EP0441652B1 - Composition détergente - Google Patents

Composition détergente Download PDF

Info

Publication number
EP0441652B1
EP0441652B1 EP91301046A EP91301046A EP0441652B1 EP 0441652 B1 EP0441652 B1 EP 0441652B1 EP 91301046 A EP91301046 A EP 91301046A EP 91301046 A EP91301046 A EP 91301046A EP 0441652 B1 EP0441652 B1 EP 0441652B1
Authority
EP
European Patent Office
Prior art keywords
sulfosuccinate
isethionate
composition according
weight
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.)
Expired - Lifetime
Application number
EP91301046A
Other languages
German (de)
English (en)
Other versions
EP0441652A1 (fr
Inventor
Karla Jean Rys
Alan Paul Greene
Frederick Sylvio Osmer
Joseph James Podgorsky
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 EP0441652A1 publication Critical patent/EP0441652A1/fr
Application granted granted Critical
Publication of EP0441652B1 publication Critical patent/EP0441652B1/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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/37—Mixtures of compounds all of which are anionic
    • 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
    • C11D1/123—Sulfonic acids or sulfuric acid esters; Salts thereof derived from carboxylic acids, e.g. sulfosuccinates
    • 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 invention relates to solid skin cleansing, detergent compositions containing acyl isethionates.
  • soap has been utilized as a skin cleanser. Soap is, however, a very harsh chemical. Irritated and cracked skin result from use of soap, especially in colder climates. There are, however, certain benefits from the use of soap including low cost, ease of manufacture into bars, and good lathering properties.
  • U.S. 4,335,025 discusses synthetic detergent bars containing critical amounts of components.
  • alkali metal salts of C8 ⁇ 16 alkyl sulfosuccinate together with a selected water soluble anionic detergent which may include a C10 ⁇ 16 acyl isethionate, a waxy extender such as a C12 ⁇ 22 fatty acid or alcohol and the like, and other optional extenders.
  • U.S. 3,901,832 discusses a detergent bar containing a monoalkyl sulfosuccinate and a specific plasticizer in detergent cakes.
  • U.S. 3,989,647 discusses a synthetic toilet bar containing selected amounts of an alkane sulfonate, a fatty acid, and a binder modifier, which may be an alkyl sulfosuccinate.
  • U.S. 4,812,253 discusses various compositions containing polymeric skin mildness aids, moisturizers, soap and selected surfactants which include acyl isethionates and alkyl sulfosuccinate.
  • the present invention aims to provide compositions with excellent skin mildness while also possessing good lather, mush and processing properties.
  • a skin cleansing toilet bar composition comprising:
  • Preferred skin cleansing compositions have acyl isethionates as the main active in combination with monoalkyl sulfosuccinates as the co-active. Such compositions can be substantially milder to the skin than previously known compositions.
  • compositions within this invention may contain some free fatty acid. They may contain some free isethionate. They may contain some soap.
  • a preferred solid skin cleansing composition comprises:
  • Preferred weight ratios of acyl isethionate to sulfosuccinates are 6:1 to 2:1 and most preferred to maintain mildness are 2:1 to 4.5:1.
  • the irritancy of the already mild main active, acyl isethionate can be reduced significantly by the incorporation of sulfosuccinates.
  • the cleansers resulting from this mixture of actives have superior skin mildness together with good bar properties such as processability, low mush, good lather, and good tactile characteristics. In addition, they are easily processable using standard manufacturing equipment. In order for processability to be good, it is usually required for the composition to have an appropriate hardness and stickiness.
  • Isethionate salts in the range of about C6-C18 such as those derived from coconut fatty acids, for example, have been employed in a number of commercial cleansing products and are known to produce a voluminous, creamy lather.
  • This active by itself, has been shown to be very mild to the skin. These actives are solid at room temperature and serve as excellent structurants when used in bar formulations.
  • the isethionate ester salts that may be employed herein are preferably acyl ester isethionates and most preferably the cocoyl ester.
  • These preferred esters may be prepared from the usual cocoyl fatty acids having a small percentage of fatty acid chains below C8 with over 95% of the carbon chain distribution being between C8 and C18 and more than half being C12 or less.
  • the acyl chain length of the esters will have at least about 90% C6-C18 and more than about 30% C14 or lower.
  • a typical cocoyl fraction will contain: Chain Length Wt.% Fatty Acid Combined As Cocoyl Isethionate C6 ⁇ 10 10-25 C12 45-55 C14 ⁇ 18 20-40 C18 unsaturated 1-15
  • the sulfosuccinates useful in the invention may be any suitable sulfosuccinate esther mono-esters (half esters) or di-esters and any alkali metal, alkaline earth metal or ammonium salt, but the sulfosuccinates are preferably monoesters and preferably prepared through an alkanolamine intermediate so as to introduce an amido group into the molecule.
  • the sulfosuccinate monoester is prepared through a monoethanolamine intermediate.
  • R in Structure 1 is derived from coconut fatty acids, but in other forms may be any convenient alkyl group.
  • the chain length distribution of coconut fatty acids is similar to that for the coco group on the isethionate.
  • the chain length distribution will contain at least 90% of C8 to C18 with more than half made up of C8 to C14.
  • a typical fatty acid distribution in the cocoyl portion is as follows: Chain Length Weight % Fatty Acid Combined As Cocoyl Amido Sulfosuccinate C6 ⁇ 10 10-25 C12 45-55 C14 ⁇ 18 20-40 C18 unsaturated 1-15
  • the sulfosuccinate of Structure 1 may conveniently be prepared by a two step reaction:
  • the relative amounts of isethionate esters to sulfosuccinate will preferably lie in the weight ratio of 2:1 to 4.5:1, or even as high as 6:1, preferably from 3:1 to 4:1, optimally about 3.5:1.
  • soap may be somewhat harsh and when present in the compositions of this invention should be at a level no higher than about 25%, preferably less than 5%, and advantageously totally absent.
  • Free fatty acids of about 8-22 carbon atoms are desirably incorporated within the compositions of the present invention. Some of these fatty acids are present to operate as superfatting agents and others as skin feel and creaminess enhancers. Fatty alcohols, fatty amides and the like may also be employed. Superfatting agents enhance lathering properties and may be selected from fatty acids of carbon atoms numbering 8-18, preferably 10-18, in an amount up to 40% by weight of the composition. Skin feel and creaminess enhancers, the most important of which is stearic acid, are also desirably present in these compositions.
  • humectants such as glycerine
  • anti wear agents such as polymer JR and natural and synthetic gums
  • germicides perfumes, colorants, dyes, pigments such as titanium dioxide, electrolytes, and water.
  • Dove toilet bars Dove is a registered trademark of Lever Brothers Co. which contains sodium cocoyl isethionate as main ingredient
  • the Flex Wash test procedure consists of three daily two minute washes of the antecubital fossa (flex area of elbow). This method is an "exaggerated use” method designed to differentiate very mild products. Erythemal response varies only slightly with temperature and humidity fluctuations making the protocol suitable for year round testing.
  • Panelist flex areas must be free of any skin condition (eczema, dryness, irritation, cuts or abrasions).
  • Any skin condition eczema, dryness, irritation, cuts or abrasions.
  • An antihistamines, anti-inflammatory drugs (more than 8 per week) or topical, oral or injectable cortisone on a regular basis was excluded from the study.
  • the panel was divided into two sub-groups which were balanced for left handedness. Group I was assigned composition "A" for the left flex and "B" for the right flex. Group II reversed the order.
  • the panelist was instructed to moisten the left flex area, the sponge and test compositions formulated as toilet bars were dampened with tap water (100 ppm calcium/magnesium ions). The sponge was then stroked over the test bar 10 times by the evaluator. The "dosed" sponge was placed in the panelist's right hand. The panelist then washed the left flex area for exactly two minutes. Thereupon, the flex was rinsed and patted dry. This washing procedure was repeated on the right arm with the appropriate composition. Thus, both arms are tested simultaneously. Washing by this procedure was repeated three times daily for 5 consecutive days for a total of 15 washes. Treatment times were scheduled 1.5 hours apart. Each test site was evaluated immediately prior to washing and 4 hours after the third daily wash.
  • the grading scale was as follows: 0 - no erythema 0.5 - barely perceptible erythema 1 - mild spotty erythema/no edema 1.5 - mild/moderate erythema/with or without edema 2 - moderate confluent erythema/with or without edema or vesiculation
  • Each test site was treated in the prescribed method until a grading of "2" or greater was attained or 15 washings had been completed. When a score of "2" or greater was attained, the treatment was discontinued on that flex.
  • Mean Rank Scores is the sum total of grade scores for 15 assessments per panelist averaged over the scores from all panelists. Thus, theoretically, the average score could range from 0 to 30; the lower score indicating absolutely no skin irritation while the 30 score being the most severe.
  • Mean Endpoint Erythema scores are the mean of the evaluation scores, for each panelist, at which the first arm received a grade of "2" or greater erythema score or at the completion of fifteen washes.
  • This example illustrates the difference in mildness between Dove and a toilet bar employing the Acyl Isethionate/Alkyl Sulfosuccinate active system, where the ratio of Isethionate to Sulfosuccinate is 2.20:1.
  • the ratio of Cocoyl Isethionate to Amido Sulfosuccinate is 3.64:1. Mildness, superior to Dove, is proven by the Flex Wash.
  • Mush - Pre-weighed bars were immersed in water for 2 hours. The increase in weight was noted. Mush was removed and the remainder of the bar was dried. After reweighing, mush was calculated as the weight of mush per 50 cm2 of surface mushed. Lower values indicated better performance.
  • test bars had the following compositions: Hand Wash Formulations BAR 1 2 3 4 5 6 7 Isethionate: Sulfosuccinate 2.87:1 2.88:1 5.19:1 3.64:1 5.12:1 3.59:1 Sodium Cocoyl Isethionate 43.6 40.9 46.7 43.7 46.1 43.1 Dove Stearic Acid 22.0 23.7 23.9 23.9 23.7 23.7 Sodium Isethionate 9.3 13.7 13.8 13.8 13.7 13.7 Disodium Cocamido MEA Sulfosuccinate 15.2 14.2 9.0 12.0 9.0 12.0 Sodium Chloride 2.6 0.35 0.35 0.35 0.35 0.35 Carbowax 8000 1.0 1.0 0.0 0.0 1.0 1.0 Perfume 1.0 1.0 1.0 1.0 1.0 1.0 1.0 Titanium Dioxide 0.5 0.5 0.5 0.5 0.5 EDTA 0.02 0.02 0.02 0.02 0.02 0.02 0.02 EHDP 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 Water 4.7

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)

Claims (10)

  1. Composition de pain de toilette pour le nettoyage de la peau comprenant :
    i) des esters acyles de sels d'acide iséthionique, la répartition de la longueur de chaîne acyle desdits esters étant au moins à 90 % de C₆ à C₁₈, et ayant plus de 30 % de C₁₄ ou moins ; et
    ii) au moins un sulfosuccinate pour lequel la proportion en poids desdits esters acyles par rapport au sulfosuccinate est de 10:1 à 2:1.
  2. Composition selon la revendication 1 dans laquelle le sulfosuccinate est un monoester.
  3. Composition selon la revendication 2 dans laquelle le sulfosuccinate est dérivé d'un monoéthalonamide.
  4. Composition selon la revendication 2 dans laquelle le sulfosuccinate est un amido sulfosuccinate.
  5. Composition selon la revendication 4 dans laquelle le sulfosuccinate est un sulfosuccinate cocoamido.
  6. Composition selon l'une quelconque des revendications précédentes dans laquelle la proportion d'ester iséthionate par rapport au sulfosuccinate est comprise entre 6:1 et 2:1.
  7. Composition selon l'une quelconque des revendications précédentes dans laquelle la proportion d'ester iséthionate par rapport au sulfosuccinate est comprise entre 4,5:1 et 3:1.
  8. Composition selon l'une quelconque des revendications précédentes dans laquelle ladite longueur de chaîne acyle a la répartition suivante : Longueur de chaîne % Poids C₆₋₁₀ 10-25 C₁₂ 45-55 C₁₄₋₁₈ 20-40 C₁₈ insaturée 1-15
  9. Composition selon l'une quelconque des revendications précédentes dans laquelle la quantité desdits esters acyles des sels d'acide iséthionate est de 20 % à 70 % en poids de la composition.
  10. Composition selon la revendication 9 qui comprend également 2 % à 40 % d'acide gras libre, 2 % à 20 % d'iséthionate de sodium et 2 % à 20 % en poids d'eau, la quantité de savon dans la composition n'étant pas supérieure à 25 % en poids et la quantité de toute autre matière dans la composition n'étant pas supérieure à 20 % en poids.
EP91301046A 1990-02-09 1991-02-08 Composition détergente Expired - Lifetime EP0441652B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US47768290A 1990-02-09 1990-02-09
US477682 1990-02-09

Publications (2)

Publication Number Publication Date
EP0441652A1 EP0441652A1 (fr) 1991-08-14
EP0441652B1 true EP0441652B1 (fr) 1995-07-19

Family

ID=23896912

Family Applications (1)

Application Number Title Priority Date Filing Date
EP91301046A Expired - Lifetime EP0441652B1 (fr) 1990-02-09 1991-02-08 Composition détergente

Country Status (8)

Country Link
EP (1) EP0441652B1 (fr)
JP (1) JP2975450B2 (fr)
AU (1) AU637668B2 (fr)
BR (1) BR9100525A (fr)
CA (1) CA2035681C (fr)
DE (1) DE69111259T2 (fr)
ES (1) ES2076462T3 (fr)
ZA (1) ZA91953B (fr)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994007988A1 (fr) * 1992-10-05 1994-04-14 Mona Industries, Inc. Barres detersives synthetiques et procede de production
AU5884694A (en) * 1993-01-19 1994-08-15 Unilever Plc Low soap bar composition
DE4409321A1 (de) * 1994-03-18 1995-09-21 Henkel Kgaa Detergensgemische
ES2201107T3 (es) * 1994-05-10 2004-03-16 THE PROCTER & GAMBLE COMPANY Composiciones para pastilla de jabon sintetica para hiogiene personal con bajos niveles de polimeros no ionicos polietileno/polipropilenglicol que mejoran la suavidad.
US5683973A (en) * 1996-02-15 1997-11-04 Lever Brothers Company, Division Of Conopco, Inc. Mild bar compositions comprising blends of higher melting point polyalkylene glycol(s) and lower melting point polyalkylene glycol(s) as processing aids
GB9623935D0 (en) * 1996-11-18 1997-01-08 Unilever Plc Aqueous cleansing composition
FR3007641B1 (fr) * 2013-06-27 2016-11-18 Oreal Composition nettoyante stable sous forme de solide souple

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1402265A (en) * 1971-08-24 1975-08-06 Colgate Palmolive Co Soap-synthetic detergent combination bars
IT1165608B (it) * 1978-01-19 1987-04-22 Unilever Nv Barra detergente, particolarmente per lavaggio personale
US4335025A (en) * 1980-02-19 1982-06-15 Witco Chemical Corporation Process for the preparation of synthetic detergent bars, and products produced thereby
DE3335705A1 (de) * 1983-10-01 1985-04-11 Chemische Werke Hüls AG, 4370 Marl Fluessiger teppichreiniger
ES2061668T3 (es) * 1987-09-17 1994-12-16 Procter & Gamble Barra de tocador para limpieza de la piel con bajo contenido de humedad.
US4954282A (en) * 1989-04-19 1990-09-04 Lever Brothers Company Acyl isethionate skin cleansing compositions

Also Published As

Publication number Publication date
EP0441652A1 (fr) 1991-08-14
CA2035681C (fr) 1998-12-08
ZA91953B (en) 1992-10-28
AU637668B2 (en) 1993-06-03
CA2035681A1 (fr) 1991-08-10
JPH04234810A (ja) 1992-08-24
AU7020691A (en) 1991-08-15
DE69111259D1 (de) 1995-08-24
DE69111259T2 (de) 1995-12-21
BR9100525A (pt) 1991-10-29
JP2975450B2 (ja) 1999-11-10
ES2076462T3 (es) 1995-11-01

Similar Documents

Publication Publication Date Title
US5372751A (en) Acyl isethionate skin cleaning compositions containing betaines, amido sulfosuccinates or combinations of the two
EP0469029B1 (fr) Compositions d'acyl-isethionate pour le nettoyage de la peau
EP0203750B2 (fr) Composition ultra-douce pour la purification de la peau
EP0308190B1 (fr) Pain de toilette nettoyant ultradoux avec un mélange de polymères sélectionnés
US4812253A (en) Ultra mild skin cleansing composition
US5096608A (en) Ultra mild skin cleansing composition
AU625494B2 (en) Skin cleansing toilet bar with low moisture content
US4695395A (en) Cleaning compositions with skin protection agents
US5076953A (en) Skin cleansing synbars with low moisture and/or selected polymeric skin mildness aids
EP0592073A2 (fr) Compositions de nettoyage corporel douces contenant un selde sodium de glyceryl sulfonaté et ethoxylé
EP0748367B1 (fr) Composition de nettoyage de la peau
EP0441652B1 (fr) Composition détergente
EP0542526B1 (fr) Compositions de nettoyage de la peau
EP0472320B1 (fr) Composition de nettoyage de la peau à base d'acyliséthionates contenant de bétaines choisies
EP0459769B1 (fr) Compositions de nettoyage avec une réduction de pâte, amélioration de la douceur ou les deux
US5108640A (en) Personal cleansing synbar with improved rinsing
WO1996036313A1 (fr) Composition liquide et aqueuse de nettoyage contenant des savons a base d'acides gras
JPH05201852A (ja) 皮膚洗浄剤組成物

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: A1

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

17P Request for examination filed

Effective date: 19911111

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: 19941011

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: 69111259

Country of ref document: DE

Date of ref document: 19950824

ET Fr: translation filed
ITF It: translation for a ep patent filed
REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2076462

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

Ref country code: CH

Payment date: 19970129

Year of fee payment: 7

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

Ref country code: SE

Payment date: 19980116

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: 19980218

Year of fee payment: 8

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

Ref country code: CH

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

Effective date: 19980228

Ref country code: LI

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

Effective date: 19980228

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: 19990209

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: 19990901

EUG Se: european patent has lapsed

Ref document number: 91301046.8

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: ES

Payment date: 20100225

Year of fee payment: 20

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

Ref country code: IT

Payment date: 20100224

Year of fee payment: 20

Ref country code: FR

Payment date: 20100303

Year of fee payment: 20

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

Ref country code: GB

Payment date: 20100224

Year of fee payment: 20

Ref country code: DE

Payment date: 20100226

Year of fee payment: 20

REG Reference to a national code

Ref country code: DE

Ref legal event code: R071

Ref document number: 69111259

Country of ref document: DE

REG Reference to a national code

Ref country code: GB

Ref legal event code: PE20

Expiry date: 20110207

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 EXPIRATION OF PROTECTION

Effective date: 20110207

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 EXPIRATION OF PROTECTION

Effective date: 20110208

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20130805

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 EXPIRATION OF PROTECTION

Effective date: 20110209