DE

Date of ref document: 19951221

ITF It: translation for a ep patent filed

Owner name: JACOBACCI & PERANI S.P.A.

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2080119

Country of ref document: ES

Kind code of ref document: T3

ET Fr: translation filed
REG Reference to a national code

Ref country code: CH

Ref legal event code: NV

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

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

Ref country code: CH

Payment date: 19960702

Year of fee payment: 7

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
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: 19970731

Ref country code: CH

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

Effective date: 19970731

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

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

Ref country code: SE

Payment date: 19980622

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: 19980713

Year of fee payment: 9

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

Ref country code: SE

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

Effective date: 19990730

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: 20000201

EUG Se: european patent has lapsed

Ref document number: 90307691.7

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

Effective date: 20000201

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: FR

Payment date: 20020619

Year of fee payment: 13

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

Ref country code: GB

Payment date: 20020710

Year of fee payment: 13

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

Ref country code: DE

Payment date: 20020730

Year of fee payment: 13

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

Ref country code: ES

Payment date: 20020807

Year of fee payment: 13

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: 20030713

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: 20030714

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: 20040203

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

Effective date: 20030713

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: 20040331

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: 20030714

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: 20050713