EP0276997B1 - Detergent composition with fabric softening properties - Google Patents

Detergent composition with fabric softening properties Download PDF

Info

Publication number
EP0276997B1
EP0276997B1 EP88300688A EP88300688A EP0276997B1 EP 0276997 B1 EP0276997 B1 EP 0276997B1 EP 88300688 A EP88300688 A EP 88300688A EP 88300688 A EP88300688 A EP 88300688A EP 0276997 B1 EP0276997 B1 EP 0276997B1
Authority
EP
European Patent Office
Prior art keywords
soap
weight
cellulose ether
composition
hlb
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
EP88300688A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0276997A2 (en
EP0276997A3 (en
Inventor
Francis Geoffrey Foster
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
Priority claimed from GB878701962A external-priority patent/GB8701962D0/en
Priority claimed from GB878723511A external-priority patent/GB8723511D0/en
Application filed by Unilever PLC, Unilever NV filed Critical Unilever PLC
Publication of EP0276997A2 publication Critical patent/EP0276997A2/en
Publication of EP0276997A3 publication Critical patent/EP0276997A3/en
Application granted granted Critical
Publication of EP0276997B1 publication Critical patent/EP0276997B1/en
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
    • C11D9/00—Compositions of detergents based essentially on soap
    • C11D9/04—Compositions of detergents based essentially on soap containing compounding ingredients other than soaps
    • C11D9/22—Organic compounds, e.g. vitamins
    • C11D9/26—Organic compounds, e.g. vitamins 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
    • C11D9/00—Compositions of detergents based essentially on soap
    • C11D9/04—Compositions of detergents based essentially on soap containing compounding ingredients other than soaps
    • C11D9/22—Organic compounds, e.g. vitamins
    • C11D9/26—Organic compounds, e.g. vitamins containing oxygen
    • C11D9/262—Organic compounds, e.g. vitamins containing oxygen containing carbohydrates
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • C11D3/225—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin etherified, e.g. CMC

Definitions

  • This invention relates to a detergent composition for treating fabrics in particular to such compositions which are capable of softening natural fibre wash load articles without causing redeposition problems on any synthetic fibre fabrics in the load.
  • the invention is directed to alkaline compositions capable of achieving an optimum balance of softening and detergency across a mixed fibre wash load.
  • Soaps are particularly attractive softening agents in view of their dual role as detergent active materials capable of removing soil from fabrics.
  • a problem associated with the deposition of organic fabric softening agents such as soap on fabrics during the wash is that to achieve a desirable degree of softening effect on fabrics, an increase in the deposition of fatty and particulate soil occurs on synthetic fabrics, leading to unsightly discolouration.
  • Products designed for cleaning fabrics often contain in addition to a detergent active material to remove soil from the fabric, an anti-redeposition material to reduce the redeposition of the removed soil from the wash liquor back onto the fabrics.
  • Sodium carboxy methyl cellulose (SCMC) is one material used for this purpose. It reduces redeposition of clay and soot (or carbon) particulate soils onto hydrophilic fabrics such as cotton but not on hydrophobic fabrics.
  • redeposition problems are particularly extreme because the redeposition problem is one of organic fatty soil together with particulate, inorganic, soil.
  • a fabric treatment composition comprising at least 10% by weight of a soap which is a salt of a Ca - C 24 saturated or unsaturated fatty acid and from 0.1% to 3% by weight of a water-soluble nonionic substituted cellulose ether derivative having an HLB (as herein defined) of between 3.1 and 4.3, preferably between 3.3 and 3.8, and a gel point (as herein defined) of less than 58 ° C, preferably between 33 ° C and 56 ° C, provided that the derivative contains substantially no hydroxyalkyl groups containing 3 or more carbon atoms, the composition yielding a pH of more than 8.0 when added to water at a concentration of 1 % by weight at 25 ° C.
  • HLB as herein defined
  • a gel point as herein defined
  • HLB is a well known measure of the hydrophilic-lyophilic balance of a material and can be calculated from its molecular structure.
  • the cellulose ether derivatives useful herein are polymers which are water-soluble at room temperature.
  • the gel point of polymers can be measured in a number of ways. In the present context the gel point is measured on a polymer solution prepared by dispersion at 60/70 ° C and cooling to 20° - 25°C at 10 g/I concentration in deionised water. 50 ml of this solution placed in a beaker is heated, with stirring, at a heating rate of approximately 5 ° C/minute. The temperature at which the solution clouds is the gel point of the cellulose ether being tested and is measured using a Sybron/Brinkmann colorimeter at 80% transmission/450 nm.
  • the degree of substitution (DS) of the anhydroglucose ring may be any value up to the theoretical maximum value of 3, but is preferably from about 1.9-2.9, there being a maximum of 3 hydroxyl groups on each anhydroglucose unit in cellulose.
  • the expression 'molar substitution' (MS) is sometimes also used in connection with these polymers and refers the number of hydroxyalkyl substituents per anhydroglucose ring and may be more than 3 when the substituents themselves carry further substituents.
  • the most highly preferred polymers have an average number of anhydroglucose units in the cellulose polymer, or weight average degree of polymerisation, from about 50 to about 1,200.
  • anhydroglucose units in the cellulose polymer or weight average degree of polymerisation, from about 50 to about 1,200.
  • cellulose ether derivatives suitable for use in the present invention are commercially available, as follows:
  • soap includes not only the usual alkali metal and alkaline earth metal salts of fatty acids, but also the organic salts which can be formed by complexing fatty acids with organic nitrogen-containing materials such as amines and derivatives thereof.
  • the soap comprises salts of higher fatty acids preferably containing from 10 to 20 carbon atoms in the molecule, or mixtures thereof.
  • Suitable soaps include sodium stearate, sodium palmitate, sodium salts of tallow, coconut oil and palm oil fatty acids and complexes between stearic and/or palmitic fatty acids and/or tallow and/or coconut oil and/or palm oil fatty acids with water-soluble alkanolamines such as ethanolamine, di- or triethanolamine, N-methylethanolamine, N-ethylethanolamine, 2-methylethanolamine and 2, 2-dimethyl ethanolamine and N-containing ring compounds such as morpholine, 2'-pyrrolidone and their methyl derivatives.
  • water-soluble alkanolamines such as ethanolamine, di- or triethanolamine, N-methylethanolamine, N-ethylethanolamine, 2-methylethanolamine and 2, 2-dimethyl ethanolamine and N-containing ring compounds such as morpholine, 2'-pyrrolidone and their methyl derivatives.
  • soaps can also be employed, such as the sodium and potassium salts of the mixed fatty acids derived from coconut oil and tallow, that is sodium and potassium tallow and coconut soap.
  • mixtures of oleate and coconut soaps in a weight ratio of between about 3:1 and 1:1.
  • the level of soap in the composition is more than 10% by weight (measured as the weight of the corresponding sodium soap). Preferably not more than 50% by weight, of soap is used to leave room in the formulation for other ingredients.
  • compositions according to the invention optionally additionally contain one or more non-soap detergent active materials, selected from anionic nonionic, zwitterionic and amphoteric synthetic detergent active materials.
  • non-soap detergent active materials selected from anionic nonionic, zwitterionic and amphoteric synthetic detergent active materials.
  • suitable detergent compounds are commercially available and are fully described in the literature, for example in "Surface Active Agents and Detergents", Volumes I and II, by Schwartz, Perry and Berch.
  • Anionic non-soap detergent active materials are usually water-soluble alkali metal salts of organic sulphates and sulphonates having alkyl radicals containing from 8 to 22 carbon atoms, the term alkyl being used to include the alkyl portion of higher acyl radicals.
  • suitable synthetic anionic detergent compounds are sodium and potassium alkyl sulphates, especially those obtained by sulphating higher (C 8 -C 18 ) alcohols produced for example from tallow or coconut oil, sodium and potassium alkyl (C 9 -C 20 ) benzene sulphonates, particularly sodium linear secondary alkyl (C 10 -C 15 ) benzene sulphonates; sodium alkyl glyceryl ether sulphates, especially those ethers of the higher alcohols derived from tallow or coconut oil and synthetic alcohols derived from petroleum; sodium coconut oil fatty monoglyceride sulphates and sulphonates; sodium and potassium salts of sulphuric acid esters of higher (C S -C 1S ) fatty alcohol-alkylene oxide, particularly ethylene oxide, reaction products; the reaction products of fatty acids such as coconut fatty acids esterified with isethionic acids and neutralised with sodium hydroxide; sodium and potassium salts of fatty acid amides of
  • Suitable nonionic detergent compounds which may be used include in particular the reaction products of compounds having a hydrophobic group and a reactive hydrogen atom, for example aliphatic alcohols, acids, amides or alkyl phenols with alkylene oxides, especially ethylene oxide either alone or with propylene oxide.
  • nonionic detergent compounds are alkyl (C 6 -C 22 ) phenols-ethylene oxide condensates, generally up to 25 EO, ie up to 25 units of ethylene oxide per molecule, the condensation products of aliphatic (C s -C 1s ) primary or secondary linear or branched alcohols with ethylene oxide, generally up to 40 EO, and products made by condensation of ethylene oxide with the reaction products of propylene oxide and ethylenediamine.
  • Other so-called nonionic detergent compounds include long tertiary amine oxides, long chain tertiary phosphine oxides and dialkyl sulphoxides.
  • Mixtures of anionic and nonionic compounds may be used in the detergent compositions, particularly to provide controlled low sudsing properties. This is beneficial for compositions intended for use in suds- intolerant automatic washing machines.
  • Amounts of amphoteric or zwitterionic detergent compounds can also be used in the compositions of the invention but this is not normally desired due to their relatively high cost. If any amphoteric or zwitterionic detergent compounds are used it is generally in small amounts.
  • the effective amount of the non-soap detergent active compound or compounds used in the composition of the present invention is generally in the range of up to 50%, preferably up to 40% by weight, most preferably not more than 30% by weight of the composition and will usually be present in a minor amount relative to the amount of the soap.
  • compositions of the invention may include a non-soap detergency builder to improve the efficiency of the detergent active, in particular to remove calcium hardness ions from the water and to provide alkalinity.
  • the builder material may be selected from precipitating builder materials (such as alkali metal carbonates, bicarbonates, borates, orthophosphates and silicates), sequestering builder materials (such as alkali metal pyrophosphates, polyphosphates, amino polyacetates, phytates, polyphospho- nates, aminopolymethylene phosphonates and polycarboxylates), ion-exchange builder materials (such as zeolites and amorphous alumino-silicates), or mixtures of any one or more of these materials.
  • precipitating builder materials such as alkali metal carbonates, bicarbonates, borates, orthophosphates and silicates
  • sequestering builder materials such as alkali metal pyrophosphates, polyphosphate
  • builder materials include sodium tripolyphosphate, mixtures thereof with sodium orthophosphate, sodium carbonate, mixtures thereof with calcite as a seed crystal, sodium citrate, zeolite and the sodium salt of nitrilo- triacetic acid.
  • the level of such builder material in the compositions of the invention may be up to 80% by weight, preferably from 20% to 70% by weight and most preferably from 30% to 60% by weight.
  • a detergent composition of the invention can contain any of the conventional additives in the amounts in which such additives are normally employed in fabric washing detergent compositions.
  • these additives include additional fabric softening agents.
  • the fabric softening agent is a mixture of soap and either a cationic fabric softening agent or a fatty amine.
  • lather boosters such as alkanolamides, particularly the monoethanolamides derived from palm kernel fatty acids and coconut fatty acids, lather depressants, oxygen-releasing bleaching agents such as sodium perborate and sodium percarbonate, peracid bleach precursors, chlorine-releasing bleaching agents such as tricloroisocyanuric acid, inorganic salts such as sodium sulphate, and, usually present in very minor amounts, fluorescent agents, perfumes including deodorant perfumes, enzymes such as cellulases, proteases and amylases, germicides and colourants.
  • lather boosters such as alkanolamides, particularly the monoethanolamides derived from palm kernel fatty acids and coconut fatty acids
  • lather depressants oxygen-releasing bleaching agents such as sodium perborate and sodium percarbonate, peracid bleach precursors, chlorine-releasing bleaching agents such as tricloroisocyanuric acid, inorganic salts such as sodium sulphate, and, usually present in very minor amounts, fluorescent
  • compositions may be in any convenient form such as bars, powders, pastes or liquids which may be aqueous or non-aqueous and structured or unstructured.
  • the detergent compositions may be prepared in any way appropriate to their physical form such as by dry-mixing the components, co-agglomerating them or dispersing them in a liquid carrier.
  • a preferred physical form is a granule incorporating a detergency builder material and this is most conveniently manufactured by spray-drying at least part of the composition.
  • the cellulose ether derivative may be incorporated either by dry mixing (optionally with other ingredients in a post-dosed adjunct) or by being included with other ingredients in a slurry and spray-drying.
  • the detergent compositions may be used in any conventional manner.
  • a dosage level of between 1 g/I and about 12 g/l is suitable. Wash temperatures from room temperature (ie about 20 ° C) to the boil may be used.
  • compositions were prepared having the following formulations. The compositions were prepared by dry mixing the stated ingredients.
  • Both compositions had a pH of above 8.0 when added to water at 25 ° C at a concentration of 1% by weight.
  • compositions were added to water at a dosage level of 5 g/l.
  • the wash liquor so prepared was used to wash a fabric load containing terry towelling and polyester monitors in a laboratory scale apparatus using 24 ° FH water, a liquor to cloth ratio of about 20:1, a wash time of 15 minutes at 50 ° C, a 2 minute flood at 50% dilution followed by three 5 minute rinses.
  • the fabric load was then line-dried.
  • the terry towelling monitors were assessed for softness subjectively by expert judges who assess softness by comparison of pairs of monitors leading to preference scores which are then adjusted to give a score of zero for the control. A positive score indicates better softness than the control.
  • the results are set out in the following table.
  • Composition C was modified by replacing the Dobanol@ 45-7EO with Dobanol® 45-9EO (which is a similar material but containing an average of 9 ethylene oxide groups per molecule) and by optionally including 2.0% of Dobaneo 113.
  • the results were as follows:
  • An alkaline composition was prepared having the following formulation by spray drying a slurry of the stated ingredients, except the sodium perborate, to form a base powder and then adding the sodium perborate thereto.
  • An alkaline composition having the following formulation was prepared by spray cooling a slurry of the stated ingredients, except the sodium tripolyphosphate and the sodium perborate, to make a base powder and then adding the remaining ingredients.
  • Liquid compositions were prepared having the following formulations:
  • liquids were prepared by mixing a comelt of oleic and lauric acids at about 60 ° C with an aque- ous/ethanol solution of EDTA, potassium hydroxide and potassium chloride. The liquids were cooled and a desired amount of cellulose ether derivative was added.
  • composition G above is modified by the addition of 2% coconut ethanolamide or 2% Dobanol® 45-7EO.
  • Examples 9 to 12 were repeated using a variety of different soaps and soap blends and using 1% or 3% Bermocoll® CST035.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Emergency Medicine (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Molecular Biology (AREA)
  • Detergent Compositions (AREA)
EP88300688A 1987-01-29 1988-01-27 Detergent composition with fabric softening properties Expired - Lifetime EP0276997B1 (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
GB878701962A GB8701962D0 (en) 1987-01-29 1987-01-29 Detergent composition
GB8701962 1987-01-29
GB878723511A GB8723511D0 (en) 1987-10-07 1987-10-07 Detergent composition
GB8723511 1987-10-07

Publications (3)

Publication Number Publication Date
EP0276997A2 EP0276997A2 (en) 1988-08-03
EP0276997A3 EP0276997A3 (en) 1988-09-21
EP0276997B1 true EP0276997B1 (en) 1990-07-18

Family

ID=26291842

Family Applications (1)

Application Number Title Priority Date Filing Date
EP88300688A Expired - Lifetime EP0276997B1 (en) 1987-01-29 1988-01-27 Detergent composition with fabric softening properties

Country Status (11)

Country Link
EP (1) EP0276997B1 (pl)
KR (1) KR910004890B1 (pl)
AU (1) AU592248B2 (pl)
BR (1) BR8800255A (pl)
CA (1) CA1329533C (pl)
DE (1) DE3860305D1 (pl)
ES (1) ES2016406B3 (pl)
IN (1) IN166783B (pl)
OA (1) OA08708A (pl)
PH (1) PH24428A (pl)
TR (1) TR23614A (pl)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB8922595D0 (en) * 1989-10-06 1989-11-22 Unilever Plc Fabric treatment composition with softening properties
DE10351325A1 (de) 2003-02-10 2004-08-26 Henkel Kgaa Wasch- oder Reinigungsmittel mit wasserlöslichem Buildersystem und schmutzablösevermögendem Cellulosederivat
WO2004069978A1 (de) * 2003-02-10 2004-08-19 Henkel Kommanditgesellschaft Auf Aktien Bleichmittelhaltige wasch- oder reinigungsmittel mit wasserlöslichem buildersystem und schmutzablösevermögendem cellulosederivat

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3920563A (en) * 1972-10-31 1975-11-18 Colgate Palmolive Co Soap-cationic combinations as rinse cycle softeners
US4298480A (en) * 1978-12-11 1981-11-03 Colgate Palmolive Co. Detergent softener compositions
US4326971A (en) * 1978-12-11 1982-04-27 Colgate Palmolive Company Detergent softener compositions
GB8519047D0 (en) * 1985-07-29 1985-09-04 Unilever Plc Detergent composition
GB8519046D0 (en) * 1985-07-29 1985-09-04 Unilever Plc Detergent compositions

Also Published As

Publication number Publication date
KR880009165A (ko) 1988-09-14
IN166783B (pl) 1990-07-14
OA08708A (en) 1989-03-31
DE3860305D1 (de) 1990-08-23
EP0276997A2 (en) 1988-08-03
CA1329533C (en) 1994-05-17
TR23614A (tr) 1990-04-30
BR8800255A (pt) 1988-09-13
KR910004890B1 (ko) 1991-07-15
AU592248B2 (en) 1990-01-04
ES2016406B3 (es) 1990-11-01
EP0276997A3 (en) 1988-09-21
AU1078288A (en) 1988-08-04
PH24428A (en) 1990-06-25

Similar Documents

Publication Publication Date Title
EP0213730B1 (en) Detergent composition with fabric softening properties
US4999129A (en) Process and composition for washing soiled polyester fabrics
EP0213729B1 (en) Detergent compositions
US4954292A (en) Detergent composition containing PVP and process of using same
US3741911A (en) Phosphate-free detergent composition
CA1084912A (en) Cellulose ethers and detergent compositions containing same
EP0426304B1 (en) Fabric treatment composition with softening properties
US4298492A (en) Built liquid detergent composition
IE43532B1 (en) Detergent compositions
EP0320296B1 (en) Fabric softening additive for detergent compositions
US5009800A (en) Fabric softening additive for detergent compositions: cellulose ether and organic fabric softener
JPH02107699A (ja) 洗剤組成物
EP0276997B1 (en) Detergent composition with fabric softening properties
AU616545B2 (en) Detergent composition with fabric softening properties
US3853779A (en) Low foaming detergent compositions
AU600654B2 (en) Detergent compositions containing polymers
SE412598B (sv) Vetskeformig tvettmedelskomposition med kraftig tvetteffekt
JPH039229B2 (pl)
JPH0229120B2 (ja) Konasetsukensoseibutsu
JPS6059960B2 (ja) 粉セツケン組成物

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: 19880905

17Q First examination report despatched

Effective date: 19890807

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: 3860305

Country of ref document: DE

Date of ref document: 19900823

ET Fr: translation filed
ITF It: translation for a ep patent filed
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
ITTA It: last paid annual fee
EAL Se: european patent in force in sweden

Ref document number: 88300688.4

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

Ref country code: CH

Payment date: 19970107

Year of fee payment: 10

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

Ref country code: SE

Payment date: 19971215

Year of fee payment: 11

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

Ref country code: NL

Payment date: 19980121

Year of fee payment: 11

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: 19980131

Ref country code: CH

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

Effective date: 19980131

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: SE

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

Effective date: 19990128

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: 19990801

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: 20021231

Year of fee payment: 16

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

Ref country code: GB

Payment date: 20030122

Year of fee payment: 16

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

Ref country code: DE

Payment date: 20030131

Year of fee payment: 16

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

Ref country code: ES

Payment date: 20030207

Year of fee payment: 16

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: 20040127

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: 20040128

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: 20040803

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

Effective date: 20040127

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: 20040930

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

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: 20050127

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20040128