EP0862609B1 - Composition de detergent pour lessive - Google Patents

Composition de detergent pour lessive Download PDF

Info

Publication number
EP0862609B1
EP0862609B1 EP96932507A EP96932507A EP0862609B1 EP 0862609 B1 EP0862609 B1 EP 0862609B1 EP 96932507 A EP96932507 A EP 96932507A EP 96932507 A EP96932507 A EP 96932507A EP 0862609 B1 EP0862609 B1 EP 0862609B1
Authority
EP
European Patent Office
Prior art keywords
detergent composition
surfactant
detergent
composition according
fabric softening
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.)
Revoked
Application number
EP96932507A
Other languages
German (de)
English (en)
Other versions
EP0862609A1 (fr
Inventor
Abid Nadim Khan-Lodhi
Christopher Whaley
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
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=10781955&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP0862609(B1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Unilever PLC, Unilever NV filed Critical Unilever PLC
Publication of EP0862609A1 publication Critical patent/EP0862609A1/fr
Application granted granted Critical
Publication of EP0862609B1 publication Critical patent/EP0862609B1/fr
Anticipated expiration legal-status Critical
Revoked 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/88—Ampholytes; Electroneutral compounds
    • C11D1/94—Mixtures with anionic, cationic or non-ionic compounds
    • 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
    • C11D1/66—Non-ionic compounds
    • C11D1/835—Mixtures of non-ionic with cationic compounds
    • 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
    • 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
    • C11D1/62—Quaternary ammonium compounds
    • 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
    • C11D1/66—Non-ionic compounds
    • C11D1/662—Carbohydrates or derivatives
    • 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
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • 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
    • C11D1/66—Non-ionic compounds
    • C11D1/75—Amino oxides
    • 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
    • C11D1/66—Non-ionic compounds
    • C11D1/755—Sulfoxides
    • 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
    • C11D1/66—Non-ionic compounds
    • C11D1/79—Phosphine oxides
    • 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
    • C11D1/88—Ampholytes; Electroneutral compounds
    • 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
    • C11D1/88—Ampholytes; Electroneutral compounds
    • C11D1/90—Betaines
    • 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
    • C11D1/88—Ampholytes; Electroneutral compounds
    • C11D1/92—Sulfobetaines ; Sulfitobetaines

Definitions

  • the present invention relates to detergent compositions.
  • the invention relates to detergent compositions that have excellent detergency properties and also soften fabrics.
  • WO95/27769 (Unilever) and WO/95/27771 (Unilever) disclose fabric conditioning compositions in which the cationic softener is combined with a nonionic or amphoteric surfactant such that when diluted 70 wt% of the fabric softening compound is in solution.
  • WO 95/0443 discloses aqueous fabric conditioning compositions which contain a quaternary ammonium compound, a cellulose and optionally a non-ionic surfactant.
  • the compositions exhibit a solubility of the cationic fabric softener of less than 70% when diluted to a total active of 5 wt%.
  • WO 94/06899 discloses detergent mixtures containing oligoglycosides and esterquats which are useful for preparing surfactants and for tertiary oil extraction.
  • a fabric softening detergent composition comprising
  • a further aspect of the invention provides the use of self-size-limiting molecular aggregates (as defined below) as a fabric softening system in a detergent composition.
  • the fabric softening system within the detergent composition of the invention is not in conventional lamellar form, and when contacted with water may be solubilised partially in the form of self-size-limiting molecular aggregates, such as micelles or micellar solutions with solid or liquid interiors or mixtures thereof. Where the composition is in a form containing water the composition itself may be at least partially in the form of self-size-limiting molecular aggregates. It is thought that it is this new structure of the fabric softening system within the detergent composition that overcomes the problems of the prior art.
  • the composition may contain a non-surfactant solubiliser for the fabric softening compound, preferably the non-surfactant solubiliser is not a volatile solvent.
  • the fabric softening compound and detergent surfactant form a transparent mix when in liquid form.
  • additional detergent ingredients may cause the composition to become cloudy. The following tests may be used to determine definitely whether or not a composition falls within the present invention.
  • liquid the detergent compositions according to the invention may be translucent.
  • Translucent in the context of this invention means that when a cell 1cm in depth is filled with the fabric softening composition, "Courier 12 point" typeface can be read through the cell.
  • a further advantage of the present invention is that the softening of the composition is enhanced over detergent compositions of the prior art comprising similar levels of fabric softening compound.
  • the detergent surfactant may be nonionic or amphoteric.
  • the detergent surfactant is a nonionic surfactant it may be characterised in terms of its phase behaviour.
  • Suitable nonionic surfactants are those for which when contacted with water, the first lyotropic liquid crystalline phase formed is normal cubic (I1) or normal cubic-bicontinuous (V1) or hexagonal (H1) or nematic (Ne1), or intermediate (Int1) phase as defined in the article by G J T Tiddy et al, J Chem Soc. Faraday Trans. 1., 79, 975, 1983 and G J T Tiddy , "Modern Trends of Colloid Science in Chemistry and Biology", Ed. H-F Eicke, 1985 Birkhauser Verlag Basel].
  • Surfactants forming L ⁇ phases at concentrations of less than 20 wt% are not suitable.
  • nonionic surfactants may be defined as substances with molecular structures consisting of a hydrophilic and hydrophobic part.
  • the hydrophobic part consists of a hydrocarbon and the hydrophilic part of strongly polar groups.
  • the nonionic surfactants of this invention are soluble in water.
  • the most preferred nonionic surfactants are alkoxylated, preferably ethoxylated compounds and carbohydrate compounds.
  • ethoxylated surfactants include ethoxylated alcohols, ethoxylated alkyl phenols, ethoxylated fatty amides and ethoxylated fatty esters.
  • Preferred nonionic ethoxylated surfactants have an HLB of from about 10 to about 20. It is advantageous if the surfactant alkyl group contains an average of at least 12 carbon atoms.
  • carbohydrate surfactants or other polyhydroxy surfactants include alkyl polyglycosides as disclosed in EP 199 765 (Henkel) and EP 238 638 (Henkel), poly hydroxy amides as disclosed in WO 93 18125 (Procter and Gamble) and WO 92/06161 (Procter and Gamble), fatty acid sugar esters (sucrose esters), sorbitan ester ethoxylates, and poly glycerol esters and alkyl lactobionamides.
  • the ratio of carbohydrate compounds to long chain alcohol ethoxylate is from 3:1 to 1:3, more preferably from 1:2 to 2:1, most preferably approximately at a ratio of 1:1.
  • the detergent surfactant agent may be amphoteric or zwitterionic which are characterised in terms of its phase behaviour.
  • Suitable detergent surfactants are amphoteric surfactants for which, when contacted within water, the first lyotropic liquid crystalline phase formed is normal cubic (I1) or normal cubic-bicontinuous (V1) or hexagonal (H1) or nematic (Nel), or intermediate (Int1) phase as defined in the article by G J T Tiddy et al, J Chem Soc. Faraday Trans. 1., 79, 975, 1983 and G J T Tiddy , "Modern Trends of Colloid Science in Chemistry and Biology", Ed. H-F Eicke, 1985 Birkhauser Verlag Basel].
  • Surfactants forming L ⁇ phases at concentrations of less than 20 wt% are not suitable.
  • amphoteric surfactants are defined as substances with molecular structures consisting of a hydrophilic and hydrophobic part.
  • the hydrophobic part consists of a hydrocarbon and the hydrophilic part consists of both a positive and a negative group.
  • Preferred amphoteric/zwitterionic surfactants include amine oxides, betaines including sulphobetaines and tegobetaines, phosphine oxides and sulphoxides.
  • Mixtures of detergent surfactants may be used.
  • the detergent surfactant is advantageously solid at room temperature as this provides crisp composition particles.
  • the detergent surfactant comprises at least 10 wt% of the total composition.
  • the fabric softening compound is suitably a water insoluble quaternary ammonium material comprising a single alkyl or alkenyl chain length equal to or greater than C 20 or, more preferably, the softening compound comprises a quaternary ammonium material having two C 12-22 alkyl or alkenyl groups connected to the quaternary ammonium head group via at least one ester link.
  • the fabric softening compound has two long chain alkyl or alkenyl chains with an average chain length equal to or greater than C 14 . More preferably each chain has an average chain length equal or greater than C 16 . Most preferably at least 50% of each long chain alkyl or alkenyl group has a chain length of C 18 .
  • the long chain alkyl or alkenyl groups of the fabric softening compound are predominantly linear.
  • the fabric softening compounds used in the compositions of the invention are molecules which provide excellent softening, characterised by chain melting -L ⁇ to L ⁇ - transition temperature greater than 25°C, preferably greater than 35°C, most preferably greater than 45°C.
  • This L ⁇ to L ⁇ transition can be measured by DSC as defined in "Handbook of Lipid Bilayers, D Marsh, CRC Press, Boca Raton Florida, 1990 (Pages 137 and 337).
  • Substantially insoluble fabric softening compounds in the context of this invention are defined as fabric softening compounds having a solubility less than 1 x 10 -3 wt% in demineralised water at 20°C.
  • the fabric softening compounds Preferably have a solubility less than 1 x 10 -4
  • the fabric softening compounds have a solubility at 20°C in demineralised water from 1 x 10 -8 to 1 x 10 -6.
  • the fabric softening compound is a water insoluble quaternary ammonium material which comprises a compound having two C 12-18 alkyl or alkenyl groups connected to the molecule via at least one an ester link. It is more preferred if the quaternary ammonium material has two ester links present.
  • the especially preferred ester-linked quaternary ammonium material for use in the invention can be represented by the formula: wherein each R 1 group is independently selected from C 1-4 alkyl, hydroxyalkyl or C 24 alkenyl groups; and wherein each R 2 group is independently selected from C 12-22 alkyl or alkenyl groups; T is or X - is any suitable anion and n is an integer from 0-5.
  • Di(tallowoyloxyethyl)dimethyl ammonium chloride available from Hoechst, is especially preferred.
  • a second preferred type of quaternary ammonium material can be represented by the formula: wherein R 1 , n, X - and R 2 are as defined above.
  • the quaternary ammonium material is biologically degradable.
  • Preferred materials of this class such as 1,2 bis[hardened tallowoyloxy]-3- trimethylammonium propane chloride and their method of preparation are, for example, described in US 4 137 180 (Lever Brothers).
  • these materials comprise small amounts of the corresponding monoester as described in US 4 137 180 for example 1-hardened tallowoyloxy -2-hydroxy -3-trimethylammonium propane chloride.
  • compositions of the invention further comprise a non-surfactant solubiliser.
  • solubilisers include propylene glycol, urea , acid amides up to and including chain lengths of C 6, citric acid and other poly carboxylic acids as disclosed in EP 0 404 471 (Unilever), glycerol, sorbitol and sucrose.
  • Particularly preferred are polyethylene glycols (PEG) having a molecular weight ranging from 200 - 6000, most preferably from 1000 to 2000.
  • the weight ratio of solubiliser to detergent surfactant is from 2:1 to 1:40.
  • the ratio of solubiliser to detergent surfactant is not greater than 1:1, more preferably not greater than 1:5.
  • the weight ratio of detergent surfactant or the weight ratio of detergent surfactant plus any solubiliser to fabric softening compound is at least 1:1, preferably at least 2:1, more preferably equal to or greater than 5:1. It is advantageous if the ratio of detergent surfactant or detergent surfactant plus any solubiliser to fabric softening compound is equal to or below 50:1, more preferably below 30:1, most preferably 15:1 or below.
  • the detergency booster is defined as any non-surfactant material that aids the detergent composition in removing soil from a fabric.
  • Typical detergency boosters include soil release and antiredeposition polymers, sequestrants and chelates, builders, enzymes and bleach systems.
  • the detergency booster is a detergency builder, it is suitably present in an amount of from 5 to 80 wt%, preferably from 20 to 80 wt%.
  • This may be any material capable of reducing the level of free calcium ions in the wash liquor and will preferably provide the compositions with other beneficial properties such as the generation of an alkaline pH and the suspension of soil removed from the fabric.
  • Preferred builders include alkali metal (preferably sodium) aluminosilicates, which may suitably be incorporated in amounts of from 5 to 80% by weight (anhydrous basis) of the composition, and may be either crystalline or amorphous or mixtures thereof, having the general formula: 0.8-1.5 Na 2 O.A1 2 O 3 .0.8-6 SiO 2
  • the preferred sodium aluminosilicates contain 1.5-3.5 SiO 2 units (in the formula above). Both the amorphous and the crystalline materials can be prepared readily by reaction between sodium silicate and sodium aluminate, as amply described in the literature.
  • Suitable crystalline sodium aluminosilicate ion-exchange detergency builders are described, for example, in GB 1 429 143 (Procter & Gamble).
  • the preferred sodium aluminosilicates of this type are the well-known commercially available zeolites A and X, and mixtures thereof.
  • Also of interest is the novel zeolite P described and claimed in EP 384070 (Unilever).
  • Phosphate-built detergent compositions are also within the scope of the invention.
  • phosphorus-containing inorganic detergency builders include the water-soluble salts, especially alkali metal pyrophosphates, orthophosphates, polyphosphates and phosphonates.
  • Specific examples of inorganic phosphate builders include sodium and potassium tripolyphosphates, orthophosphates and hexametaphosphates.
  • Inorganic builders that may be present include alkali metal (generally sodium) carbonate; while organic builders include polycarboxylate polymers such as polyacrylates, acrylic/maleic copolymers, and acrylic phosphinates; monomeric polycarboxylates such as citrates, gluconates, oxydisuccinates, glycerol mono-, di- and trisuccinates, carboxymethyloxysuccinates, carboxymethyloxymalonates, dipicolinates, hydroxyethyliminodiacetates; and organic precipitant builders such as alkyl- and alkenylmalonates and succinates, and sulphonated fatty acid salts.
  • alkali metal generally sodium
  • organic builders include polycarboxylate polymers such as polyacrylates, acrylic/maleic copolymers, and acrylic phosphinates; monomeric polycarboxylates such as citrates, gluconates, oxydisuccinates, glycerol mono-, di- and trisuccinate
  • Especially preferred supplementary builders are polycarboxylate polymers, more especially polyacrylates and acrylic/maleic copolymers, suitably used in amounts of from 0.1 to 15 wt%, especially from 0.5 to 10 wt%; and monomeric polycarboxylates, more especially citric acid and its salts, suitably used in amounts of from 0.5 to 20 wt%, more preferably from 5 to 15 wt%.
  • Preferred inorganic persalts are sodium perborate monohydrate and tetrahydrate, and sodium percarbonate, advantageously employed together with an activator.
  • Bleach activators also referred to as bleach precursors
  • Preferred examples include peracetic acid precursors, for example, tetraacetylethylene diamine (TAED), now in widespread commercial use in conjunction with sodium perborate; and perbenzoic acid precursors; for example sodium nonoyloxy benzene sulphonate (SNOBS), and sodium percarbonate.
  • TAED tetraacetylethylene diamine
  • SNOBS sodium nonoyloxy benzene sulphonate
  • the novel quaternary ammonium and phosphonium bleach activators disclosed in US 4 751 015 and US 4 818 426 are also of great interest.
  • the bleach system may also include a bleach stabiliser (heavy metal sequestrant) such as ethylenediamine tetramethylene phosphonate and diethylenetriamine pentamethylene phosphonate.
  • a bleach stabiliser such as ethylenediamine tetramethylene phosphonate and diethylenetriamine pentamethylene phosphonate.
  • Organic peroxyacids are also suitable detergency boosters. Such materials are illustrated by those disclosed in US 4 374 035, US 4 681 592, US 4 634 551, US 4 686 063, US 4 606 838, and US 4 671 891,(all Procter and Gamble). It is preferred if the organic peroxyacids are cationic, suitable peroxyacids are described in WO94/21605 (Unilever) and WO 94/01399 (Unilever).
  • peroxyacids for this invention include diperoxydodecanedioic acid (DPDA), nonylamide of peroxy-succinic acid (NAPSA), nonylamide of peroxyadipic acid (NAPAA) decyldiperoxysuccinic acid (DDPSA), 6-N-phthalimido peroxy hexonoic acid (PAP), di N,N'-tere phthaloyldi 16-amino caproic acid (TOCAP) and imidoperoxy mellitic acid (BIPTA).
  • DPDA diperoxydodecanedioic acid
  • NAPSA nonylamide of peroxy-succinic acid
  • NAPAA nonylamide of peroxyadipic acid
  • DDPSA decyldiperoxysuccinic acid
  • PAP 6-N-phthalimido peroxy hexonoic acid
  • TOCAP di N,N'-tere phthaloyldi 16-amin
  • the peroxyacid bleach is used at a level which provides an amount of available oxygen (AvO) from 0.1% to 10%, preferably from 0.5% to 5%, and most preferably from 1% to 4%, all by weight of the composition.
  • AvO available oxygen
  • the detergency booster may also be one of the detergency enzymes well-known in the art for their ability to degrade and aid in the removal of various soils and stains.
  • Suitable enzymes include the various proteases, cellulases, lipases, amylases, and mixtures thereof, which are designed to remove a variety of soils and stains from fabrics.
  • suitable proteases are Maxatase (Trade Mark), as supplied by Gist-Brocades N.V., Delft, Holland, and Alcalase (Trade Mark), Esperase (Trade Mark) and Savinase (Trade Mark), as supplied by Novo Industri A/S, Copenhagen, Denmark.
  • Detergency enzymes are commonly employed in the form of granules or marumes, optionally with a protective coating, in amounts of from about 0.1% to about 3.0% by weight of the composition.
  • the detergency booster is a soil release agent. It is advantageous if the soil release polymer is included in the formulation at levels from 0.1% to 10%, preferably 0.2% to 5%, of a soil release agent. Preferably, such a soil release agent of the present composition is a polymer.
  • Polymeric soil release agents useful in the present invention include hydroxyether cellulosic polymers, copolymeric blocks of terephthalate and polyethylene oxide or polypropylene oxide, and cationic guar gums, and the like.
  • the cellulosic derivatives that are functional as soil release agents may be characterised as certain hydroxyethers of cellulose such as Methocel® (Dow); also, certain cationic cellulose ether derivatives such as Polymer JR-125 R , JR-400 R , and JR-30M R (Union Carbide).
  • cationic guar gums such as Jaguar Plus R (Stein Hall) and Gendrive 458 R (General Mills).
  • a preferred detergent composition has a polymeric soil release agent selected from the group consisting of methyl cellulose, hydroxypropyl methylcellulose, or hydroxybutyl methylcellulose, said cellulosic polymer having a viscosity in 2% aqueous solution at 20°C of 15.10 3 to 75 Pa.s (15 to 75,000 centipoise).
  • a more preferred soil release agent is a copolymer having blocks of terephthalate and polyethylene oxide. More specifically, these polymers are comprised of repeating units of ethylene terephthalate and polyethylene oxide terephthalate at a molar ratio of ethylene terephthalate units to polyethylene oxide terephthalate units of from 25:75 to 35:65, said polyethylene oxide terephthalate containing polyethylene oxide blocks having molecular weight of from 300 to 2000. The molecular weight of this polymeric soil release agent is in the range of from 5,000 to 55,000.
  • Another preferred polymeric soil release agent is a crystallisable polyester with repeat units of ethylene terephthalate units containing 10-15% by weight of ethylene terephthalate units together with 90-50% by weight of polyoxyethylene terephthalate units, derived from a polyoxyethylene glycol of average molecular weight 300-6,000, and the molar ratio of ethylene terephthalate units to polyoxyethylene terephthalate units in the crystallizable polymeric compound is between 2:1 and 6:1.
  • this polymer include the commercially available material Zelcon R 4780 (from Dupont) and Milease R T (from ICI).
  • Highly preferred soil release agents are polymers of the generic formula: in which X can be any suitable capping group, with each X being selected from the group consisting of H, and alkyl or acyl groups containing from 1 to about 4 carbon atoms.
  • n is selected for water solubility and generally is from 6 to 113, preferably from 10 to 50.
  • u is critical to formulation in a liquid composition having a relatively high ionic strength. There should be very little material in which u is greater than 10. Furthermore there should be at least 20%, preferably at least 40% of material in which u ranges from 3 to 5.
  • the R 1 moieties are essentially 1,4-phenylene moieties.
  • the term "the R 1 moieties consist entirely of 1,4- phenylene moieties, or are partially substituted with other arylene or alkarylene moieties, alkylene moieties, alkenylene moieties, or mixtures thereof.
  • Arylene and alkarylene moieties which can be partially substituted for 1,4-phenylene include 1,3-phenylene, 1,2-phenylene, 1,8-naphtylene, 1,4-naphtylene, 2,2-biphenylene, 4,4-biphenylene and mixtures thereof.
  • Alkylene and alkenylene moieties which can be partially substituted include ethylene, 1,2-propylene, 1,4-butylene, 1,5-pentylene, 1,6-hexamethylene, 1,7-heptamethylene, 1,8-octamethylene, 1,4-cyclohexylene, and mixtures thereof.
  • the degree of partial substitution with moieties other than 1,4-phenylene should be such that the soil release properties of the compound are not adversely affected to any great extent.
  • the degree of partial substitution which can be tolerated will depend upon the backbone length of the compound, i.e., longer backbones can have greater partial substitution for 1,4-phenylene moieties.
  • compounds where the R 1 comprise from about 50 to 100% 1,4-phenylene moieties (from 0 to 50% moieties other than 1,4-phenylene) have adequate soil release activity.
  • polyesters made according to the present invention with a 40:60 mole ratio of isophtalic (1,3-phenylene) to terephthalic (1,4-phenylene) acid have adequate soil release activity.
  • the R 1 moieties consist entirely of (i.e., comprise 100%) 1,4-phenylene moieties, i.e. each R 1 moiety is 1,4-phenylene.
  • suitable ethylene or substituted ethylene moieties include ethylene, 1,2-propylene, 1,2-butylene, 1,2-hexylene, 3-methoxy-1,2-propylene and mixtures thereof.
  • the R 2 moieties are essentially ethylene moieties, 1,2-propylene moieties or mixture thereof. Inclusion of a greater percentage of ethylene moieties tends to improve the soil release activity of the compounds. Surprisingly, inclusion of a greater percentage of 1,2-propylene moieties tends to improve the water solubility of the compounds.
  • 1,2-propylene moieties or a similar branched equivalent is desirable for incorporation of any substantial part of the soil release component in the liquid fabric softener compositions.
  • each n is at least 6, but is preferably at least 10.
  • the value for each n usually ranges from 12 to 113. Typically, the value for each n is in the range of from 12 to 43.
  • a second type of preferred soil release polymers are polymers which comprises a copolymer having:
  • the detergent composition of the invention may also contain a fluorescer (optical brightener), for example, Tinopal (Trade Mark) DMS or Tinopal CBS available from Ciba-Geigy AG, Basel, Switzerland.
  • a fluorescer optical brightener
  • Tinopal DMS is disodium 4,4'bis-(2-morpholino-4-anilino-s-triazin-6-ylamino) stilbene disulphonate
  • Tinopal DBS is disodium 2,2'bis-(phenyl-styryl) disulphonate.
  • An antifoam material is advantageously included in the detergent composition of the invention, especially if the powder is primarily intended for use in front-loading drum-type automatic washing machines.
  • Suitable antifoam materials are usually in granular form, such as those described in EP 266 863A (Unilever).
  • Such antifoam granules typically comprise a mixture of silicone oil, petroleum jelly, hydrophobic silica and alkyl phosphate as antifoam active material, sorbed onto a porous absorbent water-soluble carbonate-based inorganic carrier material.
  • Antifoam granules may be present in any amount up to 5% by weight of the composition.
  • ingredients which can optionally be employed in the detergent composition of the invention include polymers containing carboxylic or sulphonic acid groups in acid form or wholly or partially neutralised to sodium or potassium salts, the sodium salts being preferred.
  • Preferred polymers are homopolymers and copolymers of acrylic acid and/or maleic acid or maleic anhydride.
  • polyacrylates polyalphahydroxy acrylates, acrylic/maleic acid copolymers, and acrylic phosphinates.
  • Other polymers which are especially preferred for use in liquid detergent compositions are deflocculating polymers such as for example disclosed in EP 346995.
  • the molecular weights of homopolymers and copolymers are generally 1000 to 150,000, preferably 1500 to 100,000.
  • the amount of any polymer may lie in the range from 0.5 to 5% by weight of the composition.
  • Other suitable polymeric materials are cellulose ethers such as carboxy methyl cellulose, methyl cellulose, hydroxy alkyl celluloses, and mixed ethers, such as methyl hydroxy ethyl cellulose, methyl hydroxy propyl cellulose, and methyl carboxy methyl cellulose. Mixtures of different cellulose ethers, particularly mixtures of carboxy methyl cellulose and methyl cellulose, are suitable.
  • Polyethylene glycol of molecular weight from 400 to 50,000, preferably from 1000 to 10,000, and copolymers of polyethylene oxide with polypropylene oxide are suitable as also are copolymers of polyacrylate with polyethylene glycol.
  • Polyvinyl pyrrolidone of molecular weight of 10,000 to 60,000, preferably of 30,000 to 50,000 and copolymers of polyvinyl pyrrolidone with other poly pyrrolidones are suitable.
  • Polyacrylic phosphinates and related copolymers of molecular weight 1000 to 100,000, in particular 3,000 to 30,000 are also suitable.
  • an amount of an alkali metal silicate particularly sodium ortho-, meta- or preferably neutral or alkaline silicate.
  • alkali metal silicates at levels, for example, of 0.1 to 10 wt%, may be advantageous in providing protection against the corrosion of metal parts in washing machines, besides providing some measure of building and giving processing benefits.
  • ingredients which may be present in the composition include fabric softening agents such as fatty amines, fabric softening clay materials, lather boosters such as alkanolamides, particularly the monoethanolamides derived from palm kernel fatty acids and coconut fatty acids; heavy metal sequestrants such as EDTA; perfumes including deodorant perfumes; germicides; pigments, colorants or coloured speckles; and inorganic salts such as sodium and magnesium sulphate.
  • Sodium sulphate, calcium carbonate may if desired be present as a filler material in amounts up to 40% by weight of the composition; however as little as 10% or less by weight of the composition of sodium sulphate, or even none at all, may be present.
  • the formulation can also contain anionic surfactant, which, at a level of up to 100 mole%, preferably 50 mole%, of the cationic softener present, may promote the softening performance of the formulation.
  • the detergent compositions according to the invention may be in any suitable form including powders, bars, liquids and pastes.
  • suitable liquid compositions may be nonaqueous or aqueous.
  • the compositions may be prepared by a number of different methods according to their physical form. In the case of granular products they may be prepared by dry-mixing, coagglomeration, spray-drying from an aqueous slurry or any combination of these methods.
  • One preferred physical form is a granule incorporating a detergency builder salt. This may be prepared by conventional granulation techniques or spray-drying.
  • compositions are in liquid form, especially preferred are transparent or translucent liquid detergents.
  • the formulations detailed below were tested in model mixed load tergotometer experiments at a liquor:cloth ratio of 25:1.
  • the fabric load used in each tergotometer pot comprised 3 pieces each of cotton terry towelling, cotton sheeting, 50/50 polycotton, and polyester, totalling 40g in weight.
  • Each tergotometer run was performed three times. Wash treatments were done at 40°C for 15 minutes and were followed by a 5 minute rinse at ambient temperature. Fabrics were line-dried, following a short spin. Three wash-rinse-dry cycles were performed for each treatment prior to softness evaluation of the terry towelling and staining of each of the other fabrics with 0.05ml olive oil (highly refined, ex Sigma Diagnostics) containing a small amount of solvent violet dye. The stains were allowed to wick out for 4 days, prior to measurement of reflectance spectra and re-washing, together with the terry towelling, using the detergent system used for the pre-treatments.
  • Softening of the fabrics was assessed by an expert panel of 4 people using a round robin paired comparison test protocol. Each panel member assessed four sets of test cloths. Each set of test cloths contained one cloth of each test system under a evaluation. Panel members were asked to assess softness on a 8 point scale. Softness scores were calculated using an "Analysis of Variance" technique. Lower values are indicative of better softening.
  • Dobanol 91-5 is C9-C11 alcohol ethoxylate (5 EO), ex Shell.
  • Soil release polymer is a copolymer of poly(ethylene glycol methyl ether), terephthalic acid, and glycerol as described in EP 752468.
  • DMDAPS is 3-(Dimethyldodecylammonio) propanesulphonate, ex Fluka.
  • Genapol C200 is coco-alcohol ethoxylate (20 EO), ex Hoechst.
  • HTTMAPC is 1,2 bis [dihardened tallowoyloxy] 1-3 trimethylammonium propane chloride.
  • the softness evaluation is shown below.
  • the formulations containing builder were prepared by shearing the ingredients together in a Moulinex blender until an homogeneous slurry was obtained.
  • the formulations containing SRP were prepared by equilibrating the ingredients together at 80°C, with occasional agitation, until an homogeneous solution/dispersion was obtained.
  • the formulations were prepared by equilibrating the ingredients together at 80°C, with occasional agitation, until an homogeneous solution/dispersion was obtained.
  • the softness of the terry towelling was assessed by a trained panel, who ranked the towels on a line scale where 8 represents harsh, unsoftened fabric and 2 represents very soft, conditioned fabric, as typical after use a large dose of a conventional rinse conditioner formulation.
  • Example 7 was a clear liquid, whilst comparative Example E was turpid and went cloudy on standing.

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)

Claims (15)

  1. Composition détergente d'adoucissement des textiles comprenant :
    i) un tensioactif détergent comprenant un tensioactif amphotère et/ou un tensioactif non ionique ;
    ii) un composé d'adoucissement des textiles sensiblement insoluble dans l'eau ayant une solubilité n'excédant pas 1 x 10-3 % en poids dans l'eau déminéralisée à 20°C et comprenant un composé ayant deux groupes alkyle ou alcényle en C12-22 reliés à un groupe de tête ammonium quaternaire via au moins une liaison ester ou un composé ammonium quaternaire comprenant une chaíne unique avec une longueur de chaíne moyenne égale à ou supérieure à C20 ;
    iii) un agent de renforcement de la détergence ;
    dans laquelle quand les constituants (i) et (ii) sont dilués dans l'eau à une concentration de 5% en poids de (i) et (ii), au moins 70% en poids du composé d'adoucissement des textiles (ii) sont en solution, et de plus dans laquelle le rapport pondéral du tensioactif détergent (i) au composé d'adoucissement des textiles (ii) est d'au moins 1:1.
  2. Composition détergente selon la revendication 1, dans laquelle le rapport du tensioactif détergent (i) au composé d'adoucissement des textiles (ii) est dans la gamme de 5:1 à 30:1.
  3. Composition détergente selon l'une quelconque des revendications précédentes, qui comprend de plus un solubilisant non tensioactif pour le composé d'adoucissement des textiles (ii).
  4. Composition détergente selon l'une quelconque des revendications précédentes, dans laquelle le tensioactif détergent est un tensioactif amphotère.
  5. Composition détergente selon l'une quelconque des revendications 1 à 3, dans laquelle le tensioactif détergent est un mélange de tensioactif non ionique et de tensioactif amphotère.
  6. Composition détergente selon l'une quelconque des revendications précédentes, dans laquelle le composé d'adoucissement des textiles (ii) comprend un composé ayant deux groupes alkyle ou alcényle en C12-22 reliés à un groupe de tête ammonium quaternaire via au moins une liaison ester.
  7. Composition détergente selon la revendication 6, dans laquelle le composé d'adoucissement des textiles est choisi parmi le chlorure de 1,2-bis(suifoyloxy durci)-3-triméthylammoniumpropane et le chlorure de di(suifoyloxyéthyl)diméthylammonium.
  8. Composition détergente selon l'une quelconque des revendications précédentes dans laquelle la quantité de tensioactif détergent (i) est au moins 10% en poids de la composition totale.
  9. Composition détergente selon l'une quelconque des revendications précédentes, dans laquelle l'agent de renforcement de détergence (iii) est choisi parmi les adjuvants, les enzymes, les agents de libération des salissures, les polymères d'anti-redéposition, les séquestrants, les chélateurs ou les systèmes de blanchiment.
  10. Composition détergente selon la revendication 9, dans laquelle l'agent de renforcement de détergence est un polymère de libération des salissures.
  11. Composition détergente selon l'une quelconque des revendications précédentes, qui est sous forme d'agrégats moléculaires à auto-limitation dimensionnelle.
  12. Composition détergente selon l'une quelconque des revendications précédentes qui est sous forme liquide.
  13. Composition détergente selon la revendication 12, qui est transparente ou translucide.
  14. Composition détergente selon l'une quelconque des revendications 1 à 12 qui est sous forme granulaire ou sous forme de poudre.
  15. Utilisation d'agrégats moléculaires à auto-limitation dimensionnelle comme des micelles ou des solutions micellaires avec des intérieurs solides ou liquides ou leurs mélanges, comme système d'adoucissement des textiles dans la composition détergente d'adoucissement des textiles de toute revendication antérieure.
EP96932507A 1995-10-04 1996-09-11 Composition de detergent pour lessive Revoked EP0862609B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
GBGB9520519.1A GB9520519D0 (en) 1995-10-04 1995-10-04 Detergent composition
GB9520519 1995-10-04
PCT/EP1996/004002 WO1997012952A1 (fr) 1995-10-04 1996-09-11 Composition de detergent pour lessive

Publications (2)

Publication Number Publication Date
EP0862609A1 EP0862609A1 (fr) 1998-09-09
EP0862609B1 true EP0862609B1 (fr) 2000-07-12

Family

ID=10781955

Family Applications (1)

Application Number Title Priority Date Filing Date
EP96932507A Revoked EP0862609B1 (fr) 1995-10-04 1996-09-11 Composition de detergent pour lessive

Country Status (11)

Country Link
EP (1) EP0862609B1 (fr)
AR (1) AR003768A1 (fr)
AU (1) AU724175B2 (fr)
BR (1) BR9610791A (fr)
CZ (1) CZ289267B6 (fr)
DE (1) DE69609346T2 (fr)
GB (1) GB9520519D0 (fr)
HU (1) HUP9900093A3 (fr)
PL (1) PL188709B1 (fr)
WO (1) WO1997012952A1 (fr)
ZA (1) ZA967834B (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB9521667D0 (en) * 1995-10-23 1996-01-03 Unilever Plc Fabric softening composition
DE102012204270A1 (de) 2012-03-19 2013-09-19 Henkel Ag & Co. Kgaa Flüssiges Waschmittel mit erhöhter Reinigungsleistung

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994006899A1 (fr) * 1992-09-11 1994-03-31 Henkel Kommanditgesellschaft Auf Aktien Melanges de detergents

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4128485A (en) * 1976-08-16 1978-12-05 Colgate-Palmolive Company Fabric softening compounds
US4259217A (en) * 1978-03-07 1981-03-31 The Procter & Gamble Company Laundry detergent compositions having enhanced greasy and oily soil removal performance
US5616553A (en) * 1993-08-12 1997-04-01 The Procter & Gamble Company Fabric conditioning compositions
CN1077134C (zh) * 1994-04-07 2002-01-02 尤尼利弗公司 织物柔软组合物
BR9507284A (pt) * 1994-04-07 1997-09-23 Unilever Nv Composição amaciadora de tecidos agente amaciador de tecido e uso de agregados moleculares auto-limitantes em tamanho

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994006899A1 (fr) * 1992-09-11 1994-03-31 Henkel Kommanditgesellschaft Auf Aktien Melanges de detergents

Also Published As

Publication number Publication date
AU7128496A (en) 1997-04-28
DE69609346D1 (de) 2000-08-17
PL188709B1 (pl) 2005-03-31
PL326004A1 (en) 1998-08-17
BR9610791A (pt) 1999-07-13
ZA967834B (en) 1997-04-04
GB9520519D0 (en) 1995-12-13
EP0862609A1 (fr) 1998-09-09
HUP9900093A2 (hu) 1999-05-28
DE69609346T2 (de) 2000-12-07
AU724175B2 (en) 2000-09-14
AR003768A1 (es) 1998-09-09
CZ289267B6 (cs) 2001-12-12
CZ101398A3 (cs) 1998-08-12
WO1997012952A1 (fr) 1997-04-10
HUP9900093A3 (en) 2000-02-28

Similar Documents

Publication Publication Date Title
EP1179038B1 (fr) Compositions assouplissantes pour textiles
EP0499434B1 (fr) Compositions détergentes
US5520839A (en) Laundry detergent composition containing synergistic combination of sophorose lipid and nonionic surfactant
EP2909295B1 (fr) Compositions détergentes pour le linge
US5417879A (en) Synergistic dual-surfactant detergent composition containing sophoroselipid
EP0262897A2 (fr) Composition détergente
JP2011524457A (ja) 洗濯組成物
CA1201258A (fr) Agent assouplisseur de tissus
EP2366008B1 (fr) Compositions de lessive
EP1590426B1 (fr) Compositions de nettoyage et de conditionnement pour blanchisserie
US6517588B2 (en) Laundry treatment for fabrics
EP0862609B1 (fr) Composition de detergent pour lessive
US5700387A (en) Fabric softening composition
EP1272601B1 (fr) Compositions de lavage pour lessive
CA2184069C (fr) Composition assouplissante pour textiles
WO2021102080A1 (fr) Polymères inhibiteurs de redéposition et compositions détergentes les contenant
WO2017102874A1 (fr) Composition de détergent liquide
EP1146110B1 (fr) Utilisation de polymères dans le nettoyage du linge
EP3327106A1 (fr) Avantage de repassage facile/anti-plis/moins de froissage au moyen de polymères cationiques et leurs dérivés
EP3272850A1 (fr) Avantage de repassage simple/anti-froissement/réduction de plis de compositions de traitement de textiles à l'aide de polymères antisalissures
CN1328366C (zh) 彩色织物的洗涤方法
EP4077612B1 (fr) Polymères inhibiteurs de redéposition et compositions détergentes les contenant
EP0849354A1 (fr) Compositions adoucissantes
EP3327108A1 (fr) Avantage de repassage facile/sans pli/moins de froissage de détergents à l'aide de bentonite ou de ses dérivés
JPH10212496A (ja) 洗濯用洗剤及び洗濯方法

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: 19980225

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): DE FR GB IT

17Q First examination report despatched

Effective date: 19990114

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

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 FR GB IT

ITF It: translation for a ep patent filed

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

REF Corresponds to:

Ref document number: 69609346

Country of ref document: DE

Date of ref document: 20000817

ET Fr: translation filed
PLBI Opposition filed

Free format text: ORIGINAL CODE: 0009260

PLBF Reply of patent proprietor to notice(s) of opposition

Free format text: ORIGINAL CODE: EPIDOS OBSO

26 Opposition filed

Opponent name: HENKEL KGAA

Effective date: 20010409

PLBF Reply of patent proprietor to notice(s) of opposition

Free format text: ORIGINAL CODE: EPIDOS OBSO

PLBF Reply of patent proprietor to notice(s) of opposition

Free format text: ORIGINAL CODE: EPIDOS OBSO

REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

PLAW Interlocutory decision in opposition

Free format text: ORIGINAL CODE: EPIDOS IDOP

APAC Appeal dossier modified

Free format text: ORIGINAL CODE: EPIDOS NOAPO

APAC Appeal dossier modified

Free format text: ORIGINAL CODE: EPIDOS NOAPO

APAA Appeal reference recorded

Free format text: ORIGINAL CODE: EPIDOS REFN

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

Ref country code: GB

Payment date: 20050908

Year of fee payment: 10

APBU Appeal procedure closed

Free format text: ORIGINAL CODE: EPIDOSNNOA9O

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

Ref country code: FR

Payment date: 20050919

Year of fee payment: 10

APAH Appeal reference modified

Free format text: ORIGINAL CODE: EPIDOSCREFNO

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

Ref country code: DE

Payment date: 20051031

Year of fee payment: 10

RDAF Communication despatched that patent is revoked

Free format text: ORIGINAL CODE: EPIDOSNREV1

RDAG Patent revoked

Free format text: ORIGINAL CODE: 0009271

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: PATENT REVOKED

27W Patent revoked

Effective date: 20050913

GBPR Gb: patent revoked under art. 102 of the ep convention designating the uk as contracting state

Free format text: 20050913

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

Ref country code: IT

Payment date: 20060930

Year of fee payment: 11