EP0434460A1 - Composition détergente - Google Patents

Composition détergente Download PDF

Info

Publication number
EP0434460A1
EP0434460A1 EP19900314160 EP90314160A EP0434460A1 EP 0434460 A1 EP0434460 A1 EP 0434460A1 EP 19900314160 EP19900314160 EP 19900314160 EP 90314160 A EP90314160 A EP 90314160A EP 0434460 A1 EP0434460 A1 EP 0434460A1
Authority
EP
European Patent Office
Prior art keywords
soap
detergent composition
organic solvent
composition according
fatty acyl
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
EP19900314160
Other languages
German (de)
English (en)
Other versions
EP0434460B1 (fr
Inventor
Robert Stanley Lee
Terry Instone
John George Chambers
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 EP0434460A1 publication Critical patent/EP0434460A1/fr
Application granted granted Critical
Publication of EP0434460B1 publication Critical patent/EP0434460B1/fr
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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/006—Detergents in the form of bars or tablets containing mainly surfactants, but no builders, e.g. syndet bar
    • 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
    • C11D10/00—Compositions of detergents, not provided for by one single preceding group
    • C11D10/04—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
    • C11D10/042—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap based on anionic surface-active compounds and soap
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/126—Acylisethionates

Definitions

  • the present invention relates to a solid detergent composition, particularly to a toilet bar containing soap in combination with a non-soap detergent.
  • Appropriate selection of soap components ensures a bar having acceptable lathering and physical properties. It has however been shown that soap can be somewhat harsh to the skin.
  • Alternative surfactants to soap have therefore been investigated to provide skin cleansing compositions that are more mild to the skin.
  • a number of proposals have been made to provide solid skin cleansing compositions containing a mixture of soap and mild surfactants. There is however a tendency for the mild surfactants to affect adversely the physical properties of the bar in terms for example of its rate of wear and mush characteristics.
  • the alternative bar making process comprising forming a melt of the constituent ingredients and pouring the melt either into individual moulds or into large frames for subsequent cutting into smaller portions has usually been reserved for low volume specialist bars. It has for example been employed as a means of achieving transparent soap bars. Frequently however the desire to achieve bars of high transparency has been at the expense of other bar properties. Traditionally transparent soap bars have been achieved by use of a volatile solvent such as ethanol, a solution of soap and other ingredients in the ethanol being cast into the moulds or frames and then left for a number of months for the ethanol to evaporate.
  • a volatile solvent such as ethanol
  • the initial solution is semi-opaque and only becomes transparent as the alcohol evaporates.
  • the process however is costly due to the long maturing time required and results in misshapen bars due to the loss of solvent.
  • the resulting bars moreover tend to have user properties inferior to conventional opaque bars produced by the milling and stamping route.
  • a detergent composition in solid form comprising 15 to 35 wt% soap, 5 to 50 wt% non-soap surfactant which is fatty acyl isethionate or a mixture of fatty acyl isethionate and a lesser amount of other mild surfactant, 5 to 50 wt% water and 5 to 50 wt% organic solvent, wherein the organic solvent comprises more than 50 wt% methanol, ethanol, propanol or mixtures thereof.
  • 'mild surfactant we mean a surfactant that solubilises less than 500 mg N/100 cm3 in a zein test.
  • the zein test employed is as described by E Gotte, Proc. Int. Cong. Surface Active Subs., 4th, Brussels, 3, 89-90 (1964).
  • the present invention thus provides a detergent composition in solid form containing both soap and a mild surfactant and a volatile alcohol solvent.
  • the composition is suitably in bar form and can, but need not be, transparent.
  • the present composition can thus provide a toilet bar that is milder to the skin than a conventional all soap bar. Due to the present formulation the bars in use have improved physical characteristics, in particular the bars have a reduced tendency to develop a soft surface layer on contact with water and hence are less messy and mushy.
  • the soap component is an essential element of the present composition. It is preferably at a level between 20 and 30 wt% with respect to the whole composition.
  • the soap component comprises more than 8 wt%, preferably more than 15 wt%, with respect to the total composition, soaps having a saturated fatty acid chain length of C16 or more.
  • substantially the entire soap component can comprise soaps having a saturated chain length of C16 or more.
  • Such soaps are relatively water insoluble and provide a structure to the present solid composition.
  • the ratio of soluble soaps i.e. soaps having a chain length of C14 or less or unsaturated C18 soaps
  • Suitable sources of soap include traditional soap making materials.
  • hardened tallow soap comprising an approximate 1: 1 mixture of saturated C16 and C18 soaps provides a useful source of appropriate water insoluble soaps.
  • the soaps employed are preferably sodium soaps, but potassium, ammonium or substituted ammonium soaps could be employed instead either in whole or in part.
  • Fatty acyl isethionates used in this invention have acyl groups containing 8 to 22 carbon atoms. Acyl chain length is usually 8 to 18 carbon atoms. This isethionate may well be a mixture of compounds of varying acyl chain length.
  • the solubilising cation of the fatty acyl isethionate is preferably sodium but other possibilities include potassium, ammonium and substituted ammonium.
  • the amount of fatty acyl isethionate is preferably between 20 and 40 wt%, more preferably between 20 or 25 and 35 wt% with respect to the whole composition.
  • Other mild surfactants may possibly be included in amounts which are less than the amount of fatty acyl isethionate, and which are such that the total of non-soap surfactant does not exceed 50 wt% based on the whole composition.
  • mild surfactant if any, should satisfy the zein test, as mentioned.
  • mild surfactants include sarcosinates, amine oxides, ether sulphates, coconut diethanolamide, alcohol ethoxylates, sulphosuccinates and mixtures thereof.
  • the zein test is a measure of irritancy and provides a classification in terms of the amount of nitrogen found in the supernatant after equilibration of 40 cm3 of a 1 wt% surfactant solution with 2 g of zein powder at 35°C for 1 hour.
  • a mild surfactant to be one which yields a value of less than 500 mg nitrogen per 100 cm3.
  • any surfactant is employed in compositions of the present invention yields a value of less than 400 mg nitrogen per 100 cm3. These values are based on zein having a total N content of 700 mg N per 5 gm of zein powder.
  • the test is easy to perform and is increasingly being employed by commercial suppliers of surfactants as an indication of the irritancy of their products.
  • the organic solvent component is preferably present at a level between 10 and 40 wt%, more preferably at a level between 10 and 25 wt%, with respect to the whole composition and can if desired comprise wholly the C1 to C3 monohydric alcohols recited above.
  • the recited C1 to C 3 monohydric alcohol(s) comprise at least 75 wt% of the organic solvent component.
  • the organic solvent is present a level in total of less than 10 wt%, suitably methanol, ethanol, propanol or mixture thereof is present at a level to comprise more than 5 wt% with respect to the total bar composition.
  • the presence of these solvents in a major amount in the solvent component is essential to achieve a solid composition having the desired physical properties.
  • the presence of the defined solvent increases the solubility of the surfactant and the soap in a melt during its preparation, and hence the quantity that can be included, but not at the expense of finished bar properties.
  • other ingredients that could be included in the organic solvent include sugars, linear and branched polyols and cyclic polyols. Particular examples include sucrose, fructose, glucose, glycerol, diethyleneglycol, propyleneglycol, triethyleneglycol, sorbitol, mannitol and polyethyleneglycols having a molecular weight between 400 and 6000. Whether or not any such other ingredients are included will depend on the desired end product. Their presence may for example be helpful in modifying the feel and in-use properties of the bar and if desired in enhancing the transparency of the bar.
  • the water employed in compositions of this invention is preferably distilled or deionised. Within the above stated range it is present in an amount to balance the other ingredients present to 100 wt%.
  • the composition includes some free fatty acid having a carbon chain length in the range 8 to 22 carbon atoms.
  • saturated C16 and C18 acids may be used.
  • the amount may be at least 10% or 15% by weight based on the fatty acyl isethionate. The amount will not generally exceed 40% by weight based on the fatty acyl isethionate.
  • the ratio of fatty acid (neutral) soap in the composition may lie in a range from 0.05: 1 to 0.4: 1. Preferably it does not exceed 0.25: 1.
  • ingredients that can be present in the present solid composition include those conventionally employed in soap manufacture. They include antioxidants, preservatives, dyes, pearlescers, opacifiers and perfumes.
  • compositions are suitable for manufacture by forming a melt of the constituent ingredients and casting the melt.
  • One possibility is to cast the melt into large moulds or frames for subsequent cutting into smaller portions or directly into moulds which define a bar shape.
  • the melt is poured directly into separate moulds which comprise the packaging means for the subsequently set bars.
  • Such moulds can for example comprise rigid or semi-rigid plastic packaging or can even be flexible sachets which adapt to the internal pressure exerted by the melt.
  • packaging means can be air-tightly sealed and, if for example transparent, provide an attractive means to display the finished product.
  • the melt is heated to 70 to 85°C in order to ensure full dissolution of all the ingredients.
  • the soap component is admixed with the other ingredients already in the form of a melt at 70 to 85°C.
  • the present invention provides a process for making a detergent composition in solid form comprising forming a melt at 70 to 85°C comprising 15 to 35 wt% soap, 5 to 50 wt% non-soap surfactant which is fatty acyl isethionate or a mixture of fatty acyl isethionate and a lesser amount of other mild surfactant, 5 to 50 wt% water and 5 to 50 wt% organic solvent, the organic solvent comprising more than 50 wt% methanol, ethanol, propanol or mixtures thereof, and casting the melt into moulds.
  • Bars were made from seven formulations as given in the Table below. In each case a melt was formed at 80°C of all the ingredients excluding the soap, to which the soap was added to ensure full dissolution. The resulting melts were cast into moulds and allowed to set.
  • the bars obtained in each case were firm in appearance and felt firm when handled. They were assessed for mildness by the zein test referred to above. They were also assessed for formation of a mushy surface in use. This was assessed by a test in which each bar is twisted 18 times in gloved hands after immersion in a bowl of water at 30°C. The procedure is repeated 8 times a day for 4 days by a panel of testers. At the end of the fourth day, the bars are left overnight in a drained tray. On the fifth day, the face of the bar which has been in contact with the tray is prodded by an experienced worker. The number score given in the table reflects the depth and area of indentation achieved, the higher the number, the greater the indentation and hence the worse the mush properties.
  • the fatty acid sodium soap is a 1: 1 mixture of saturated C16 and C18 soaps derived from hardened tallow.
  • the free fatty acids were a similar mixture of saturated C16 and C18 fatty acids.
  • the sodium fatty acyl isethionate is sodium cocoyl isethionate.
  • Industrial methylated spirit is a mixture of ethanol and methanol in 9: 1 ratio.
  • Dobanol 91-8 is a C9-C11 alcohol ethoxylate with average 8EO.
  • non-soap surfactants employed score as follows on the above defined zein test.
  • Lather volume was determined by an objective test and by means of a panel assessment.
  • the panel also assessed creaminess of the lather. No significant difference could be detected between the lathering properties of the two compositions.

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)
  • Cosmetics (AREA)
EP19900314160 1989-12-21 1990-12-21 Composition détergente Expired - Lifetime EP0434460B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB898928902A GB8928902D0 (en) 1989-12-21 1989-12-21 Detergent bar
GB8928902 1989-12-21

Publications (2)

Publication Number Publication Date
EP0434460A1 true EP0434460A1 (fr) 1991-06-26
EP0434460B1 EP0434460B1 (fr) 1995-07-19

Family

ID=10668316

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19900314160 Expired - Lifetime EP0434460B1 (fr) 1989-12-21 1990-12-21 Composition détergente

Country Status (9)

Country Link
EP (1) EP0434460B1 (fr)
JP (1) JP2592547B2 (fr)
AU (1) AU638301B2 (fr)
BR (1) BR9006524A (fr)
CA (1) CA2032754C (fr)
DE (1) DE69021032T2 (fr)
ES (1) ES2075174T3 (fr)
GB (1) GB8928902D0 (fr)
ZA (1) ZA9010281B (fr)

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0507559A2 (fr) * 1991-04-03 1992-10-07 Unilever Plc Composition détergente
FR2694569A1 (fr) * 1992-08-10 1994-02-11 Icc France Article d'hygiène solide et transparent, notamment sous forme de pain dermatologique, et son procédé de préparation.
JPH0762388A (ja) * 1993-08-25 1995-03-07 P & P F:Kk 透明状固型洗浄剤組成物
US5482643A (en) * 1993-05-19 1996-01-09 Lever Brothers Company, Division Of Conopco, Inc. Soap bars made with ternary system of fatty isethionate ester, fatty acid, and water
US5500155A (en) * 1994-03-18 1996-03-19 Henkel Kommanditgesellschaft Auf Aktien Detergent mixtures of fatty acid isethionate salts and fatty alcohols
AU669882B2 (en) * 1992-02-05 1996-06-27 Procter & Gamble Company, The Stable pumpable synthetic detergent composition and process for the storage thereof
US5981451A (en) * 1998-09-23 1999-11-09 Lever Brothers Company Non-molten-mix process for making bar comprising acyl isethionate based solids, soap and optional filler
WO2001030959A1 (fr) * 1999-10-25 2001-05-03 Unilever Plc Composition de detergence moulee
WO2002031099A1 (fr) * 2000-10-13 2002-04-18 Unilever Plc Composition detergente sous forme solide
WO2002053689A2 (fr) * 2000-12-29 2002-07-11 Unilever Plc Composition detergente amelioree
US10758750B2 (en) 2015-07-29 2020-09-01 Conopco, Inc. Cleansing composition with improved availability of benefit agent

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4206069A (en) * 1976-04-22 1980-06-03 Colgate-Palmolive Company Transparent detergent pellets
US4663070A (en) * 1985-01-25 1987-05-05 Lever Brothers Company Process for preparing soap-acyl isethionate toilet bars
US4695395A (en) * 1984-09-25 1987-09-22 Lever Brothers Company Cleaning compositions with skin protection agents
EP0287300A2 (fr) * 1987-04-13 1988-10-19 Unilever Plc Compositions de nettoyage
US4832861A (en) * 1988-05-27 1989-05-23 Lever Brothers Company Soap compositions of enhanced antimicrobial effectiveness

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2348967A1 (fr) * 1976-04-22 1977-11-18 Colgate Palmolive Co Composition detergente solide pour nettoyage localise

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4206069A (en) * 1976-04-22 1980-06-03 Colgate-Palmolive Company Transparent detergent pellets
US4695395A (en) * 1984-09-25 1987-09-22 Lever Brothers Company Cleaning compositions with skin protection agents
US4663070A (en) * 1985-01-25 1987-05-05 Lever Brothers Company Process for preparing soap-acyl isethionate toilet bars
EP0287300A2 (fr) * 1987-04-13 1988-10-19 Unilever Plc Compositions de nettoyage
US4832861A (en) * 1988-05-27 1989-05-23 Lever Brothers Company Soap compositions of enhanced antimicrobial effectiveness

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0507559A2 (fr) * 1991-04-03 1992-10-07 Unilever Plc Composition détergente
EP0507559A3 (en) * 1991-04-03 1993-01-07 Unilever Plc Detergent composition
AU669882B2 (en) * 1992-02-05 1996-06-27 Procter & Gamble Company, The Stable pumpable synthetic detergent composition and process for the storage thereof
FR2694569A1 (fr) * 1992-08-10 1994-02-11 Icc France Article d'hygiène solide et transparent, notamment sous forme de pain dermatologique, et son procédé de préparation.
US5482643A (en) * 1993-05-19 1996-01-09 Lever Brothers Company, Division Of Conopco, Inc. Soap bars made with ternary system of fatty isethionate ester, fatty acid, and water
JPH0762388A (ja) * 1993-08-25 1995-03-07 P & P F:Kk 透明状固型洗浄剤組成物
US5500155A (en) * 1994-03-18 1996-03-19 Henkel Kommanditgesellschaft Auf Aktien Detergent mixtures of fatty acid isethionate salts and fatty alcohols
US5981451A (en) * 1998-09-23 1999-11-09 Lever Brothers Company Non-molten-mix process for making bar comprising acyl isethionate based solids, soap and optional filler
WO2001030959A1 (fr) * 1999-10-25 2001-05-03 Unilever Plc Composition de detergence moulee
US6365567B1 (en) 1999-10-25 2002-04-02 Unilever Home & Personal Care Usa Melt cast solid shaped detergent bar compositions with high water content
WO2002031099A1 (fr) * 2000-10-13 2002-04-18 Unilever Plc Composition detergente sous forme solide
AU2001291892B2 (en) * 2000-10-13 2006-03-16 Unilever Plc Solid shaped detergent composition
WO2002053689A2 (fr) * 2000-12-29 2002-07-11 Unilever Plc Composition detergente amelioree
WO2002053689A3 (fr) * 2000-12-29 2002-10-10 Unilever Plc Composition detergente amelioree
AU2002219186B2 (en) * 2000-12-29 2005-11-03 Unilever Plc Detergent composition
AU2002219186B8 (en) * 2000-12-29 2005-11-17 Unilever Plc Detergent composition
US10758750B2 (en) 2015-07-29 2020-09-01 Conopco, Inc. Cleansing composition with improved availability of benefit agent

Also Published As

Publication number Publication date
AU6829790A (en) 1991-06-27
JP2592547B2 (ja) 1997-03-19
EP0434460B1 (fr) 1995-07-19
CA2032754A1 (fr) 1991-06-22
GB8928902D0 (en) 1990-02-28
AU638301B2 (en) 1993-06-24
CA2032754C (fr) 1996-12-10
JPH06228599A (ja) 1994-08-16
ZA9010281B (en) 1992-08-26
DE69021032T2 (de) 1995-11-30
DE69021032D1 (de) 1995-08-24
ES2075174T3 (es) 1995-10-01
BR9006524A (pt) 1991-10-01

Similar Documents

Publication Publication Date Title
US4165293A (en) Solid transparent cleanser
US5264144A (en) Freezer personal cleansing bar with selected fatty acid soaps for improved mildness and good lather
CA2131308C (fr) Barre de savon a ph neutre
CA2011126C (fr) Pain de detergent
KR100235692B1 (ko) 투명한 개인용 세정 바
US6255265B1 (en) Low synthetic soap bars comprising organic salts and polyalkylene glycol
US5264145A (en) Personal cleansing freezer bar with selected fatty acid soaps and synthetic surfactant for reduced bathtub ring, improved mildness, and good lather
WO1993019159A1 (fr) SAVONNETTE A pH EGAL A CELUI DE LA PEAU
KR100831810B1 (ko) 높은 함량의 액체 연화제를 포함하는 피부 세정 바아
WO1996004361A1 (fr) Procede de fabrication de barres transparentes pour l'hygiene personnelle
US6458751B1 (en) Skin cleansing bar comprising a fatty alcohol with low mush
EP0434460B1 (fr) Composition détergente
JP2574592B2 (ja) 石鹸組成物及び固形石鹸製造方法
AU699797B2 (en) Soap bars containing polyalkylene glycol and fatty acid
EP0459769B1 (fr) Compositions de nettoyage avec une réduction de pâte, amélioration de la douceur ou les deux
KR20060126540A (ko) 가공성이 좋으며 거품이 잘 형성되는 지방산 비누/지방산바
EP0405664B1 (fr) Produit pour le nettoyage corporel avec polymère cationique à groupe amine encombrante et odeur compatible
US6228822B1 (en) Synthetic detergent base material and synthetic detergent bar produced therefrom
AU667733B2 (en) Improved freezer personal cleansing bar with selected fatty acid soaps for improved mildness and good lather
JPH0741798A (ja) 固型石けん組成物
NZ248471A (en) A "freezer" soap bar comprising mostly na and k soaps of: myristic, palmitic and stearic acids plus oleic and/or lauric acid and/or minor fatty acid soap; water; and optionally a lathering synthetic surfactant and a sugar

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

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

17P Request for examination filed

Effective date: 19911005

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: 19940923

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: 69021032

Country of ref document: DE

Date of ref document: 19950824

ET Fr: translation filed
REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2075174

Country of ref document: ES

Kind code of ref document: T3

ITF It: translation for a ep patent filed
NLT2 Nl: modifications (of names), taken from the european patent patent bulletin

Owner name: UNILEVER N.V.

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

Ref country code: CH

Payment date: 19961203

Year of fee payment: 7

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

Ref country code: FR

Payment date: 19971110

Year of fee payment: 8

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

Ref country code: SE

Payment date: 19971117

Year of fee payment: 8

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

Ref country code: DE

Payment date: 19971124

Year of fee payment: 8

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

Ref country code: GB

Payment date: 19971126

Year of fee payment: 8

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

Ref country code: ES

Payment date: 19971211

Year of fee payment: 8

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

Ref country code: NL

Payment date: 19971218

Year of fee payment: 8

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: 19971231

Ref country code: CH

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

Effective date: 19971231

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: GB

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

Effective date: 19981221

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: 19981222

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: 19990701

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

Effective date: 19981221

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: 19990831

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

Effective date: 19990701

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: DE

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

Effective date: 19991001

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: 19991222

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20000114

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: 20051221