EP0653480B1 - Beim Waschen weichmachende Zusammensetzungen - Google Patents

Beim Waschen weichmachende Zusammensetzungen Download PDF

Info

Publication number
EP0653480B1
EP0653480B1 EP93309041A EP93309041A EP0653480B1 EP 0653480 B1 EP0653480 B1 EP 0653480B1 EP 93309041 A EP93309041 A EP 93309041A EP 93309041 A EP93309041 A EP 93309041A EP 0653480 B1 EP0653480 B1 EP 0653480B1
Authority
EP
European Patent Office
Prior art keywords
detergent composition
alkyl
weight
acid
polymers
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
EP93309041A
Other languages
English (en)
French (fr)
Other versions
EP0653480A1 (de
Inventor
Christopher David Buckley
Allyson Jane Hindson
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.)
Procter and Gamble Co
Original Assignee
Procter and Gamble Co
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=8214602&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP0653480(B1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Priority to EP93309041A priority Critical patent/EP0653480B1/de
Priority to DK93309041T priority patent/DK0653480T3/da
Priority to PT93309041T priority patent/PT653480E/pt
Priority to ES93309041T priority patent/ES2141138T3/es
Priority to AT93309041T priority patent/ATE188989T1/de
Priority to DE69327654T priority patent/DE69327654T2/de
Priority to EP93203611A priority patent/EP0628624A1/de
Priority to AU79743/94A priority patent/AU7974394A/en
Priority to PCT/US1994/011512 priority patent/WO1995013348A1/en
Publication of EP0653480A1 publication Critical patent/EP0653480A1/de
Publication of EP0653480B1 publication Critical patent/EP0653480B1/de
Application granted granted Critical
Priority to GR20000400817T priority patent/GR3033126T3/el
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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
    • C11D17/065—High-density particulate detergent 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0021—Dye-stain or dye-transfer inhibiting 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
    • C11D3/3776—Heterocyclic compounds, e.g. lactam
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3792—Amine oxide containing polymers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38609—Protease or amylase in solid compositions only

Definitions

  • the present invention relates to detergent compositions containing a silicate softening system. More in particular, the present invention relates to softening through the wash detergent compositions comprising layered silicates and flocculating polymers.
  • Detergent compositions providing fabric softening throughout the wash cycle have been described in art.
  • clays are well known as fabric softening agents through the wash.
  • the relative ability of the softening clays to meet various performance criteria is very much depending on the presence and concentration of adjunct detergent ingredients.
  • An example of such adjunct detergent ingredient is the presence of nonionic surfactants. Said nonionic surfactants, when used at substantial concentrations inhibit the deposition of the clay onto the fabric. So far it was therefore necessary to limit the level of nonionic surfactants in clay containing softening through the wash compositions.
  • Polymers have been used within detergent compositions to inhibit dye transfer.
  • examples of such polymers are vinylpyrrolidone polymers such as described EP-A-265 257 and EP-A-508 034.
  • vinylpyrrolidone polymers tend to interact with the clays formulated therewith. Accordingly, the dye transfer inhibiting performance of the polymers and the softening performance of the clays are negatively affected.
  • polyvinylpyrrolidone polymers are very compatible with the silicate softening system in that the dye transfer inhibiting performance of the polymers is not negatively affected in the presence of the silicate softening system.
  • the softening performance of layered silicates formulated with dye transfer inhibiting polymers has been maintained.
  • an alternative softening system is obtained which provides softening through the wash performance without adversely affecting the overall detergency performance of the detergent formulated therewith.
  • Layered silicates have been described in WO-A-92/03525 and WO-A-92/18594 as builders in detergent compositions, which may comprise certain polymeric compounds. Accordingly, the present invention allows to use the silicates in a dual function, e.g. builder and softener thereby facilitating the formulation of compact detergents.
  • the present invention relates to detergent compositions comprising layered silicate and flocculating polymers, as in the appended claims and to the use of layered silicate and flocculating polymers for providing fabric softening as in the appended claim 9.
  • compositions of the present invention comprise as an essential element a crystalline layered sodium silicate having the general formula NaMSi x O 2x+1 yH 2 O wherein
  • the softening system herein comprises a flocculating agent.
  • the compositions herein comprise preferably from 0.05% to 20% by weight of the silicate, of flocculating agent, if its molecular weight is 150.000-800.000 and preferably from 0.005% to 2%, by weight of the silicate, if its molecular weight is from 800.000 to 5 million. Most of these materials are fairly long chain polymers and copolymers.
  • the flocculating agents used in the present invention are polymers and copolymers selected from those derived from monomers selected from ethylene oxide, acrylamide, acrylic acid, dimethylamino ethyl methacrylate, vinyl alcohol, vinyl pyrrolidone, ethylene imine or mixtures thereof. Gums, like guar gum, are suitable as well as optional flocculating agents.
  • polymers of ethylene oxide, acryl amide, or acrylic acid are preferred.
  • the polymers should be fairly long chain, i.e., have a weight average molecular weight of at least 100,000.
  • the weight average molecular weight of the polymers should not exceed 10 million.
  • clay is present in the detergent compositions according to the present invention by less than 5% by weight of the detergent composition. More preferably, the clay is present in the detergent composition by less than than 1%, most preferably the detergent composition is substantially free of clay.
  • a wide range of surfactants can be used in the detergent compositions.
  • Polyethylene, polypropylene, and polybutylene oxide condensates of alkyl phenols are suitable for use as the nonionic surfactant of the surfactant systems of the present invention, with the polyethylene oxide condensates being preferred.
  • These compounds include the condensation products of alkyl phenols having an alkyl group containing from 6 to 14 carbon atoms, preferably from 8 to 14 carbon atoms, in either a straight-chain or branched-chain configuration with the alkylene oxide.
  • the ethylene oxide is present in an amount equal to from 5 to 25 moles, more preferably from 3 to 15 moles, of ethylene oxide per mole of alkyl phenol.
  • nonionic surfactants of this type include IgepalTM CO-630, marketed by the GAF Corporation; and TritonTM X-45, X-114, X-100 and X-102, all marketed by the Rohm & Haas Company. These surfactants are commonly referred to as alkylphenol alkoxylates (e.g., alkyl phenol ethoxylates).
  • the condensation products of primary and secondary aliphatic alcohols with from 1 to 25 moles of ethylene oxide are suitable for use as the nonionic surfactant of the nonionic surfactant systems of the present invention.
  • the alkyl chain of the aliphatic alcohol can either be straight or branched, primary or secondary, and generally contains from 8 to 22 carbon atoms.
  • nonionic surfactants of this type include TergitolTM 15-S-9 (the condensation product of C 11 -C 15 linear alcohol with 9 moles ethylene oxide), TergitolTM 24-L-6 NMW (the condensation product of C 12 -C 14 primary alcohol with 6 moles ethylene oxide with a narrow molecular weight distribution), both marketed by Union Carbide Corporation; NeodolTM 45-9 (the condensation product of C 14 -C 15 linear alcohol with 9 moles of ethylene oxide), NeodolTM 23-6.5 (the condensation product of C 12 -C 13 linear alcohol with 6.5 moles of ethylene oxide), NeodolTM 45-7 (the condensation product of C 14 -C 15 linear alcohol with 7 moles of ethylene oxide), NeodolTM 45-4 (the condensation product of C 14 -C 15 linear alcohol with 4 moles of ethylene oxide) marketed by Shell Chemical Company, and KyroTM EOB (the condensation product of C 13 -C 15 alcohol with 9 moles ethylene oxide), marketed by The Procter
  • nonionic surfactant of the surfactant systems of the present invention are the alkylpolysaccharides disclosed in U.S. Patent 4,565,647, Llenado, issued January 21, 1986, having a hydrophobic group containing from 6 to 30 carbon atoms, preferably from 10 to 16 carbon atoms and a polysaccharide, e.g. a polyglycoside, hydrophilic group containing from 1.3 to 10, preferably from 1.3 to 3, most preferably from 1.3 to 2.7 saccharide units.
  • Any reducing saccharide containing 5 or 6 carbon atoms can be used, e.g., glucose, galactose and galactosyl moieties can be substituted for the glucosyl moieties (optionally the hydrophobic group is attached at the 2-, 3-, 4-, etc. positions thus giving a glucose or galactose as opposed to a glucoside or galactoside).
  • the intersaccharide bonds can be, e.g., between the one position of the additional saccharide units and the 2-, 3-, 4-, and/or 6- positions on the preceding saccharide units.
  • a polyalkyleneoxide chain joining the hydrophobic moiety and the polysaccharide moiety.
  • the preferred alkyleneoxide is ethylene oxide.
  • Typical hydrophobic groups include alkyl groups, either saturated or unsaturated, branched or unbranched containing from 8 to 18, preferably from 10 to 16, carbon atoms.
  • the alkyl group is a straight chain saturated alkyl group.
  • the alkyl group can contain up to 3 hydroxy groups and/or the polyalkyleneoxide chain can contain up to 10, preferably less than 5, alkyleneoxide moieties.
  • Suitable alkyl polysaccharides are octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, and octadecyl, di-, tri-, tetra-, penta-, and hexaglucosides, galactosides, lactosides, glucoses, fructosides, fructoses and/or galactoses.
  • Suitable mixtures include coconut alkyl, di-, tri-, tetra-, and pentaglucosides and tallow alkyl tetra-, penta-, and hexaglucosides.
  • the preferred alkylpolyglycosides have the formula R 2 O(C n H 2n O) t (glycosyl) x wherein R 2 is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups contain from 10 to 18, preferably from 12 to 14, carbon atoms; n is 2 or 3, preferably 2; t is from 0 to 10, preferably 0; and x is from 1.3 to 10, preferably from 1.3 to 3, most preferably from 1.3 to 2.7.
  • the glycosyl is preferably derived from glucose.
  • the alcohol or alkylpolyethoxy alcohol is formed first and then reacted with glucose, or a source of glucose, to form the glucoside (attachment at the 1-position).
  • the additional glycosyl units can then be attached between their 1-position and the preceding glycosyl units 2-, 3-, 4- and/or 6-position, preferably predominately the 2-position.
  • condensation products of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol are also suitable for use as the additional nonionic surfactant of the nonionic surfactant systems of the present invention.
  • the hydrophobic portion of these compounds will preferably have a molecular weight of from 1500 to 1800 and will exhibit water insolubility.
  • the addition of polyoxyethylene moieties to this hydrophobic portion tends to increase the water solubility of the molecule as a whole, and the liquid character of the product is retained up to the point where the polyoxyethylene content is about 50% of the total weight of the condensation product, which corresponds to condensation with up to 40 moles of ethylene oxide.
  • Examples of compounds of this type include certain of the commercially-available PluronicTM surfactants, marketed by BASF.
  • nonionic surfactant of the nonionic surfactant system of the present invention are the condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylenediamine.
  • the hydrophobic moiety of these products consists of the reaction product of ethylenediamine and excess propylene oxide, and generally has a molecular weight of from 2500 to 3000. This hydrophobic moiety is condensed with ethylene oxide to the extent that the condensation product contains from 40% to 80% by weight of polyoxyethylene and has a molecular weight of from 5,000 to 11,000.
  • this type of nonionic surfactant include certain of the commercially available TetronicTM compounds, marketed by BASF.
  • Preferred for use as the nonionic surfactant of the surfactant systems of the present invention are polyethylene oxide condensates of alkyl phenols, condensation products of primary and secondary aliphatic alcohols with from about 1 to 25 moles of ethylene oxide, alkylpolysaccharides, and mixtures thereof. Most preferred are C 8 -C 14 alkyl phenol ethoxylates having from 3 to 15 ethoxy groups and C 8 -C 18 alcohol ethoxylates (preferably C 10 avg.) having from 2 to 10 ethoxy groups, and mixtures thereof.
  • Highly preferred nonionic surfactants are polyhydoxy fatty acid amide surfactants.
  • nonionic surfactants are poly hydroxy fatty acid amide surfactants of the formula wherein R 1 is H, or R 1 is C 1-4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl or a mixture thereof, R 2 is C 5-31 hydrocarbyl, and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative thereof.
  • R 1 is methyl
  • R 2 is a straight C 11-15 alkyl or alkenyl chain such as coconut alkyl or mixtures thereof
  • Z is derived from a reducing sugar such as glucose, fructose, maltose, lactose, in a reductive amination reaction.
  • the nonionic surfactant systems of the present invention act to improve the greasy/oily stain removal properties of such laundry detergent compositions across a broad range of laundry conditions.
  • Suitable anionic surfactants include alkyl alkoxylated sulfate surfactants hereof are water soluble salts or acids of the formula RO(A) m SO 3 M wherein R is an unsubstituted C 10 -C 24 alkyl or hydroxyalkyl group having a C 10 -C 24 alkyl component, preferably a C 12 -C 20 alkyl or hydroxyalkyl, more preferably C 12 -C 18 alkyl or hydroxyalkyl, A is an ethoxy or propoxy unit, m is greater than zero, typically between 0.5 and 6, more preferably between 0.5 and 3, and M is H or a cation which can be, for example, a metal cation (e.g., sodium, potassium, lithium, calcium, magnesium, etc.), ammonium or substituted-ammonium cation.
  • R is an unsubstituted C 10 -C 24 alkyl or hydroxyalkyl group having a C 10 -C 24 alkyl
  • Alkyl ethoxylated sulfates as well as alkyl propoxylated sulfates are contemplated herein.
  • Specific examples of substituted ammonium cations include methyl-, dimethyl, trimethyl-ammonium cations and quaternary ammonium cations such as tetramethyl-ammonium and dimethyl piperidinium cations and those derived from alkylamines such as ethylamine, diethylamine, triethylamine, mixtures thereof, and the like.
  • Exemplary surfactants are C 12 -C 18 alkyl polyethoxylate (1.0) sulfate (C 12 -C 18 E(1.0)M), C 12 -C 18 alkyl polyethoxylate (2.25) sulfate (C 12 -C 18 E(2.25)M), C 12 -C 18 alkyl polyethoxylate (3.0) sulfate (C 12 -C 18 E(3.0)M), and C 12 -C 18 alkyl polyethoxylate (4.0) sulfate (C 12 -C 18 E(4.0)M), wherein M is conveniently selected from sodium and potassium.
  • Suitable anionic surfactants to be used are alkyl ester sulfonate surfactants including linear esters of C 8 -C 20 carboxylic acids (i.e., fatty acids) which are sulfonated with gaseous SO 3 according to "The Journal of the American Oil Chemists Society", 52 (1975), pp. 323-329.
  • Suitable starting materials would include natural fatty substances as derived from tallow, palm oil, etc.
  • the preferred alkyl ester sulfonate surfactant especially for laundry applications, comprise alkyl ester sulfonate surfactants of the structural formula : wherein R 3 is a C 8 -C 20 hydrocarbyl, preferably an alkyl, or combination thereof, R 4 is a C 1 -C 6 hydrocarbyl, preferably an alkyl, or combination thereof, and M is a cation which forms a water soluble salt with the alkyl ester sulfonate.
  • Suitable salt-forming cations include metals such as sodium, potassium, and lithium, and substituted or unsubstituted ammonium cations, such as monoethanolamine, diethanolamine, and triethanolamine.
  • R 3 is C 10 -C 16 alkyl
  • R 4 is methyl, ethyl or isopropyl.
  • methyl ester sulfonates wherein R 3 is C 10 -C 16 alkyl.
  • alkyl sulfate surfactants hereof are water soluble salts or acids of the formula ROSO 3 M wherein R preferably is a C 10 -C 24 hydrocarbyl, preferably an alkyl or hydroxyalkyl having a C 10 -C 20 alkyl component, more preferably a C 12 -C 18 alkyl or hydroxyalkyl, and M is H or a cation, e.g., an alkali metal cation (e.g. sodium, potassium, lithium), or ammonium or substituted ammonium (e.g.
  • R preferably is a C 10 -C 24 hydrocarbyl, preferably an alkyl or hydroxyalkyl having a C 10 -C 20 alkyl component, more preferably a C 12 -C 18 alkyl or hydroxyalkyl
  • M is H or a cation, e.g., an alkali metal cation (e.g. sodium, potassium, lithium), or ammonium or substituted
  • alkylamines such as ethylamine, diethylamine, triethylamine, and mixtures thereof, and the like.
  • alkyl chains of C 12 -C 16 are preferred for lower wash temperatures (e.g. below about 50°C) and C 16-18 alkyl chains are preferred for higher wash temperatures (e.g. above about 50°C).
  • anionic surfactants useful for detersive purposes can also be included in the laundry detergent compositions of the present invention.
  • These can include salts (including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts) of soap, C 9 -C 20 linear alkylbenzenesulfonates, C 8 -C 22 primary of secondary alkanesulfonates, C 8 -C 24 olefinsulfonates, sulfonated polycarboxylic acids prepared by sulfonation of the pyrolyzed product of alkaline earth metal citrates, e.g., as described in British patent specification No.
  • alkylpolyglycolethersulfates (containing up to 10 moles of ethylene oxide); alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, paraffin sulfonates, alkyl phosphates, isethionates such as the acyl isethionates, N-acyl taurates, alkyl succinamates and sulfosuccinates, monoesters of sulfosuccinates (especially saturated and unsaturated C 12 -C 18 monoesters) and diesters of sulfosuccinates (especially saturated and unsaturated C 6 -C 12 diesters), acyl sarcosinates, sulfates of alkylpolysaccharides such as the sul
  • Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tall oil. Further examples are described in "Surface Active Agents and Detergents" (Vol. I and II by Schwartz, Perry and Berch). A variety of such surfactants are also generally disclosed in U.S. Patent 3,929,678, issued December 30, 1975 to Laughlin, et al. at Column 23, line 58 through Column 29, line 23.
  • the laundry detergent compositions of the present invention typically comprise from 1% to 40%, preferably from 3% to 20% by weight of such anionic surfactants.
  • the laundry detergent compositions of the present invention may also contain cationic, ampholytic, zwitterionic, and semi-polar surfactants, as well as nonionic surfactants other than those already described herein.
  • Preferred cationic surfactant systems include nonionic and ampholytic surfactants.
  • Cationic detersive surfactants suitable for use in the laundry detergent compositions of the present invention are those having one long-chain hydrocarbyl group.
  • cationic surfactants include the ammonium surfactants such as alkyldimethylammonium halogenides, and those surfactants having the formula : [R 2 (OR 3 ) y ][R 4 (OR 3 ) y ] 2 R 5 N + X - wherein R 2 is an alkyl or alkyl benzyl group having from 8 to 18 carbon atoms in the alkyl chain, each R 3 is selected from the group consisting of -CH 2 CH 2 -, -CH 2 CH(CH 3 )-, -CH 2 CH(CH 2 OH)-, -CH 2 CH 2 CH 2 -, and mixtures thereof; each R 4 is selected from the group consisting of C 1 -C 4 alkyl, C 1 -C 4 hydroxyalkyl, benzyl ring structures formed by joining the two R 4 groups, -CH 2 CHOH-CHOHCOR 6 CHOHCH 2 OH wherein R 6 is any hexose or hexos
  • the preferred alkyl chain length for R 1 is C 12 -C 15 particularly where the alkyl group is a mixture of chain lengths derived from coconut or palm kernel fat or is derived synthetically by olefin build up or OXO alcohols synthesis.
  • Preferred groups for R 2 R 3 and R 4 are methyl and hydroxyethyl groups and the anion X may be selected from halide, methosulphate, acetate and phosphate ions.
  • the laundry detergent compositions of the present invention typically comprise from 0% to 25%, preferably from 3% to 15% by weight of such cationic surfactants.
  • Ampholytic surfactants are also suitable for use in the laundry detergent compositions of the present invention. These surfactants can be broadly described as aliphatic derivatives of secondary or tertiary amines, or aliphatic derivatives of heterocyclic secondary and tertiary amines in which the aliphatic radical can be straight- or branched-chain.
  • One of the aliphatic substituents contains at least 8 carbon atoms, typically from 8 to 18 carbon atoms, and at least one contains an anionic water-solubilizing group, e.g. carboxy, sulfonate, sulfate. See U.S. Patent No. 3,929,678 to Laughlin et al., issued December 30, 1975 at column 19, lines 18-35, for examples of ampholytic surfactants.
  • the laundry detergent compositions of the present invention typically comprise from 0% to 15%, preferably from 1% to 10% by weight of such ampholytic surfactants.
  • Zwitterionic surfactants are also suitable for use in laundry detergent compositions. These surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. See U.S. Patent No. 3,929,678 to Laughlin et al., issued December 30, 1975 at column 19, line 38 through column 22, line 48, for examples of zwitterionic surfactants.
  • the laundry detergent compositions of the present invention typically comprise from 0% to 15%, preferably from 1% to 10% by weight of such zwitterionic surfactants.
  • Semi-polar nonionic surfactants are a special category of nonionic surfactants which include water-soluble amine oxides containing one alkyl moiety of from 10 to 18 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from 1 to 3 carbon atoms; water-soluble phosphine oxides containing one alkyl moiety of from about 10 to 18 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from 1 to 3 carbon atoms; and water-soluble sulfoxides containing one alkyl moiety of from 10 to 18 carbon atoms and a moiety selected from the group consisting of alkyl and hydroxyalkyl moieties of from 1 to 3 carbon atoms.
  • Semi-polar nonionic detergent surfactants include the amine oxide surfactants having the formula wherein R 3 is an alkyl, hydroxyalkyl, or alkyl phenyl group or mixtures therof containing from 8 to 22 carbon atoms; R 4 is an alkylene or hydroxyalkylene group containing from 2 to 3 carbon atoms or mixtures thereof; x is from 0 to 3; and each R 5 is an alkyl or hydroxyalkyl group containing from 1 to 3 carbon atoms or a polyethylene oxide group containing from 1 to 3 ethylene oxide groups.
  • the R 5 groups can be attached to each other, e.g., through an oxygen or nitrogen atom, to form a ring structure.
  • amine oxide surfactants in particular include C 10 -C 18 alkyl dimethyl amine oxides and C 8 -C 12 alkoxy ethyl dihydroxy ethyl amine oxides.
  • the laundry detergent compositions of the present invention typically comprise from 0% to 15%, preferably from 1% to 10% by weight of such semi-polar nonionic surfactants.
  • the present invention further provides laundry detergent compositions comprising at least 1% by weight, preferably from 3% to 65%, more preferably from about 10% to 25% by weight of total surfactants.
  • compositions according to the present invention may further comprise a builder system.
  • a builder system Any conventional builder system is suitable for use herein including aluminosilicate materials, polycarboxylates and fatty acids, materials such as ethylenediamine tetraacetate, metal ion sequestrants such as aminopolyphosphonates, particularly ethylenediamine tetramethylene phosphonic acid and diethylene triamine pentamethylenephosphonic acid.
  • phosphate builders can also be used herein. Suitable builders can be an inorganic ion exchange material, commonly an inorganic hydrated aluminosilicate material, more particularly a hydrated synthetic zeolite such as hydrated zeolite A, X, B or HS.
  • Suitable polycarboxylates containing one carboxy group include lactic acid, glycolic acid and ether derivatives thereof as disclosed in Belgian Patent Nos. 831,368, 821,369 and 821,370.
  • Polycarboxylates containing two carboxy groups include the water-soluble salts of succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid, diglycollic acid, tartaric acid, tartronic acid and fumaric acid, as well as the ether carboxylates described in German Offenlegenschrift 2,446,686, and 2,446,687 and U.S. Patent No. 3,935,257 and the sulfinyl carboxylates described in Belgian Patent No. 840,623.
  • Polycarboxylates containing three carboxy groups include, in particular, water-soluble citrates, aconitrates and citraconates as well as succinate derivatives such as the carboxymethyloxysuccinates described in British Patent No. 1,379,241, lactoxysuccinates described in Netherlands Application 7205873, and the oxypolycarboxylate materials such as 2-oxa-1,1,3-propane tricarboxylates described in British Patent No. 1,387,447.
  • Polycarboxylates containing four carboxy groups include oxydisuccinates disclosed in British Patent No. 1,261,829, 1,1,2,2-ethane tetracarboxylates, 1,1,3,3-propane tetracarboxylates and 1,1,2,3-propane tetracarboxylates.
  • Polycarboxylates containing sulfo substituents include the sulfosuccinate derivatives disclosed in British Patent Nos. 1,398,421 and 1,398,422 and in U.S. Patent No. 3,936,448, and the sulfonated pyrolysed citrates described in British Patent No. 1,082,179, while polycarboxylates containing phosphone substituents are disclosed in British Patent No. 1,439,000.
  • Alicyclic and heterocyclic polycarboxylates include cyclopentane-cis,cis,cis-tetracarboxylates, cyclopentadienide pentacarboxylates, 2,3,4,5-tetrahydrofuran - cis, cis, cis-tetracarboxylates, 2,5-tetrahydrofuran -cis - dicarboxylates, 2,2,5,5-tetrahydrofuran - tetracarboxylates, 1,2,3,4,5,6-hexane -hexacarboxylates and and carboxymethyl derivatives of polyhydric alcohols such as sorbitol, mannitol and xylitol.
  • Aromatic polycarboxylates include mellitic acid, pyromellitic acid and the phtalic acid derivatives disclosed in British Patent No. 1,425,343.
  • the preferred polycarboxylates are hydroxycarboxylates containing up to three carboxy groups per molecule, more particularly citrates.
  • Preferred builder systems for use in the present compositions include a mixture of a water-insoluble aluminosilicate builder such as zeolite A or of a layered silicate (SKS-6), and a water-soluble carboxylate chelating agent such as citric acid.
  • a suitable chelant for inclusion in the detergent compositions in accordance with the invention is ethylenediamine-N,N'-disuccinic acid (EDDS) or the alkali metal, alkaline earth metal, ammonium, or substituted ammonium salts thereof, or mixtures thereof.
  • EDDS compounds are the free acid form and the sodium or magnesium salt thereof. Examples of such preferred sodium salts of EDDS include Na 2 EDDS and Na 4 EDDS. Examples of such preferred magnesium salts of EDDS include MgEDDS and Mg 2 EDDS. The magnesium salts are the most preferred for inclusion in compositions in accordance with the invention.
  • Preferred builder systems include a mixture of a water-insoluble aluminosilicate builder such as zeolite A, and a watersoluble carboxylate chelating agent such as citric acid.
  • a water-insoluble aluminosilicate builder such as zeolite A
  • a watersoluble carboxylate chelating agent such as citric acid.
  • Other builder materials that can form part of the builder system for use in granular compositions the purposes of the invention include inorganic materials such as alkali metal carbonates, bicarbonates, silicates, and organic materials such as the organic phosphonates, amiono polyalkylene phosphonates and amino polycarboxylates.
  • Other suitable water-soluble organic salts are the homo- or co-polymeric acids or their salts, in which the polycarboxylic acid comprises at least two carboxyl radicals separated from each other by not more than two carbon atoms.
  • Polymers of this type are disclosed in GB-A-1,596,756.
  • Examples of such salts are polyacrylates of MW 2000-5000 and their copolymers with maleic anhydride, such copolymers having a molecular weight of from 20,000 to 70,000, especially about 40,000.
  • Detergency builder salts are normally included in amounts of from 10% to 80% by weight of the composition preferably from 20% to 70% and most usually from 30% to 60% by weight.
  • Detergent ingredients that can be included in the detergent compositions of the present invention include bleaching agents. These bleaching agent components can include one or more oxygen bleaching agents and, depending upon the bleaching agent chosen, one or more bleach activators. When present bleaching compounds will typically be present at levels of from 1% to 10%, of the detergent composition. In general, bleaching compounds are optional components in non-liquid formulations, e.g. granular detergents. If present, the amount of bleach activators will typically be from 0.1% to 60%, more typically from about 0.5% to 40% of the bleaching composition.
  • the bleaching agent component for use herein can be any of the bleaching agents useful for detergent compositions including oxygen bleaches as well as others known in the art.
  • this invention further provides a method for cleaning fabrics, fibers, textiles, at temperatures below about 50°C, especially below about 40°C, with a detergent composition containing polyamine N-oxide containing polymers, optional auxiliary detersive surfactants, optional detersive adjunct ingredients, and a bleaching agent.
  • a detergent composition containing polyamine N-oxide containing polymers, optional auxiliary detersive surfactants, optional detersive adjunct ingredients, and a bleaching agent.
  • the bleaching agent suitable for the present invention can be an activated or non-activated bleaching agent.
  • oxygen bleaching agent that can be used encompasses percarboxylic acid bleaching agents and salts thereof. Suitable examples of this class of agents include magnesium monoperoxyphthalate hexahydrate, the magnesium salt of meta-chloro perbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid and diperoxydodecanedioic acid.
  • Such bleaching agents are disclosed in U.S. Patent 4,483,781, U.S. Patent Application 740,446, European Patent Application 0,133,354 and U.S. Patent 4,412,934.
  • Highly preferred bleaching agents also include 6-nonylamino-6-oxoperoxycaproic acid as described in U.S. Patent 4,634,551.
  • bleaching agents that can be used encompasses the halogen bleaching agents.
  • hypohalite bleaching agents include trichloro isocyanuric acid and the sodium and potassium dichloroisocyanurates and N-chloro and N-bromo alkane sulphonamides. Such materials are normally added at 0.5-10% by weight of the finished product, preferably 1-5% by weight.
  • the bleaches suitable for the present invention include peroxygen bleaches.
  • suitable water-soluble solid peroxygen bleaches include hydrogen peroxide releasing agents such as hydrogen peroxide, perborates, e.g. perborate monohydrate, perborate tetrahydrate, persulfates, percarbonates, peroxydisulfates, perphosphates and peroxyhydrates.
  • Preferred bleaches are percarbonates and perborates.
  • the hydrogen peroxide releasing agents can be used in combination with bleach activators such as tetraacetylethylenediamine (TAED), nonanoyloxybenzenesulfonate (NOBS, described in US-A-4,412,934), 3,5,-trimethylhexanoloxybenzenesulfonate (ISONOBS, described in EP-A-120,591) or pentaacetylglucose (PAG), which are perhydrolyzed to form a peracid as the active bleaching species, leading to improved bleaching effect.
  • bleach activators such as tetraacetylethylenediamine (TAED), nonanoyloxybenzenesulfonate (NOBS, described in US-A-4,412,934), 3,5,-trimethylhexanoloxybenzenesulfonate (ISONOBS, described in EP-A-120,591) or pentaacetylglucose (PAG), which are perhydro
  • the hydrogen peroxide may also be present by adding an enzymatic system (i.e. an enzyme and a substrate therefore) which is capable of generating hydrogen peroxide at the beginning or during the washing and/or rinsing process.
  • an enzymatic system i.e. an enzyme and a substrate therefore
  • Such enzymatic systems are disclosed in EP Patent Application 91202655.6 filed October 9, 1991.
  • peroxygen bleaches suitable for the present invention include organic peroxyacids such as percarboxylic acids.
  • Bleaching agents other than oxygen bleaching agents are also known in the art and can be utilized herein.
  • One type of non-oxygen bleaching agent of particular interest includes photoactivated bleaching agents such as the sulfonated zinc and/or aluminum phthalocyanines. These materials can be deposited upon the substrate during the washing process. Upon irradiation with light, in the presence of oxygen, such as by hanging clothes out to dry in the daylight, the sulfonated zinc phthalocyanine is activated and, consequently, the substrate is bleached.
  • Preferred zinc phthalocyanine and a photoactivated bleaching process are described in U.S. Patent 4,033,718.
  • detergent compositions will contain 0.025% to 1.25%, by weight, of sulfonated zinc phthalocyanine.
  • detergent ingredients that can be included are detersive enzymes which can be included in the detergent formulations for a wide variety of purposes including removal of protein-based, carbohydrate-based, or triglyceride-based stains, for example, and prevention of refugee dye transfer.
  • the enzymes to be incorporated include proteases, amylases, lipases, cellulases, and peroxidases, as well as mixtures thereof.
  • Other types of enzymes may also be included. They may be of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin.
  • Enzymes are normally incorporated at levels sufficient to provide up to 5 mg by weight, more typically 0.05 mg to 3 mg, of active enzyme per gram of the composition.
  • proteases are the subtilisins which are obtained from particular strains of B.subtilis and B.licheniforms.
  • proteases suitable for removing protein-based stains that are commercially available include those sold under the tradenames Alcalase, Savinase and Esperase by Novo Industries A/S (Denmark) and Maxatase by International Bio-Synthetics, Inc. (The Netherlands) and FN-base by Genencor, Optimase and Opticlean by MKC.
  • Protease A is described in European Patent Application 130,756.
  • Protease B is described in European Patent Application Serial No. 87303761.8.
  • Amylases include, for example, -amylases obtained from a special strain of B.licheniformis, described in more detail in British Patent Specification No. 1,296,839 (Novo).
  • Amylolytic proteins include, for example, Rapidase, Maxamyl (International Bio-Synthetics, Inc.) and Termamyl (Novo Industries).
  • the cellulases usable in the present invention include both bacterial or fungal cellulase. Preferably, they will have a pH optimum of between 5 and 9.5. Suitable cellulases are disclosed in U.S. Patent 4,435,307, Barbesgoard et al, which discloses fungal cellulase produced from Humicola insolens. Suitable cellulases are also disclosed in GB-A-2.075.028 ; GB-A-2.095.275 and DE-A-2.247.832.
  • cellulases examples include cellulases produced by a strain of Humicola insolens (Humicola grisea var. thermoidea), particularly the Humicola strain DSM 1800, and cellulases produced by a fungus of Bacillus N or a cellulase 212-producing fungus belonging to the genus Aeromonas, and cellulase extracted from the hepatopancreas of a marine mollusc (Dolabella Auricula Solander).
  • Other suitable cellulases are cellulases originated from Humicola Insulens having a molecular weight of about 50KDa, an isoelectric point of 5.5 and containing 415 amino acids.
  • Especially suitable cellulase are the cellulase having color care benefits.
  • Examples of such cellulases are cellulase described in European patent application No. 91202879.2, filed November 6, 1991 Carezyme (Novo).
  • Suitable lipase enzymes for detergent usage include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as disclosed in British Patent 1,372,034.
  • Suitable lipases include those which show a positive immunological cross-reaction with the antibody of the lipase, produced by the microorganism Pseudomonas fluorescent IAM 1057. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade name Lipase P "Amano,” hereinafter referred to as "Amano-P".
  • Especially suitable Lipase are lipase such as M1 Lipase (Ibis) and Lipolase (Novo).
  • Peroxidase enzymes are used in combination with oxygen sources, e.g. percarbonate, perborate, persulfate, hydrogen peroxide, etc. They are used for "solution bleaching", i.e. to prevent transfer of dyes of pigments removed from substrates during wash operations to other substrates in the wash solution.
  • Peroxidase enzymes are known in the art, and include, for example, horseradish peroxidase, ligninase, and haloperoxidase such as chloro- and bromo-peroxidase.
  • Peroxidase-containing detergent compositions are disclosed, for example, in PCT Internation Application WO 89/099813 and in European Patent application EP No. 91202882.6, filed on November 6, 1991.
  • an enzyme stabilization system is preferably utilized.
  • Enzyme stabilization techniques for aqueous detergent compositions are well known in the art.
  • one technique for enzyme stabilization in aqueous solutions involves the use of free calcium ions from sources such as calcium acetate, calcium formate and calcium propionate.
  • Calcium ions can be used in combination with short chain carboxylic acid salts, preferably formates. See, for example, U.S. patent 4,318,818. It has also been proposed to use polyols like glycerol and sorbitol.
  • Alkoxy-alcohols dialkylglycoethers, mixtures of polyvalent alcohols with polyfunctional aliphatic amines (e.g., such as diethanolamine, triethanolamine, di-isopropanolamime, etc.), and boric acid or alkali metal borate.
  • Enzyme stabilization techniques are additionally disclosed and exemplified in U.S. patent 4,261,868, U.S. Patent 3,600,319, and European Patent Application Publication No. 0 199 405, Application No. 86200586.5.
  • Non-boric acid and borate stabilizers are preferred.
  • Enzyme stabilization systems are also described, for example, in U.S. Patents 4,261,868, 3,600,319 and 3,519,570.
  • enzyme oxidation scavengers which are described in Copending European Patent application N 92870018.6 filed on January 31, 1992.
  • enzyme oxidation scavengers are ethoxylated tetraethylene polyamines.
  • Especially preferred detergent ingredients are combinations with technologies which also provide a type of color care benefit.
  • Examples to these technologies are polyvinylpyrrolidone polymers such as described in EP-A-0 508 034.
  • the detergent compositions herein may contain a polyvinylpyrrolidone ("PVP") having an average molecular weight of from 5,000 to 400,000, preferably from 5,000 to 200,000, more preferably from 5,000 to 50,000, and most preferably from 5,000 to 20,000.
  • PVP polyvinylpyrrolidone
  • Suitable polyvinylpyrrolidones are commercially available from GAF Corporation, New York, NY and Montreal, Canada under the product names PVP K-15 (average molecular weight of 10,000), PVP K-30 (average molecular weight of 40,000), PVP K-60 (average molecular weight of 160,000), and PVP K-90 (average molecular weight of 360,000). PVP K-15 is also available from ISP Corporation. Other suitable polyvinylpyrrolidones which are commercially available from BASF Cooperation include Sokalan HP 165 and Sokalan HP 12. Polyvinylpyrrolidones known to persons skilled in the detergent field; see for example EP-A-262,897 and EP-A-256,696.
  • the amount of polyvinylpyrrolidone used in the present detergent compositions should be from 0.01% to 5% by weight of the detergent, preferably from 0.05% to 3% by weight, and more preferably from 0.1% to 2% by weight.
  • the amount of polyvinylpyrrolidone delivered in the wash solution is from 0.5 ppm to 300 ppm, preferably from 1 ppm to 60 ppm, more preferably from 1 ppm to 30 ppm, and most preferably from 1 ppm to 20 ppm.
  • Preferred polymers for inhibiting dye transfer are polyamine-N-oxide containing polymers such as described in EP-A- 0579 295.
  • the amine N-oxide polymers of the present invention typically have a ratio of amine to the amine N-oxide of 10:1 to 1:1,000,000.
  • the amount of amine oxide groups present in the polyamine oxide containing polymer can be varied by appropriate copolymerization or by appropriate degree of N-oxidation.
  • the ratio of amine to amine N-oxide is from 2:3 to 1:1,000,000. More preferably from 1:4 to 1:1,000,000, most preferably from 1:7 to 1:1,000,000.
  • the average molecular weight is within the range of 500 to 1,000,000; preferably from 1,000 to 50,000, more preferably from 2,000 to 30,000, most preferably from 3,000 to 20,000.
  • the polyamine N-oxide containing polymers of the present invention are typically present from 0.001 to 10%, more preferably from 0.01 to 2%, most preferred from 0.05 to 1% by weight of the detergent composition.
  • N-vinylimidazole N-vinylpyrrolidone copolymers such as described in EP-A-0628624.
  • the N-vinylimidazole N-vinylpyrrolidone polymers have an average molecular weight range from 5000-1,000,000, preferably from 20 000-200,000.
  • Highly preferred polymers for use in detergent compositions according to the present invention comprise a polymer selected from N-vinylimidazole N-vinylpyrrolidone copolymers wherein said polymer has an average molecular weight range from 5,000 to 50,000 more preferably from 8,000 to 30,000, most preferably from 10,000 to 20,000.
  • metallo catalysts are described in copending European Patent application No. 92870181.2.
  • a suds suppressor exemplified by silicones, and silica-silicone mixtures.
  • Silicones can be generally represented by alkylated polysiloxane materials while silica is normally used in finely divided forms exemplified by silica aerogels and xerogels and hydrophobic silicas of various types. These materials can be incorporated as particulates in which the suds suppressor is advantageously releasably incorporated in a water-soluble or water-dispersible, substantially non-surface-active detergent impermeable carrier.
  • the suds suppressor can be dissolved or dispersed in a liquid carrier and applied by spraying on to one or more of the other components.
  • a preferred silicone suds controlling agent is disclosed in Bartollota et al. U.S. Patent 3 933 672.
  • Other particularly useful suds suppressors are the self-emulsifying silicone suds suppressors, described in German Patent Application DTOS 2 646 126 published April 28, 1977.
  • An example of such a compound is DC-544, commercially available from Dow Corning, which is a siloxane-glycol copolymer.
  • Especially preferred suds controlling agent are the suds suppressor system comprising a mixture of silicone oils and 2-alkyl-alcanols. Suitable 2-alkyl-alcanols are 2-butyl-octanol which are commercially available under the trade name Isofol 12 R.
  • Such suds suppressor system are described in Copending European Patent application N 92870174.7 filed 10 November, 1992.
  • compositions can comprise a silicone/silica mixture in combination with fumed nonporous silica such as Aerosil R .
  • suds controlling agents comprise a silicone antifoam compound, a carrier material and an organic coating material further containing glycerol at a weight ratio with the silicone antifoam compound of 1:2 to 3:1.
  • the suds suppressors described above are normally employed at levels of from 0.001% to 2% by weight of the composition, preferably from 0.01% to 1% by weight.
  • detergent compositions may be employed, such as soil-suspending agents soil-release agents, optical brighteners, abrasives, bactericides, tarnish inhibitors, coloring agents, and non-encapsulated and encapsulated perfumes.
  • encapsulating materials are water soluble capsules which consist of a matrix of polysaccharide and polyhydroxy compounds such as described in GB-A- 1,464,616.
  • Suitable water soluble encapsulating materials comprise dextrins derived from ungelatinized starch acid-esters of substituted dicarboxylic acids such as described in US-A- 3,455,838. These acid-ester dextrins are,preferably, prepared from such starches as waxy maize, waxy sorghum, sago, tapioca and potato. Suitable examples of said encapsulating materials include N-Lok manufactured by National Starch. The N-Lok encapsulating material consisits of a modified maize starch and glucose. The starch is modified by adding monofunctional substituted groups such as octenyl succinic acid anhydride.
  • Antiredeposition and soil suspension agents suitable herein include cellulose derivatives such as methylcellulose, carboxymethylcellulose and hydroxyethylcellulose, and homo- or co-polymeric polycarboxylic acids or their salts.
  • Polymers of this type include the polyacrylates and maleic anhydrideacrylic acid copolymers previously mentioned as builders, as well as copolymers of maleic anhydride with ethylene, methylvinyl ether or methacrylic acid, the maleic anhydride constituting at least 20 mole percent of the copolymer. These materials are normally used at levels of from 0.5% to 10% by weight, more preferably from 0.75% to 8%, most preferably from 1% to 6% by weight of the composition.
  • Preferred optical brighteners are anionic in character, examples of which are disodium 4,4'-bis-(2-diethanolamino-4-anilino -s- triazin-6-ylamino)stilbene-2:2' disulphonate, disodium 4, - 4'-bis-(2-morpholino-4-anilino-s-triazin-6-ylaminostilbene-2:2 1 - disulphonate, disodium 4,4' - bis-(2,4-dianilino-s-triazin-6-ylamino)stilbene-2:2' - disulphonate, monosodium 4',4'' -bis-(2,4-dianilino-s-triazin-6 ylamino)stilbene-2-sulphonate, disodium 4,4' -bis-(2-anilino-4-(N-methyl-N-2-hydroxyethylamino)-s-triazin-6-ylamino)stilbene-2,2' -
  • polyethylene glycols particularly those of molecular weight 1000-10000, more particularly 2000 to 8000 and most preferably about 4000. These are used at levels of from 0.20% to 5% more preferably from 0.25% to 2.5% by weight. These polymers and the previously mentioned homo- or co-polymeric polycarboxylate salts are valuable for improving whiteness maintenance, fabric ash deposition, and cleaning performance on clay, proteinaceous and oxidizable soils in the presence of transition metal impurities.
  • Soil release agents useful in compositions of the present invention are conventionally copolymers or terpolymers of terephthalic acid with ethylene glycol and/or propylene glycol units in various arrangements. Examples of such polymers are disclosed in the commonly assigned US Patent Nos. 4116885 and 4711730 and European Published Patent Application No. 0 272 033.
  • a particular preferred polymer in accordance with EP-A-0 272 033 has the formula (CH 3 (PEG) 43 ) 0.75 (POH) 0.25 [T-PO) 2.8 (T-PEG) 0.4 ]T(PO- H) 0.25 ((PEG) 43 CH 3 ) 0.75 where PEG is -(OC 2 H 4 )O-,PO is (OC 3 H 6 O) and T is (pcOC 6 H 4 CO).
  • modified polyesters as random copolymers of dimethyl terephtalate, dimethyl sulfoisophtalate, ethylene glycol and 1-2 propane diol, the end groups consisting primarily of sulphobenzoate and secondarily of mono esters of ethylene glycol and/or propane-diol.
  • the target is to obtain a polymer capped at both end by sulphobenzoate groups, "primarily", in the present context most of said copolymers herein will be end-capped by sulphobenzoate groups.
  • some copolymers will be less than fully capped, and therefore their end groups may consist of monoester of ethylene glycol and/or propane 1-2 diol, thereof consist “secondarily” of such species.
  • the selected polyesters herein contain about 46% by weight of dimethyl terephtalic acid, about 16% by weight of propane - 1,2 diol, about 10% by weight ethylene glycol, about 13% by weight of dimethyl sulfobenzoic acid and about 15% by weight of sulfoisophtalic acid, and have a molecular weight of about 3.000.
  • the polyesters and their method of preparation are described in detail in EPA 311 342.
  • the detergent compositions according to the invention can be in liquid, paste, gels, bars or granular forms.
  • Granular compositions according to the present invention can also be in "compact form", i.e. they may have a relatively higher density than conventional granular detergents, i.e. from 550 to 950 g/l; in such case, the granular detergent compositions according to the present invention will contain a lower amount of "inorganic filler salt", compared to conventional granular detergents; typical filler salts are alkaline earth metal salts of sulphates and chlorides, typically sodium sulphate; "compact" detergents typically comprise not more than 10% filler salt.
  • liquid compositions according to the present invention can also be in "concentrated form", in such case, the liquid detergent compositions according to the present invention will contain a lower amount of water, compared to conventional liquid detergents.
  • the water content of the concentrated liquid detergent is less than 30%, more preferably less than 20%, most preferably less than 10% by weight of the detergent compositions.
  • the present invention also relates to a process for inhibiting dye transfer from one fabric to another of solubilized and suspended dyes encountered during fabric laundering operations involving colored fabrics.
  • the process comprises contacting fabrics with a laundering solution as hereinbefore described.
  • the process of the invention is conveniently carried out in the course of the washing process.
  • the washing process is preferably carried out at 5 °C to 75 °C, especially 20 to 60, but the polymers are effective at up to 95°C and higher temperatures.
  • the pH of the treatment solution is preferably from 7 to 11, especially from 7.5 to 10.5.
  • the process and compositions of the invention can also be used as detergent additive products. Such additive products are intended to supplement or boost the performance of conventional detergent compositions.
  • the detergent compositions according to the present invention include compositions which are to be used for cleaning substrates, such as fabrics, fibers, hard surfaces, skin etc., for example hard surface cleaning compositions (with or without abrasives), laundry detergent compositions, automatic and non automatic dishwashing compositions.
  • the efficiency of the layered silicate/flocculating polymer combination as a softening system was assessed by measuring the softening performance.
  • the softening performance was measured by a launderometer test.
  • the test procedure was as follows : 3.5 kg of clean fabric laundry loads were washed in an automatic drum washing machine Miel 423 at 60°C.
  • the hardness of the water was 2mM Calcium and the composition concentration was 0.7% in the wash liquor.
  • a granular detergent composition according to the present invention is prepared, having the following compositions : % by weight of the total detergent composition Linear alkyl benzene sulphonate 13.70 Tallow alkyl sulphate 5.9 C 45 alcohol 7 times ethoxylated 4.00 Trisodium citrate 5.00 Zeolite 26.00 Maleic acid actylic acid copolymer 4.9 Diethylenetriaminepentamethylene Phosphonic acid 0.6 Protease 1.5 carboxymethylcellulose 1.5 suds supressor (silicone) 0.3
  • Example I demonstrates the softening performance of the layered silicate in combination with the flocculating polymer versus compositions containing layered silicate without flocculating polymers.
  • the flocculating polymer that was used is polyethylene oxide having an average molecular weight of 300,000.
  • the layered silicate that was used is layered silicate (SKS-6).
  • PSU values for the softening performance (reference IA). Bleeding fabric composition: 100% cotton) and PSU values IB IC ID PSU 0 0 1.5
  • the efficiency of the silicate softening system was assessed by measuring the softening and cleaning performance.
  • the softening and cleaning performance was measured by a launderometer test.
  • the test procedure was as follows : 3.5 kg of clean fabric laundry loads were washed in an automatic drum washing machine Miel 423 at 60°C.
  • the hardness of the water was 2mM Calcium and the composition concentration was 0.7% in the wash liquor.
  • the cleaning performance is not negatively affected by the presence of the silicate softening system.
  • a compact granular detergent composition according to the present invention is prepared, having the following formulation: % by weight of the total detergent composition A B C D E Linear alkyl benzene sulphonate 11.40 - - - 5 Polyhydroxy fatty acid amide - 10 - 5 5 Alkyl alkoxylated sulfate - - 9 9 9 Tallow alkyl sulphate 1.80 1.80 1.80 4 4 C 45 alkyl sulphate 3.00 3.00 3.00 - - C 45 alcohol 7 times ethoxylated 4.00 4.00 4.00 - - Tallow alcohol 11 times ethoxylated 1.80 1.80 1.80 5 5 Dispersant 0.07 0.07 0.07 0.07 Silicone fluid 0.80 0.80 0.80 0.80 0.80 0.80 0.80 Trisodium citrate 14.00 14.00 14.00 14.00 14.00 14.00 Citric acid 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00 Zeolite 32.50 32.50 32.50 32.50 32.50
  • Example I (A/B/C/D/E)
  • Example I A/B/C/D/E
  • a liquid detergent composition according to the present invention is prepared, having the following compositions : % by weight of the total detergent composition A B C D Linear alkylbenzene sulfonate 10 - - - Polyhydroxy fatty acid amide - 5 - 3 Alkyl alkoxylated sulfate - - 9 4 Alkyl sulphate 4 8 4 15 Fatty alcohol (C 12 -C 15 ) ethoxylate 12 12 12 5 Fatty acid 10 10 10 10 10 10 Oleic acid 4 4 4 - Citric acid 1 1 1 1 1 1 1 1 1 Diethylenetriaminepentamethylene phosphonic acid 1.5 1.5 1.5 1.5 NaOH 3.4 3.4 3.4 3.4 Propanediol 1.5 1.5 1.5 1.5 1.5 1.5 Ethanol 10 10 10 Ethoxylated tetraethylene pentamine 0.7 0.7 0.7 0.7 Thermamyl R 300 KNU/g 0.1 0.1 0.1 0.1 Carezyme R 5000 CEVU/g 0.02 0.02 0.02 0.02 Pro
  • a compact granular detergent composition according to the present invention is prepared, having the following formulation: % by weight of the total detergent composition A B C D E Linear alkyl benzene sulphonat 11.40 - - - - Polyhydroxy fatty acid amide - 10 - - - Alkyl alkoxylated sulfate - - 9 9 9 Tallow alkyl sulphate 1.80 1.80 1.80 1.80 C 45 alkyl sulphate 3.00 3.00 3.00 3.00 3.00 3.00 3.00 C 45 alcohol 7 times ethoxylate 4.00 4.00 4.00 4.00 4.00 4.00 4.00 Tailors alcohol 11 times ethoxylated 1.80 1.80 1.80 1.80 1.80 1.80 Dispersant 0.07 0.07 0.07 0.07 Silicone fluid 0.80 0.80 0.80 0.80 0.80 0.80 0.80 Trisodium citrate 14.00 14.00 14.00 14.00 14.00 14.00 Citric acid 3.00 3.00 3.00 3.00 3.00 3.00 3.00 Zeolite 32.50 32.50
  • a liquid detergent composition according to the present invention is prepared, having the following compositions : % by weight off the total detergent composition A B C D Linear alkylbenzene sulfonate 10 - - - Polyhydroxy fatty acid amide - 5 - 3 Alkyl alkoxylated sulfate - - 9 4 Alkyl sulphate 4 8 4 15 Fatty alcohol (C 12 -C 15 ) ethoxylate 12 12 12 5 Fatty acid 10 10 10 10 10 10 Oleic acid 4 4 4 - Citric acid 1 1 1 1 1 1 1 1 1 Diethylenetriaminepentamethylene phosphonic acid 1.5 1.5 1.5 1.5 NaOH 3.4 3.4 3.4 3.4 Propanediol 1.5 1.5 1.5 1.5 1.5 Ethanol 10 10 10 Ethoxylated tetraethylene pentamine 0.7 0.7 0.7 0.7 Thermamyl R 300 KNU/g 0.1 0.1 0.1 0.1 Carezyme R 5000 CEVU/g 0.02 0.02 0.02 0.02 Prot
  • compositions Example II (A/B/C/D), III (A/B/C/D/E) and IV (A/B/C/D) were very good at displaying excellent cleaning and detergency performance with outstanding color-care performance on colored fabrics and mixed loads of colored and white fabrics.

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 (9)

  1. Detergenzzusammensetzung, welche ein kristallines Schichtsilikat der Formel NaMSixO2x+1 yH2O , worin M für Natrium oder Wasserstoff steht, x eine Zahl von 1,9 bis 4 darstellt und y eine Zahl von 0 bis 20 ist; und ein flockendes Polymer umfaßt, welches Polymer unter Polymeren und Copolymeren ausgewählt ist, die sich von Monomeren herleiten, welche unter Ethylenoxid, Acrylamid, Acrylsäure, Dimethylaminoethylmethacrylat, Vinylalkohol, Vinylpyrrolidon, Ethylenimin oder Gemischen hievon ausgewählt sind, dadurch gekennzeichnet, daß die genannte Detergenzzusammensetzung weniger als 5% an Ton, bezogen auf das Gewicht der Detergenzzusammensetzung, umfaßt, und durch die Maßgabe, daß das flockende Polymer kein Polyvinylpyrrolidonpolymer mit einem mittleren Molekulargewicht bis zu 700.000 ist.
  2. Detergenzzusammensetzung nach Anspruch 1, worin x einen Wert von 2 besitzt.
  3. Detergenzzusammensetzung nach den Ansprüchen 1 bis 2, worin M Natrium darstellt.
  4. Detergenzzusammensetzung nach den Ansprüchen 1 bis 3, worin das Silikat α-, β-, γ- oder δ-Na2Si2O5 ist.
  5. Detergenzzusammensetzung nach den Ansprüchen 1 bis 4, worin das flockende Polymer ein Polymer aus Ethylenoxid, Acrylamid oder Acrylsäure ist.
  6. Detergenzzusammensetzung nach den Ansprüchen 1 bis 5, welche ferner dadurch gekennzeichnet ist, daß der Ton in einer Menge von weniger als 1 Gew.-% der Detergenzzusammensetzung vorhanden ist, stärker bevorzugt, daß die Detergenzzusammensetzung im wesentlichen davon frei ist.
  7. Detergenzzusammensetzung nach den Ansprüchen 1 bis 6, welche ferner grenzflächenaktive Mittel, Gerüststoffe und Enzyme umfaßt.
  8. Detergenzzusammensetzung nach den Ansprüchen 1 bis 7, welche in der Form einer Flüssigkeit, eines Granulats, einer Paste, eines Riegels oder eines Gels vorliegt.
  9. Verwendung eines kristallinen Schichtsilikats der Formel NaMSixO2x+1 yH2O , worin M für Natrium oder Wasserstoff steht, x eine Zahl von 1,9 bis 4 darstellt und y eine Zahl von 0 bis 20 ist; und eines flockenden Polymers, welches unter Polymeren und Copolymeren ausgewählt ist, die sich von Monomeren herleiten, welche unter Ethylenoxid, Acrylamid, Acrylsäure, Dimethylaminoethylmethacrylat, Vinylalkohol, Vinylpyrrolidon, Ethylenimin oder Gemischen hievon ausgewählt sind, in einer Detergenzzusammensetzung zur Gewährleistung der Gewebeweichmachung.
EP93309041A 1993-06-09 1993-11-11 Beim Waschen weichmachende Zusammensetzungen Revoked EP0653480B1 (de)

Priority Applications (10)

Application Number Priority Date Filing Date Title
EP93309041A EP0653480B1 (de) 1993-11-11 1993-11-11 Beim Waschen weichmachende Zusammensetzungen
DK93309041T DK0653480T3 (da) 1993-11-11 1993-11-11 Blødgøring gennem vaskesammensætningerne
PT93309041T PT653480E (pt) 1993-11-11 1993-11-11 Efeito amaciador obtido atraves das composicoes de lavagem
ES93309041T ES2141138T3 (es) 1993-11-11 1993-11-11 Suavizado a traves de composiciones de lavado.
AT93309041T ATE188989T1 (de) 1993-11-11 1993-11-11 Beim waschen weichmachende zusammensetzungen
DE69327654T DE69327654T2 (de) 1993-11-11 1993-11-11 Beim Waschen weichmachende Zusammensetzungen
EP93203611A EP0628624A1 (de) 1993-06-09 1993-12-21 Protease enthaltende Waschmittelzusammensetzungen mit Zusätzen zur Verhinderung der Farbstoffübertragung
AU79743/94A AU7974394A (en) 1993-11-11 1994-10-11 Softening through the wash compositions
PCT/US1994/011512 WO1995013348A1 (en) 1993-11-11 1994-10-11 Softening through the wash compositions
GR20000400817T GR3033126T3 (en) 1993-11-11 2000-03-31 Softening through the wash compositions.

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP93309041A EP0653480B1 (de) 1993-11-11 1993-11-11 Beim Waschen weichmachende Zusammensetzungen

Publications (2)

Publication Number Publication Date
EP0653480A1 EP0653480A1 (de) 1995-05-17
EP0653480B1 true EP0653480B1 (de) 2000-01-19

Family

ID=8214602

Family Applications (1)

Application Number Title Priority Date Filing Date
EP93309041A Revoked EP0653480B1 (de) 1993-06-09 1993-11-11 Beim Waschen weichmachende Zusammensetzungen

Country Status (9)

Country Link
EP (1) EP0653480B1 (de)
AT (1) ATE188989T1 (de)
AU (1) AU7974394A (de)
DE (1) DE69327654T2 (de)
DK (1) DK0653480T3 (de)
ES (1) ES2141138T3 (de)
GR (1) GR3033126T3 (de)
PT (1) PT653480E (de)
WO (1) WO1995013348A1 (de)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100371760B1 (ko) † 1994-09-13 2003-03-15 카오카부시키가이샤 세탁방법및의류용세제조성물
DE19524451A1 (de) * 1995-07-07 1997-01-09 Henkel Kgaa Farbübertragungsinhibierendes Waschmittel
GB9605534D0 (en) * 1996-03-15 1996-05-15 Unilever Plc Detergent compositions
US5880081A (en) * 1997-04-07 1999-03-09 Gopalkrishnan; Sridhar Concentrated built liquid detergents containing a dye-transfer inhibiting additive
DE19819187A1 (de) * 1998-04-30 1999-11-11 Henkel Kgaa Festes maschinelles Geschirrspülmittel mit Phosphat und kristallinen schichtförmigen Silikaten
EP1894993A1 (de) * 2006-08-28 2008-03-05 Süd-Chemie Ag Waschmitteladditiv auf der Basis von Tonmineralien und PVP-haltigen Copolymeren
WO2018127390A1 (en) * 2017-01-06 2018-07-12 Unilever N.V. Stain removing composition

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0299575A1 (de) * 1987-07-14 1989-01-18 The Procter & Gamble Company Detergenszusammensetzungen
EP0313146A2 (de) * 1987-10-19 1989-04-26 The Procter & Gamble Company Reinigungsmittel

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2854484A1 (de) * 1978-12-16 1980-06-26 Bayer Ag Stabile waessrige zeolith-suspensionen
DE3416669A1 (de) * 1984-05-05 1985-11-07 Hoechst Ag, 6230 Frankfurt Weichmachendes waschmittel
DE3627773A1 (de) * 1986-08-16 1988-02-18 Hoechst Ag Phosphatfreies geschirrspuelmittel
US5108646A (en) * 1990-10-26 1992-04-28 The Procter & Gamble Company Process for agglomerating aluminosilicate or layered silicate detergent builders
DE4034131C2 (de) * 1990-10-26 1999-08-26 Henkel Kgaa Gerüststoff für Waschmittel
DE4109247A1 (de) * 1991-03-21 1992-09-24 Henkel Kgaa Fluessiges oder pastenfoermiges waschmittel
GB9108639D0 (en) * 1991-04-23 1991-06-12 Procter & Gamble Particulate detergent compositions
US5259994A (en) * 1992-08-03 1993-11-09 The Procter & Gamble Company Particulate laundry detergent compositions with polyvinyl pyrollidone

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0299575A1 (de) * 1987-07-14 1989-01-18 The Procter & Gamble Company Detergenszusammensetzungen
EP0313146A2 (de) * 1987-10-19 1989-04-26 The Procter & Gamble Company Reinigungsmittel

Also Published As

Publication number Publication date
DE69327654T2 (de) 2000-08-31
ATE188989T1 (de) 2000-02-15
PT653480E (pt) 2000-07-31
GR3033126T3 (en) 2000-08-31
DE69327654D1 (de) 2000-02-24
ES2141138T3 (es) 2000-03-16
AU7974394A (en) 1995-05-29
DK0653480T3 (da) 2000-04-17
EP0653480A1 (de) 1995-05-17
WO1995013348A1 (en) 1995-05-18

Similar Documents

Publication Publication Date Title
US5458809A (en) Surfactant-containing dye transfer inhibiting compositions
EP0581753B1 (de) Polymere Dispergiermittel enthaltende Zusammensetzungen zur Verhinderung der Farbstoffübertragung
EP0635565B1 (de) Die Farbstoffübertragung hemmende Waschmittelzusammensetzungen
US5912221A (en) Laundry detergent composition comprising substantially water-insoluble polymeric dye transfer inhibiting agent
EP0756001A1 (de) Waschmittelzusammensetzungen enthaltend eine spezifische Amylase une ein spezifisches oberflächenaktives System
US5710119A (en) Detergent compositions inhibiting dye transfer comprising copolymers of N-vinylimidazole and N-vinylpyrrolidone
EP0635566B1 (de) Die Farbstoffübertragung hemmende Waschmittelzusammensetzungen
EP0587550B1 (de) Tenside enthaltende Zusammensetzungen zur Verhinderung der Farbstoffübertragung
US5710118A (en) Detergent compostions inhibiting dye transfer comprising copolymers of n-vinylimidazole and n-vinylpyrrolidone
EP0628624A1 (de) Protease enthaltende Waschmittelzusammensetzungen mit Zusätzen zur Verhinderung der Farbstoffübertragung
EP0704523A1 (de) Betain enthaltende Zusammensetzungen zur Verhinderung der Farbstoffübertragung
EP0653480B1 (de) Beim Waschen weichmachende Zusammensetzungen
EP0719856B1 (de) Beim Waschen weichmachende Waschmittelzusammensetzungen
US5883064A (en) Protease containing dye transfer inhibiting composition
EP0687733A1 (de) Detergenzusammensetzung die Wolle-kompatible-hochalkalische Proteasen enthält
EP0798371A1 (de) Reinigungsmittelzusammensetzungen enthaltend eine spezifische Amylase und Alkylpolyglukosidtenside
WO1994002580A1 (en) Surfactant-containing dye transfer inhibiting compositions
EP0800570B1 (de) Waschmittelzusammensetzung mit wasserunlöslichem, entfärbungshemmendem polymerwirkstoff
EP0664332B1 (de) Waschmittelzusammensetzungen zur Verhinderung der Farbstoffübertragung
US5922082A (en) Detergent composition containing wool compatible high alkaline proteases
WO1994002578A1 (en) Dye transfer inhibiting compositions comprising polymeric dispersing agents
EP0635563A1 (de) Zusammensetzungen zur Verhinderung der Farbstoffübertragung mit Wascheweichspülmittel
WO1997016513A1 (en) Liquid laundry detergent compositions containing alkyl polyether glyceryl sulfates/sulfonates
WO1995033026A1 (en) Dye transfer inhibiting compositions containing oleoyl sarcosinate
EP0587549B1 (de) Zusammensetzungen zur Verhinderung der Farbstoffübertragung die Bleichmittel enthalten

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): AT BE CH DE DK ES FR GB GR IE IT LI LU NL PT SE

17P Request for examination filed

Effective date: 19951021

17Q First examination report despatched

Effective date: 19980126

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): AT BE CH DE DK ES FR GB GR IE IT LI LU NL PT SE

REF Corresponds to:

Ref document number: 188989

Country of ref document: AT

Date of ref document: 20000215

Kind code of ref document: T

REG Reference to a national code

Ref country code: CH

Ref legal event code: NV

Representative=s name: RITSCHER & SEIFERT

Ref country code: CH

Ref legal event code: EP

REF Corresponds to:

Ref document number: 69327654

Country of ref document: DE

Date of ref document: 20000224

ET Fr: translation filed
REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

ITF It: translation for a ep patent filed

Owner name: ING. C. GREGORJ S.P.A.

REG Reference to a national code

Ref country code: DK

Ref legal event code: T3

REG Reference to a national code

Ref country code: PT

Ref legal event code: SC4A

Free format text: AVAILABILITY OF NATIONAL TRANSLATION

Effective date: 20000412

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: 20001019

NLR1 Nl: opposition has been filed with the epo

Opponent name: HENKEL KGAA

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

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

Ref country code: DK

Payment date: 20020916

Year of fee payment: 10

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

Ref country code: GR

Payment date: 20020927

Year of fee payment: 10

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

Ref country code: GB

Payment date: 20021002

Year of fee payment: 10

Ref country code: AT

Payment date: 20021002

Year of fee payment: 10

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

Ref country code: PT

Payment date: 20021003

Year of fee payment: 10

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

Ref country code: NL

Payment date: 20021011

Year of fee payment: 10

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

Ref country code: IE

Payment date: 20021023

Year of fee payment: 10

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

Ref country code: LU

Payment date: 20021024

Year of fee payment: 10

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

Ref country code: FR

Payment date: 20021105

Year of fee payment: 10

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

Ref country code: SE

Payment date: 20021106

Year of fee payment: 10

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

Ref country code: ES

Payment date: 20021118

Year of fee payment: 10

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

Ref country code: DE

Payment date: 20021127

Year of fee payment: 10

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

Ref country code: BE

Payment date: 20021213

Year of fee payment: 10

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

Ref country code: CH

Payment date: 20021223

Year of fee payment: 10

RDAH Patent revoked

Free format text: ORIGINAL CODE: EPIDOS REVO

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: 20030226

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

Free format text: 20030226

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

REG Reference to a national code

Ref country code: SE

Ref legal event code: ECNC

NLR2 Nl: decision of opposition

Effective date: 20030226

REG Reference to a national code

Ref country code: PT

Ref legal event code: MF4A

Effective date: 20031103