EP0771346B1 - Utilisation de compositions detergents - Google Patents

Utilisation de compositions detergents Download PDF

Info

Publication number
EP0771346B1
EP0771346B1 EP95943495A EP95943495A EP0771346B1 EP 0771346 B1 EP0771346 B1 EP 0771346B1 EP 95943495 A EP95943495 A EP 95943495A EP 95943495 A EP95943495 A EP 95943495A EP 0771346 B1 EP0771346 B1 EP 0771346B1
Authority
EP
European Patent Office
Prior art keywords
fatty acid
alkyl
acid
carbon atoms
group containing
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
EP95943495A
Other languages
German (de)
English (en)
Other versions
EP0771346A1 (fr
Inventor
Bernd Fabry
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.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
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 Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP0771346A1 publication Critical patent/EP0771346A1/fr
Application granted granted Critical
Publication of EP0771346B1 publication Critical patent/EP0771346B1/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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0094—High foaming compositions
    • 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
    • C11D1/38—Cationic compounds
    • C11D1/65—Mixtures of anionic with cationic compounds
    • C11D1/652—Mixtures of anionic compounds with carboxylic amides or alkylol amides
    • 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
    • C11D1/38—Cationic compounds
    • C11D1/52—Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
    • C11D1/525—Carboxylic amides (R1-CO-NR2R3), where R1, R2 or R3 contain two or more hydroxy groups per alkyl group, e.g. R3 being a reducing sugar rest

Definitions

  • the invention relates to the use of detergent mixtures with synergistic enhancement of Cleaning and foaming power, containing fatty acid N-alkylpolyhydroxyalkylamides and sulfosuccinates for the production of hair shampoos.
  • Fatty acid N-alkylpolyhydroxyalkylamides and in particular fatty acid N-methylglucamides are nonionic surfactants which are used, for example, for the production of hand dishwashing detergents because of their good application profile.
  • the use of these substances has been the subject of a large number of publications. Their use as a thickener is known, for example, from European patent application EP-A1 0285768 (Hüls).
  • French published patent application FR-A 1580491 (Henkel) describes aqueous detergent mixtures based on sulfates and / or sulfonates, nonionic surfactants and, if appropriate, soaps, which contain fatty acid N-alkylglucamides as foam regulators.
  • EP-A 0112046 discloses well foaming detergent compositions comprising dialkyl sulfosuccinates and fatty acid dialkanolamides which can be used in shampoos.
  • Preparations are also known from international patent application WO 93/21293 , which can contain N-containing surfactants, sulfosuccinates and a Diels-Alder adduct. The mixtures can also be used as shampoos.
  • fatty acid N-alkylpolyhydroxyalkylamides can also be used in combination have cleaning and foaming power with other preferably anionic surfactants, that are not always satisfactory.
  • the object of the invention was then to provide detergent mixtures based on fatty acid N-alkylpolyhydroxyalkylamides for the manufacture of hair shampoos that are available through a have improved cleaning and foaming power without this advantage due to reduced performance must be paid for in other properties relevant to application technology.
  • the fatty acid N-alkylpolyhydroxyalkylamides are known substances which can usually be obtained by reductive amination of a reducing sugar with an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride; they follow the formula (I) : in which R 1 CO stands for an aliphatic acyl radical with 6 to 22 carbon atoms, R 2 for an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 12 carbon atoms and 3 to 10 hydroxyl groups.
  • R 1 CO stands for an aliphatic acyl radical with 6 to 22 carbon atoms
  • R 2 for an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms
  • [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 12 carbon atoms and 3 to 10 hydroxy
  • the fatty acid N-alkylpolyhydroxyalkylamides are preferably derived from reducing sugars having 5 or 6 carbon atoms, in particular from glucose.
  • the preferred fatty acid N-alkylpolyhydroxyalkylamides are therefore fatty acid N-alkylglucamides as represented by the formula (II) :
  • the fatty acid N-alkylpolyhydroxyalkylamides used are preferably glucamides of the formula (II) in which R 2 is an alkyl group and R 1 CO is the acyl radical of caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmoleic acid, stearic acid, isostearic acid, Oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, arachic acid, gadoleic acid, behenic acid or erucic acid or their technical mixtures.
  • Fatty acid N-alkylglucamides of the formula (II) which are obtained by reductive amination of glucose with methylamine and subsequent acylation with lauric acid or C 12/14 coconut fatty acid or a corresponding derivative are particularly preferred.
  • the polyhydroxyalkylamides can also be derived from maltose and palatinose.
  • Sulfosuccinates which are also referred to as sulfosuccinic acid esters, are known anionic surfactants which can be obtained by the relevant methods of preparative organic chemistry. They follow formula (III) in which R 3 is an alkyl and / or alkenyl radical having 6 to 22 carbon atoms, R 4 is R 3 or X, m and n independently of one another are 0 or numbers from 1 to 10 and X is an alkali or alkaline earth metal, ammonium, Alkylammonium or Glucammonium stands.
  • R 3 is an alkyl and / or alkenyl radical having 6 to 22 carbon atoms
  • R 4 is R 3 or X
  • m and n independently of one another are 0 or numbers from 1 to 10
  • X is an alkali or alkaline earth metal, ammonium, Alkylammonium or Glucammonium stands.
  • maleic acid but preferably maleic anhydride, which are esterified in the
  • the mono / diester ratio can be adjusted by varying the amount of alcohol and the temperature.
  • bisulfite is added, which is usually carried out in the solvent methanol.
  • Typical examples are sulfosuccinic acid monoesters and / or diesters in the form of their sodium salts which are derived from fatty alcohols having 8 to 18, preferably 8 to 10 or 12 to 14, carbon atoms; the fatty alcohols can be etherified with an average of 1 to 10 and preferably 1 to 5 moles of ethylene oxide and have both a conventional and preferably a narrowed homolog distribution.
  • Examples include di-n-octyl sulfosuccinate and monolauryl 3EO sulfosuccinate in the form of their sodium salts.
  • the preparation of the mixtures which are preferably aqueous and then have a solids content of 5 up to 70, preferably 25 to 50 wt .-%, is usually done by stirring aqueous Solutions, pastes or concentrates of the input materials, if necessary at a slightly elevated temperature.
  • aqueous Solutions pastes or concentrates of the input materials, if necessary at a slightly elevated temperature.
  • spray-dried powder of the two components and then paste or solutions of both ingredients together spray drying and / or subject to granulation. All of these cases are purely mechanical processes, a chemical reaction does not take place.
  • the hair shampoos can be 10 to 30% by weight on the agent - contain detergent mixtures as well as usual auxiliaries and additives.
  • the shampoos can primarily contain other anionic, nonionic, cationic, amphoteric and / or zwitterionic surfactants as auxiliaries and additives.
  • anionic surfactants are alkylbenzenesulfonates, alkanesulfonates, olefin sulfonates, alkyl ether sulfonates, glycerol ether, ⁇ -methyl ester sulfonates, sulfofatty acids, alkyl sulfates, fatty alcohol ether sulfates, Glycerol ether, Hydroxymischethersulfate, monoglyceride (ether) sulfates, fatty acid amide (ether) sulfates, mono- and dialkyl sulfosuccinamates, sulfotriglycerides, amide soaps , Ether carboxylic acids and their salts, fatty acid isethionates, fatty acid sarcos,
  • anionic surfactants contain polyglycol ether chains, they can have a conventional, but preferably a narrow, homolog distribution.
  • Typical examples of nonionic surfactants are fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, fatty acid polyglycol esters, fatty acid amide polygylcol ethers, fatty amine polyglycol ethers, alkoxylated triglycerides, alk (en) yloligoglycosides, fatty acid-N-alkylglucamides, protein hydrolysate, sorbate ester products, in particular vegetable ester ester-based sorbate products, especially vegetable-based ester esters, sorbate-based ester products (especially vegetable-based ester esters).
  • nonionic surfactants contain polyglycol ether chains, they can have a conventional, but preferably a narrow, homolog distribution.
  • Typical examples of cationic surfactants are quaternary ammonium compounds and ester quats, in particular quaternized fatty acid trialkanolamine ester salts.
  • Typical examples of amphoteric or zwitterionic surfactants are alkyl betaines, alkyl amido betaines, aminopropionates, aminoglycinates, imidazolinium betaines and sulfobetaines. The surfactants mentioned are exclusively known compounds.
  • the shampoos can contain emulsifiers such as alkoxylated fatty alcohols or sorbitan esters as auxiliaries and additives.
  • emulsifiers such as alkoxylated fatty alcohols or sorbitan esters as auxiliaries and additives.
  • Superfatting agents may be used such as polyethoxylated lanolin derivatives, lecithin derivatives and fatty acid alkanolamides, the latter also serving as foam stabilizers.
  • Suitable thickeners are, for example, polysaccharides, in particular xanthan gum, guar guar, agar agar, alginates and tyloses, carboxymethyl cellulose and hydroxyethyl cellulose, and also higher molecular weight polyethylene glycol mono diesters of fatty acids, polyacrylates, polyvinyl alcohol and polyvinyl pyrrolidone, and electrolytes such as sodium chloride and ammonium chloride.
  • Biogenic active substances are understood to mean, for example, plant extracts, protein hydrolyzates and vitamin complexes.
  • Common film formers are, for example, chitosan, microcrystalline chitosan, quaternized chitosan, polyvinylpyrrolidone, vinylpyrrolidone / vinyl acetate copolymers, polymers of the acrylic acid series, quaternary cellulose derivatives and similar compounds.
  • Suitable preservatives are, for example, phenoxyethanol, formaldehyde solution, parabens, pentadiol or sorbic acid.
  • Suitable pearlizing agents are, for example, glycol distearic esters, such as ethylene, but also fatty acid monoglycol esters.
  • the dyes which can be used are the substances which are suitable and approved for cosmetic purposes, as compiled, for example, in the publication " Cosmetic Dyes” by the Dye Commission of the German Research Foundation, published by Verlag Chemie, Weinheim, 1984, pp . 81-106 . These dyes are usually used in concentrations of 0.001 to 0.1% by weight, based on the mixture as a whole.
  • the total proportion of auxiliaries and additives can be 1 to 50, preferably 5 to 40,% by weight, based on the composition.

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 (5)

  1. Utilisation de mélanges détergents contenant
    (a) des N-alkylpolyhydroxyalkylamides d'acides gras et
    (b) des sulfosuccinates
    dans un rapport pondéral de 80:20 à 20:80 pour la fabrication de shampooings capillaires.
  2. Utilisation selon la revendication 1,
    caractérisée en ce qu'
    on utilise des N-alkylpolyhydroxyalkylamides d'acides gras de formule (I),
    Figure 00110001
    dans laquelle R1CO représente un radical acylaliphatique ayant de 6 à 22 atomes de carbone, R2 représente un radical alkyle ou hydroxyalkyle ayant de 1 à 4 atomes de carbone et [Z] représente un radical polyhydroxyalkyle linéaire ou ramifié ayant de 3 à 12 atomes de carbone et de 3 à 10 groupes hydroxyle.
  3. Utilisation selon les revendications 1 et 2,
    caractérisée en ce qu'
    on utilise comme composant (a) des n-alkylglucamides d'acides gras.
  4. Utilisation selon les revendications 1 à 3,
    caractérisée en ce qu'
    on utilise comme composant (b) des sulfosuccinates de formule (III),
    Figure 00120001
    dans laquelle R3 représente un radical alkyle et/ou alcényle ayant de 6 à 22 atomes de carbone, R4 représente R3 ou X, m et n représentent indépendamment l'un de l'autre 0 ou des nombres de 1 à 10 et X représente un métal alcalin ou alcalino-terreux, l'ammonium, un alkylammonium ou le glucammonium.
  5. Utilisation selon les revendications 1 à 4,
    caractérisée en ce qu'
    on utilise les composants (a) et (b) dans un rapport pondéral de 50:50 à 25:75.
EP95943495A 1994-07-19 1995-07-10 Utilisation de compositions detergents Expired - Lifetime EP0771346B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4425449 1994-07-19
DE4425449A DE4425449A1 (de) 1994-07-19 1994-07-19 Detergensgemische mit verbesserter Reinigungsleistung
PCT/EP1995/002677 WO1996002620A1 (fr) 1994-07-19 1995-07-10 Melanges detergents a pouvoir ameliore de lavage

Publications (2)

Publication Number Publication Date
EP0771346A1 EP0771346A1 (fr) 1997-05-07
EP0771346B1 true EP0771346B1 (fr) 1999-10-20

Family

ID=6523534

Family Applications (1)

Application Number Title Priority Date Filing Date
EP95943495A Expired - Lifetime EP0771346B1 (fr) 1994-07-19 1995-07-10 Utilisation de compositions detergents

Country Status (4)

Country Link
EP (1) EP0771346B1 (fr)
DE (2) DE4425449A1 (fr)
ES (1) ES2138762T3 (fr)
WO (1) WO1996002620A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB9800850D0 (en) * 1998-01-15 1998-03-11 Courtaulds Plc Methods of manufacturing and collecting cellulosic particles
GB0509810D0 (en) * 2005-05-16 2005-06-22 Reckitt Benckiser Nv Aqueous cleaning compositions

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NZ206211A (en) * 1982-11-16 1986-04-11 Unilever Plc Foaming liquid detergent compositions containing sulphosuccinic acid esters
CZ283685B6 (cs) * 1990-09-28 1998-06-17 The Procter And Gamble Company Čistící prostředek obsahující alkylsulfát a polyhydroxyamid mastné kyseliny
DE4301358C2 (de) * 1992-01-30 1995-08-10 Hermann Scheler Verpackungsfreies Waschmittel, insbesondere Körper- und/oder Textilwaschmittel
GB9207799D0 (en) * 1992-04-09 1992-05-27 Procter & Gamble Aqueous compositions
EP0572723A1 (fr) * 1992-06-02 1993-12-08 The Procter & Gamble Company Compositions détergentes liquides structurées
DE4224714A1 (de) * 1992-07-27 1994-02-03 Henkel Kgaa Schäumende Detergensgemische
US5545354A (en) * 1992-09-01 1996-08-13 The Procter & Gamble Company Liquid or gel dishwashing detergent containing a polyhydroxy fatty acid amide, calcium ions and an alkylpolyethoxypolycarboxylate
EP0665874A1 (fr) * 1992-10-13 1995-08-09 The Procter & Gamble Company Composition detergente sous forme liquide ou de gel pour lave-vaisselle contenant une amide d'acide gras polyhydroxy et certains elements
DE4238211C2 (de) * 1992-11-12 1997-11-13 Henkel Kgaa Verwendung von Detergensgemischen, enthaltend kationische Zuckertenside und weitere Tenside, zur Herstellung von Avivagemitteln
DE4315810A1 (de) * 1993-05-12 1994-11-17 Henkel Kgaa Wäßrige Detergensgemische
CA2168346A1 (fr) * 1993-07-28 1995-02-09 Katherine Margaret Wansborough Concentre peu irritant pour soins de la peau

Also Published As

Publication number Publication date
WO1996002620A1 (fr) 1996-02-01
DE59507095D1 (de) 1999-11-25
EP0771346A1 (fr) 1997-05-07
DE4425449A1 (de) 1996-01-25
ES2138762T3 (es) 2000-01-16

Similar Documents

Publication Publication Date Title
DE4400632C1 (de) Tensidgemische und diese enthaltende Mittel
EP0910329B1 (fr) Concentres aqueux a lustre nacre
EP0652931B1 (fr) Melanges detergents moussants
EP0941060B1 (fr) Preparations cosmetiques
DE4428823A1 (de) Schäumende Detergensgemische
EP0910328B1 (fr) Concentres aqueux a lustre nacre
EP0912700B1 (fr) Concentres aqueux de lustre nacre
EP0508038B1 (fr) Sulfosuccinates d'esters d'acide citrique, d'alcools gras et d'éthers polyglycoliques, procédé pour leur préparation et leur utilisation
EP0771346B1 (fr) Utilisation de compositions detergents
EP0846752A2 (fr) Dispersion aqueuse à aspect nacré à bon écoulement avec de l'acide béhénique comme composant donnant l'aspect nacré
EP0843713B1 (fr) Shampooings doux
EP0777714B1 (fr) Shampooings pour les cheveux
EP0999822B1 (fr) Concentres aqueux nacres
DE4433070C1 (de) Milde Detergensgemische
EP0930872B1 (fr) Dispersions aqueuses de lustre perlaire
DE4424823A1 (de) Starkschäumende Detergensgemische
EP0970168A2 (fr) Savons detersifs synthetiques
EP1000135B1 (fr) Concentres de lustre perlaire aqueux
EP0858320A1 (fr) Preparations cosmetiques
EP0776653A1 (fr) Compositions cosmétiques et/ou pharmaceutiques contenant des amides d'acides gras polyhydroxyle

Legal Events

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

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19970110

AK Designated contracting states

Kind code of ref document: A1

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

17Q First examination report despatched

Effective date: 19971007

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

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

REF Corresponds to:

Ref document number: 59507095

Country of ref document: DE

Date of ref document: 19991125

ET Fr: translation filed
ITF It: translation for a ep patent filed

Owner name: STUDIO JAUMANN P. & C. S.N.C.

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2138762

Country of ref document: ES

Kind code of ref document: T3

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

Effective date: 20000124

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

Ref country code: GB

Payment date: 20000705

Year of fee payment: 6

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

Ref country code: FR

Payment date: 20000711

Year of fee payment: 6

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

Ref country code: NL

Payment date: 20000728

Year of fee payment: 6

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: GB

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

Effective date: 20010710

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

Ref country code: ES

Payment date: 20010719

Year of fee payment: 7

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: 20020201

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

Effective date: 20010710

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: 20020329

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

Effective date: 20020201

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: ES

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

Effective date: 20020711

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20030811

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

Ref country code: DE

Payment date: 20050707

Year of fee payment: 11

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: 20050710

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: 20070201