EP0736085B2 - Percarbonat , amylase und protease enthaltende waschmittelzusammensetzungen - Google Patents

Percarbonat , amylase und protease enthaltende waschmittelzusammensetzungen Download PDF

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Publication number
EP0736085B2
EP0736085B2 EP95905359A EP95905359A EP0736085B2 EP 0736085 B2 EP0736085 B2 EP 0736085B2 EP 95905359 A EP95905359 A EP 95905359A EP 95905359 A EP95905359 A EP 95905359A EP 0736085 B2 EP0736085 B2 EP 0736085B2
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Prior art keywords
percarbonate
amylase
composition
textiles
alkyl
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EP0736085B1 (de
EP0736085A4 (de
EP0736085A1 (de
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Michael Alan John Moss
Christiaan Arthur Jacques Kamiel Thoen
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Procter and Gamble Co
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Procter and Gamble Co
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Priority claimed from EP93203611A external-priority patent/EP0628624A1/de
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    • 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
    • C11D1/83—Mixtures of non-ionic with anionic 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
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/146—Sulfuric acid esters
    • 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/128—Aluminium silicates, e.g. zeolites
    • 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
    • C11D3/38—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
    • 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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3942—Inorganic per-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
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic 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
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29—Sulfates of polyoxyalkylene ethers
    • 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

Definitions

  • the present invention relates to detergent compositions containing coated percarbonate bleach, amylase and protease enzymes at narrowly defined ratios, to provide synergistic stain removal performance, in particular on specific stains such as starch-based stains, and blood stains.
  • the inorganic perhydrate bleach most widely used in laundry detergent compositions is sodium perborate in the form of either the monohydrate or tetrahydrate.
  • concerns about the impact of boron salts on the environment have led to an increasing interest in other perhydrate salts, of which sodium percarbonate is the most readily available.
  • Detergent compositions containing sodium percarbonate are known in the art.
  • Sodium percarbonate is an attractive perhydrate for use in detergent compositions because it dissolves readily in water, is weight efficient and, after giving up its available oxygen, provides a useful source of carbonate ions for detergency purposes.
  • amylase enzymes in detergent compositions is known, although such use has been mainly described in perborate-based formulations.
  • enzymes including amylase in percarbonate-based compositions is known from e.g. JP 57028197 ; WO-A-94/01521 and WO-A-94/03554 .
  • DE 1 940 654 relates to enzyme - containing automatic detergents comprising a peroxy conpound wherein such peroxy compound is enveloped in water soluble cellulose ethers and/or esters.
  • US 4, 620, 936 discloses a midly alkaline enzymatic detergent clearing composition adapted for use in automatic dishwashing machines, comprising (a) or anylolytic enzyme, (b) sodium triphosphate, (c) sodium carbonate and/or borax, (d) sodium silicate, (e) a peroxy compound blesch, (f) a stabilising agent, and optionally but preferably (g) a proteolytic enzyme and/or (h) a low- to non-foaming nonionic surfactant and/or (i) a fatty acid having a chain length of C 12-18 , the amounts of components (b), (c) and (d) being so adjusted that the composition will have sufficient builder and buffering capacity to maintain a solution pH of from 9.3 to 10.8.
  • EP 504 091 relates to a phosphate - free automatic dishwashing composition
  • a phosphate - free automatic dishwashing composition comprising nonionic tenside, carboxylic acid, water-soluble alkalin compound and bleach, for excellent tea stain removing ability.
  • US 4, 969, 927 is directed to a process for the machine-washing of fabrics according to which a dispersing and diffusing device of the reusable type is filled with a particular product which is active during the washing.
  • particulate stains such as peat clay, mud, fertilizing soil, high organic content clay.
  • laundry detergent compositions including laundry additives and automatic dishwashing compositions are encompassed by the term "detergent compositions" herein.
  • Methods of treatment of textile are also encompassed.
  • the laundry detergent or automatic dishwashing compositions herein typically contain from 1% to 40%, preferably from 3% to 30% by weight, most preferably from 5% to 25% by weight of an alkali metal percarbonate bleach (when expresssed on an AvOx basis of 13.5%) in the form of particles having a mean size from 250 to 900 micrometers, preferably 500 to 700 micrometers.
  • Laundry additives typically contain from 20 to 80% of said percarbonate particles.
  • the alkali metal percarbonate bleach is usually in the form of the sodium salt.
  • Sodium percarbonate is an addition compound having a formula corresponding to 2Na 2 CO 3 3H 2 O 2 .
  • the coatings are (a) a mixed salt of an alkali metal sulphate and carbonate, (b) sodium silicate of SiO 2 :Na 2 O ratio from 1.6:1 to 2.8:1, and (c) magnesium silicate.
  • Such coatings together with coating processes have previously been described in GB-1,466,799 , granted to Interox on 9th March 1977.
  • the weight ratio of the mixed salt coating material to percarbonate lies in the range from 1:2000 to 1:4, more preferably from 1:99 to 1:9, and most preferably from 1:49 to 1:19.
  • the mixed salt is of sodium sulphate and sodium carbonate which has the general formula Na2SO4.n.Na2CO3 wherein n is from 0.1 to 3, preferably n is from 0.3 to 1.0 and most preferably n is from 0.2 to 0.5.
  • compositions herein further comprise as an essential ingredient an amylase enzyme (expressed on an activity of about 60KNU/g) in a weight ratio of percarbonate (expressed on an activity basis of 13.5% AvOx) to amylase of 1:2 to 300:1, preferably 1:2 to 200:1.
  • an amylase enzyme expressed on an activity of about 60KNU/g
  • percarbonate expressed on an activity basis of 13.5% AvOx
  • An even more preferred ratio is 1:2 to 60:1 while the most preferred ratio is 20:1 to 40:1.
  • the amylase enzyme can be incorporated into the compositions of the present invention at a level of from 0,1% to 2%, preferably at a level of from 0,1% to 1% by weight.
  • Preferred amylases include, for example, ⁇ -amylases obtained from a special strain of B. licheniforms, described in more detail in GB-1,296,839 (Novo Nordisk).
  • Preferred commercially available amylases include for example, Rapidase®, sold by International Bio-Synthetics Inc. and Termamyl®, sold by Novo Nordisk A/S.
  • the detergent compositions herein also contain a protease enzyme (expressed on an activity of about 4KNPU/g) in a weight ratio of protease to percarbonate (expressed on an activity basis of 13.5% AvOx) of from 2:1 to 1:10.
  • a protease enzyme expressed on an activity of about 4KNPU/g
  • a weight ratio of protease to percarbonate expressed on an activity basis of 13.5% AvOx
  • Preferred commercially available protease enzymes include those sold under the trade names Alcalase and Savinase by Novo Nordisk A/S (Denmark) and Maxatase by International Bio-Synthetics, Inc. (The Netherlands).
  • the laundry detergent compositions herein also comprise a surface-active agent and a builder.
  • the detergent compositions of the present invention contain one or more anionic surfactants as described below.
  • 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., methyl-, dimethyl-, and trimethyl ammonium cations and quaternary ammonium cations, such as tetramethylammonium and dimethyl piperidinium cations and quaternary ammonium cations derived from alkylamines such as ethylamine, diethylamine, triethylamine, and mixtures thereof ).
  • 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.), ammonium or substitutedammonium cation.
  • 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 ethoxylated sulfates as well as alkyl propoxylated sulfates are contemplated herein.
  • Specific examples of substituted ammonium cations include methyl-, dimethyl-, trimethylammonium and quaternary ammonium cations, such as tetramethylanmonium, dimethyl piperidinium and cations derived from alkanolamines such as ethylamine, diethylamine, triethylamine, mixtures thereof.
  • 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.
  • 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 alkylbenzenesulphonates, C 8 -C 22 primary or secondary alkanesulphonates, C 8 -C 24 olefinsulphonates, sulphonated polycarboxylic acids prepared by sulphonation of the pyrolyzed product of alkaline earth metal citrates, e.g., as described in British patent specification No.
  • salts including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts
  • C 9 -C 20 linear alkylbenzenesulphonates C 8 -C 22 primary or secondary alkanesulphonates
  • alkylpolyglycolethersulfates (containing up to 10 moles of ethylene oxide); alkyl ester sulfonates such as C 14-16 methyl ester sulfonates; 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 sulfosuccinate (especially saturated and unsaturated C 12 -C 18 monoesters) diesters of sulfosuccinate (especially saturated and unsaturated C 6 -C 14 diesters), acyl sarcosinates, sulfates of alkylpolysacc
  • 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 given 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.
  • Preferred surfactants for use in the compositions herein are the alkyl sulfates, alkyl alkoxylated sulfates, and mixtures thereof.
  • the laundry detergent compositions of the present invention comprise from 1 % to 40 %, preferably from 3 % to 20 % by weight of such anionic surfactants.
  • the present laundry detergent compositions preferably also comprise a nonionic surfactant.
  • nonionic surfactant While any nonionic surfactant may be normally employed in the present invention, two families of nonionics have been found to be particularly useful. These are nonionic surfactants based on alkoxylated (especially ethoxylated) alcohols, and those nonionic surfactants based on amidation products of fatty acid esters and N-alkyl polyhydroxy amine. The amidation products of the esters and the amines are generally referred to herein as polyhydroxy fatty acid amides. Particularly useful in the present invention are mixtures comprising two or more nonionic surfactants wherein at Least one nonionic surfactant is selected from each of the groups of alkoxylated alcohols and the polyhydroxy fatty acid amides.
  • Suitable nonionic surfactants include compounds produced by the condensation of alkylene oxide groups (hydrophilic in nature) with an organic hydrophobic compound, which may be aliphatic or alkyl aromatic in nature.
  • the length of the polyoxyalkylene group which is condensed with any particular hydrophobic group can be readily adjusted to yield a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements.
  • nonionic surfactants such as the polyethylene oxide condensates of alkyl phenols, e.g., the condensation products of alkyl phenols having an alkyl group containing from 6 to 16 carbon atoms, in either a straight chain or branched chain configuration, with from 4 to 25 moles of ethylene oxide per mole of alkyl phenol.
  • Preferred nonionics are the water-soluble condensation products of aliphatic alcohols containing from 8 to 22 carbon atoms, in either straight chain or branched configuration, with an average of up to 25 moles of ethylene oxide per mole of alcohol.
  • Particularly preferred are the condensation products of alcohols having an alkyl group containing from 9 to 15 carbon atoms with from 2 to 10 moles of ethylene oxide per mole of alcohol; and condensation products of propylene glycol with ethylene oxide.
  • the nonionic surfactant system herein can also include a polyhydroxy fatty acid amide component.
  • Polyhydroxy fatty acid amides may be produced by reacting a fatty acid ester and an N-alkyl polyhydroxy amine.
  • the preferred amine for use in the present invention is N-(R1)-CH2(CH2OH)4-CH2-OH and the preferred ester is a C12-C20 fatty acid methyl ester. Most preferred is the reaction product of N-methyl glucamine with C12-C20 fatty acid methyl ester.
  • Nonionic surfactant systems and granular detergents made from such systems have been described in WO 92 6160 , published on 16th April, 1992.
  • This application describes (example 15) a granular detergent composition prepared by fine dispersion. mixing in an Eirich RV02 mixer which comprises N-methyl glucamide (10%), nonionic surfactant (10%).
  • the polyhydroxy fatty acid amide may be present in compositions of the present invention at a level of from 0% to 50% by weight of the detergent component or composition, preferably from 5% to 40% by weight, even more preferably from 10% to 30% by weight.
  • 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, including the semi-polar nonionic amine oxides described below.
  • 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 R2 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 COH
  • 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, derivates 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 columns 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 af alkyl groups and hydroxyalkyl groups containing from 1 to 3 carbon atoms; water-soluble phosphine 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.
  • Semi-polar nonionic detergent surfactants include the amine oxide surfactants having the formula :
  • compositions herein preferably contain a builder, most preferably non-phosphate detergent builders. These can include, but are not restricted to alkali metal carbonates, bicarbonates, silicates, aluminosilicates, carboxylates and mixtures of any of the foregoing.
  • the builder system is present in an amount of from 25% to 80% by weight of the composition, more preferably from 30% to 60% by weight.
  • Suitable silicates are those having an SiO 2 : Na 2 O ratio in the range from 1.6 to 3.4, the so-called amorphous silicates of SiO 2 ; Na 2 O ratios from 2.0 to 2.8 being preferred.
  • crystalline layered sodium silicates of general formula NaMSi x O 2x )+1 ⁇ y H2O wherein M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20.
  • Crystalline layered sodium silicates of this type are disclosed in EP-A-0164514 and methods for their preparation are disclosed in DE-A-3417649 and DE-A-3742043 .
  • x in the-general formula above has a value of 2,3 or 4 and is preferably 2. More preferably M is sodium and y is 0 and a preferred example of this formula comprises the form of Na 2 Si 2 O 5 .
  • Crystalline layered silicates are incorporated either as dry mixed solids, or as solid components of agglomerates with other components.
  • preferred sodium aluminosilicate zeolites have the unit cell formula Na z [(AlO 2 ) z ⁇ (SiO 2 ) y ] ⁇ xH 2 O wherein z and y are at least about 6, the molar ratio of z to y is from 1.0 to 0.4 and x is from 10 to 264.
  • Amorphous hydrated aluminosilicate materials useful herein have the empirical formula M z (zAlO 2 ⁇ ySiO 2 ) wherein M is sodium, potassium, ammonium or substituted ammonium, z is from 0.5 to 2 and y is 1, said material having a magnesium ion exchange capacity of at least 50 milligram equivalents of CaCO 3 hardness per gram of anhydrous aluminosilicate. Hydrated sodium Zeolite A with a particle size of from 1 to 10 microns is preferred.
  • the aluminosilicate ion exchange builder materials herein are in hydrated form and contain from 10% to 28% of water by weight if crystalline, and potentially even higher amounts of water if amorphous. Highly preferred crystalline aluminosilicate ion exchange materials contain from 18% to 22% water in their crystal matrix.
  • the crystalline aluminosilicate ion exchange materials are further characterized by a particle size diameter of from 0.1 micron to 10 microns. Amorphous materials are often smaller, e.g., down to less than 0.01 micron.
  • Preferred ion exchange materials have a particle size diameter of from 0.2 micron to 4 microns.
  • the term "particle size diameter" herein represents the average particle size diameter by weight of a given ion exchange material as determined by conventional analytical techniques such as, for example, microscopic determination utilizing a scanning electron microscope.
  • Aluminosilicate ion exchange materials useful in the practice of this invention are commercially available.
  • the aluminosilicates useful in this invention can be crystalline or amorphous in structure and can be naturally occurring aluminosilicates or synthetically derived.
  • a method for producing aluminosilicate ion exchange materials is discussed in U.S. Pat. No. 3,985,669 , Krummel et al., issued Oct. 12, 1976.
  • Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite X, P and MAP, the latter species being described in EPA 384070.
  • the crystalline aluminosilicate ion exchange material is a Zeolite.
  • A having the formula Na 12 [(AlO 2 ) 12 (SiO2) 12 ] ⁇ xH 2 O wherein x is from 20 to 30, especially 27 and has a particle size generally less than about 5 microns.
  • Suitable carboxylate builders containing one carboxy group include lactic acid, glycollic 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 , and the 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 US 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 carboxymethyl derivatives of polyhydric alcohols such as sorbitol, mannitol and xylitol.
  • Aromatic polycarboxylates include mellitic acid, pyromellitic acid and the phtalic acid derivates disclosed in British Patent No. 1,425,343 .
  • the preferred polycarboxylates are hydroxycarboxylates containing up to three carboxy groups per molecule, more particularly citrates.
  • the parent acids of the monomeric or oligomeric polycarboxylate chelating agents or mixtures thereof with their salts, e.g. citric acid or citrate/citric acid mixtures are also-contemplated as components of builder systems useful in the present invention.
  • compositions are preferably in a compact form, having a bulk density of at least 650 g/l, but can also be in a conventional form, with densities in a range of from 200 g/l to 700 g/l.
  • Automatic dishwashing compositions typically contain, in addition to the percarbonate, the amylase enzyme and the anionic surfactant of the invention, a builder, such as described above, and a source of alkalinity, such as silicate or carbonate, those ingredients amounting to up to 70% of the formulation.
  • Optional ingredients include polymers and other enzymes.
  • Laundry Additive Compositions typically contain in addition to the percarbonate, the amylase enzyme and the anionic surfactant of the invention, a builder and a source of alkalinity.
  • ingredients which are known for use in detergent compositions may also be used as optional ingredients in the various embodiments of the present invention, such as bleach activators, other bleaching agents, polymers, other enzymes, suds suppressing agents, as well as dyes, fillers, optical brighteners, pH adjusting agents, non builder alkalinity sources, enzyme stability agents, hydrotopes, perfumes.
  • compositions especially the laundry detergent compositions/additives, preferably contain from 1% to 20% by weight of the composition, preferably from 2% to 15% by weight, most preferably from 3 to 10 by weight of a peroxyacid bleach activator.
  • Peroxyacid bleach activators as additional bleaching components in accordance with the invention can be selected from a wide range of class and are preferably those containing one or more N-or O-acyl groups.
  • Suitable classes include anhydrides, esters, amides, and acylated derivatives of imidazoles and oximes, and examples of useful materials within these classes are disclosed in GB-A-1586789 .
  • the most preferred classes are esters such as are disclosed in GB-A-836 988 , 864,798 , 1 147 871 and 2 143 231 and amides such as are disclosed in GB-A-855 735 and 1 246 338 .
  • Particularly preferred bleach activator compounds as additional bleaching components in accordance with the invention are the N,N,N'N'-tetra acetylated compounds of the formula where x can be O or an integer between 1 and 6.
  • TAMD tetra acetyl methylene diamine
  • TAED tetra acetyl ethylene diamine
  • TAHD Tetraacetyl hexylene diamine
  • R 1 is an aryl or alkaryl group with from 1 to 14 carbon atoms
  • R 2 is an alkylene, arylene, and alkarylene group containing from 1 to 14 carbon atoms
  • R 5 is H or an alkyl, aryl, or alkaryl group containing 1 to 10 carbon atoms and L can be essentially any leaving group.
  • R 1 preferably contains from 6 to 12 carbon atoms.
  • R 2 preferably contains from 4 to 8 carbon atoms.
  • R 1 may be straight chain or branched alkyl, substituted aryl or alkylaryl containing branching, substitution, or both and may be sourced from either synthetic sources or natural sources including for example, tallow fat. Analogous structural variations are permissible for R 2 . The substitution can include alkyl, aryl, halogen, nitrogen, sulphur and other typical substituent groups or organic compounds.
  • R 5 is preferably H or methyl. R 1 and R 5 should not contain more than 18 carbon atoms total. Amide substituted bleach activator compounds of this type are described in EP-A-0170386 .
  • Another class of bleach activators to use in combination with percarbonate comprises C 8 , C 9 , and/or C 10 (6-octanamidocaproyl) oxybenzenesulfonate, 2-phenyl-(4H)3,1 benzoxazin-4-one, benzoyllactam preferably benzoylcaprolactam and nonanoyl lactam preferably nonanoyl caprolactam.
  • compositions herein may also contain another bleaching system such as perborate and activator, or a preformed organic peracid or perimidic acid, such as N,N-phthaloylaminoperoxy caproic acid, 2-carboxyphtaloylaminoperoxy caproic acid, N,N phthaloylaminoperoxy valeric -acid, Nonyl amide of peroxy adipic acid, 1,12 diperoxydodecanedoic acid, Peroxybenzoic acid and ring substituted peroxybenzoic acid, Monoperoxyphtalic acid (magnesium salt, hexhydrate), Diperoxybrassylic acid.
  • another bleaching system such as perborate and activator, or a preformed organic peracid or perimidic acid, such as N,N-phthaloylaminoperoxy caproic acid, 2-carboxyphtaloylaminoperoxy caproic acid, N,N phthaloylaminoperoxy valeric -a
  • organic polymers some of which also may function as builders to improve detergency. Included among such polymers may be mentioned sodium carboxy-lower alkyl celluloses, sodium lower alkyl celluloses and sodium hydroxy-lower alkyl celluloses, such as sodium carboxymethyl cellulose, sodium methyl cellulose and sodium hydroxypropyl cellulose, polyvinyl alcohols (which often also include some polyvinyl acetate), polyacrylamides, polyacrylates and various copolymers, such as those of maleic and acrylic acids. Molecular weights for such polymers vary widely but most are within the range of 2,000 to 100,000. Also very useful are terpolymers of maleic/acrylic acid and vinyl alcohol having a molecular weight ranging from 3.000 to 70.000.
  • Polymeric polycarboxylate builders are set forth in U.S. Patent 3,308,067 , Diehl, issued March 7, 1967. Such materials include the water-soluble salts of homo-and copolymers of aliphatic carboxylic acids such as maleic acid, itaconic acid, mesaconic acid, fumaric acid, aconitic acid, citraconic acid and methylenemalonic acid.
  • polymers suitable for use herein include species known as soil release polymers, such as described in EPA 185 427 and EPA 311 342. Still other polymers suitable for use herein include dye transfer inhibition polymers such as polyvinylpyrrolidone, polyvinylpyrridine, N-oxide, N-vinylpyrrolidone, N-imidazole, polyvinyloxozolidone or polyvinylimidazole.
  • Enzymatic materials other than amylases and proteases can be incorporated into the detergent compositions herein. Suitable are lipases, cellulases and mixtures thereof.
  • a suitable lipase enzyme is manufactured and sold by Novo Nordisk A/S (Denmark) under the trade name Lipolase R and mentioned along with other suitable lipases in EP-A-0258068 (Novo Nordisk A/S).
  • Suitable cellulases are described in e.g. WO-92/13057 (Novo).
  • Starch-based stains include chocolate stains, as well as typical kitchen stains such as mayonnaise, mustard, ice-cream, dairy products. Such stains are very difficult to remove at low temperature, and the present invention provides for a method of treating textiles at all temperatures, including at low temperature, wherein a detergent composition according to the above description is used.
  • the invention also encompasses a similar method for treating fabrics to remove blood stains and fabrics stained with stains rich in blood.
  • particulate stains for instance peat clay, mud, high organic content clay mainly found in socks, sportswear.
  • Mucin_or mucin-protein based stains include female secretions and handkerchief stains (bronchial mucus). Such stains are very difficult to remove at low temperature, and the present invention provides for a method of treating textiles at all temperatures, including at low temperature, wherein a detergent composition according to the above description is used.
  • the method for treating fabrics is typically a laundry machine washing operation, and can be conducted by any method well known in the art; a particularly preferred method includes the use of a reusable dispensing device, in which the detergent composition is put before the washing cycle, and which is placed in the drum of the washing machine together with the clothes to be washed, before starting the washing machine.
  • Composition III IV V Zeolite A 15.0 15.0 Na2SO4 0.0 5.0 LAS 3.0 3.0 DTPMA 0.4 0.5 CMC 0.4 0.4 Maleic acrylic copolymer 4.0 4.0 45AS 11.0 LAS 6.0 5.0 TAS 3.0 2.0 Na2 Silicate 4.0 4.0 Zeolite A 10.0 15.0 13.0 CMC 0.5 Maleic acrylic copolymer 2.0 Na2 Carbonate 9.0 7.0 7.0 Perfume 0.3 0.3 0.5 AE7 4.0 4.0 4.0 AE3 2.0 2.0 2.0 Maleic acrylic copolymer 3.0 SKS 6 12.0 Citrate 10.0 0.0 8.0 Na Bicarbonate 7.0 3.0 5.0 Na2 Carbonate 8.0 5.0 7.0 PVP 0 0.5 0 PVPVI 0.2 0 0.25 PVNO 0.3 0 0.4 Savinase (4.0KNPU/g) 1.0 1.0 1.30 Lipolase (100.000LU/L) 0.4 0.4 0.4 Amylase (Termamyl) 60KNU/g 0.5 0.6 0.6 Carezyme
  • Example 1 blood based stain removal
  • Example 2 stain removal from chocolate ice cream
  • Example 3 blood based stain removal
  • Example 5 particulate stain removal

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Claims (12)

  1. Granuläre Reinigungsmittelzusammensetzung, umfassend ein Alkalimetallpercarbonat und ein Amylaseenzym in einem Gewichtsverhältnis von Percarbonat (ausgedrückt als 13,5% AvOx) zu Amylase (ausgedrückt bezüglich einer Aktivität von etwa 60 KNU/g) im Bereich von 1:2 bis 300:1, dadurch gekennzeichnet, daß die Zusammensetzung 1 bis 40% des Gewichts der Zusammensetzung eines anionischen Tensids und ein Proteaseenzym in einem Gewichtsverhältnis von Percarbonat (ausgedrückt als 13,5% AvOx) zu Protease (ausgedrückt bezüglich einer Aktivität von etwa 4 KNPU/g) von 1:2 bis 10:1 umfaßt, wobei das Percarbonat eine Beschichtung aufweist, bestehend aus a) Mischsalz aus Alkalimetallsulfat und -carbonat, oder (b) Natriumsilikat mit einem SiO2:Na2O-Verhältnis von 1,6:1 bis 2,8:1, oder (c) Magnesiumsilikat.
  2. Zusammensetzung nach Anspruch 1, wobei das Gewichtsverhältnis von Percarbonat zu Amylase 1:2 bis 60:1 beträgt.
  3. Zusammensetzung nach Anspruch 2, wobei das Gewichtsverhältnis von Percarbonat zu Amylase 20:1 bis 40:1 beträgt.
  4. Zusammensetzung nach den Ansprüchen 1-3, wobei das Percarbonat eine durchschnittliche Teilchengröße von 250 bis 900 µm aufweist.
  5. Zusammensetzung nach den Ansprüchen 1-4, bei der es sich um eine Wäschewaschmittelzusammensetzung handelt, welche einen Builder, 3 bis 30 Gew.-% Percarbonat und 0,1 bis 1% Amylase enthält.
  6. Zusammensetzung nach den Ansprüchen 1-4, bei der es sich um eine Zusammensetzung zum maschinellen Geschirrspülen handelt, enthaltend einen Builder, 3 bis 30 Gew.-% Percarbonat und 0,1 bis 1% Amylase.
  7. Zusammensetzung nach den Ansprüchen 1-4, bei der es sich um ein Wäschewaschmitteladditiv handelt, das 20 bis 80% des Percarbonats und 0,1 bis 2% Amylase enthält.
  8. Verfahren zur Entfernung von Stärke enthaltenden Flecken aus Textilien, wobei die Textilien mit einer Waschmittelzusammensetzung gemäß Anspruch 5 behandelt werden.
  9. Verfahren zum Entfernen von Blutflecken aus Textilien, wobei die Textilien mit einer Waschmittelzusammensetzung gemäß Anspruch 5 behandelt werden.
  10. Verfahren zum Entfernen von teilchenförmigen Flecken aus Textilien, wobei die Textilien mit einer Waschmittelzusammensetzung gemäß Anspruch 5 behandelt werden.
  11. Verfahren zum Entfernen von Mucin oder Mucin-Protein enthaltenden Flecken aus Textilien, wobei die Textilien mit einer Waschmittelzusammensetzung gemäß Anspruch 5 behandelt werden.
  12. Verfahren nach den Ansprüchen 8, 9, 10 oder 11, wobei die Waschmittelzusammensetzung zusammen mit der zu waschenden Wäsche in eine wiederverwendbare Dispensiervorrichtung gegeben wird.
EP95905359A 1993-12-21 1994-12-15 Percarbonat , amylase und protease enthaltende waschmittelzusammensetzungen Expired - Lifetime EP0736085B2 (de)

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Applications Claiming Priority (6)

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EP93203611A EP0628624A1 (de) 1993-06-09 1993-12-21 Protease enthaltende Waschmittelzusammensetzungen mit Zusätzen zur Verhinderung der Farbstoffübertragung
EP93203611 1993-12-21
EP94870041 1994-03-04
EP94870041 1994-03-04
EP95905359A EP0736085B2 (de) 1993-12-21 1994-12-15 Percarbonat , amylase und protease enthaltende waschmittelzusammensetzungen
PCT/US1994/014294 WO1995017495A1 (en) 1993-12-21 1994-12-15 Detergent compositions containing percarbonate and amylase

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EP0736085A4 EP0736085A4 (de) 1997-03-19
EP0736085B1 EP0736085B1 (de) 2002-02-20
EP0736085B2 true EP0736085B2 (de) 2009-12-16

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WO1996026261A1 (en) * 1995-02-18 1996-08-29 Albright & Wilson Uk Limited Enzyme detergents
CZ283797A3 (cs) * 1995-03-11 1998-02-18 The Procter & Gamble Company Čistící prostředek obsahující polymerní karboxylovou sloučeninu, chelatující činidlo a enzym amylasu
RU2182164C2 (ru) * 1996-03-27 2002-05-10 Солвей Интерокс (Сосьете Аноним) Перкарбонат натрия, способ выбора перкарбоната натрия, композиция моющего средства
EP0896998A1 (de) * 1997-08-14 1999-02-17 The Procter & Gamble Company Wäschewaschmittelzusammensetzungen mit Polysaccharidgummiabbauendem Enzym
DE19824688A1 (de) * 1998-06-03 1999-12-09 Henkel Kgaa Amylase und Percarbonat enthaltende Wasch- und Reinigungsmittel
US6420331B1 (en) 1998-06-10 2002-07-16 Procter & Gamble Company Detergent compositions comprising a mannanase and a bleach system
DE50107849D1 (de) 2000-07-28 2005-12-01 Henkel Kgaa Neues amylolytisches enzym aus bacillus sp. a 7-7 (dsm 12368) sowie wasch- und reinigungsmittel mit diesem neuen amylolytischen enzym
DE10160319B4 (de) * 2001-12-07 2008-05-15 Henkel Kgaa Tensidgranulate und Verfahren zur Herstellung von Tensidgranulaten
ITBO20030710A1 (it) * 2003-11-24 2005-05-25 Gd Spa Macchina e metodo per realizzare una confezione ripiegando
TR201810838T4 (tr) * 2007-06-22 2018-08-27 Unilever Nv Granüllü enzimatik deterjan bileşimleri.
JP5431896B2 (ja) * 2009-12-11 2014-03-05 花王株式会社 漂白剤組成物
DE102011005697A1 (de) * 2011-03-17 2012-09-20 Henkel Ag & Co. Kgaa Geschirspülmittel

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GB1466799A (en) † 1973-04-20 1977-03-09 Interox Particulate peroxygen compounds
WO1992006163A1 (en) † 1990-10-06 1992-04-16 The Procter & Gamble Company Detergent compositions
WO1993004159A1 (en) † 1991-08-16 1993-03-04 Kommentus Ecogreen Aktiebolag Stabilizing percarbonate in detergents
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EP0635566A1 (de) † 1993-07-23 1995-01-25 The Procter & Gamble Company Die Farbstoffübertragung hemmende Waschmittelzusammensetzungen
EP0651052A1 (de) † 1993-11-03 1995-05-03 The Procter & Gamble Company Waschmittelzusammensetzungen für Geschirrspülmaschinen
EP0651053A1 (de) † 1993-11-03 1995-05-03 The Procter & Gamble Company Detergenszusammensetzungen für Wäsche
EP0710714A2 (de) † 1994-11-05 1996-05-08 The Procter & Gamble Company Bleichmittelzusammensetzungen

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US3637339A (en) † 1968-03-07 1972-01-25 Frederick William Gray Stain removal
GB1466799A (en) † 1973-04-20 1977-03-09 Interox Particulate peroxygen compounds
US5219549A (en) † 1990-05-25 1993-06-15 Mitsubishi Gas Chemical Company, Inc. Bleaching detergent composition
WO1992006163A1 (en) † 1990-10-06 1992-04-16 The Procter & Gamble Company Detergent compositions
WO1993004159A1 (en) † 1991-08-16 1993-03-04 Kommentus Ecogreen Aktiebolag Stabilizing percarbonate in detergents
WO1994001521A1 (en) † 1992-07-14 1994-01-20 The Procter & Gamble Company Process of dispensing a high bulk density percarbonate-containing laundry detergent
EP0635566A1 (de) † 1993-07-23 1995-01-25 The Procter & Gamble Company Die Farbstoffübertragung hemmende Waschmittelzusammensetzungen
EP0651052A1 (de) † 1993-11-03 1995-05-03 The Procter & Gamble Company Waschmittelzusammensetzungen für Geschirrspülmaschinen
EP0651053A1 (de) † 1993-11-03 1995-05-03 The Procter & Gamble Company Detergenszusammensetzungen für Wäsche
EP0710714A2 (de) † 1994-11-05 1996-05-08 The Procter & Gamble Company Bleichmittelzusammensetzungen

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DE69429930D1 (de) 2002-03-28
JPH09507509A (ja) 1997-07-29
EP0736085B1 (de) 2002-02-20
CN1352235A (zh) 2002-06-05
WO1995017495A1 (en) 1995-06-29
CA2176697C (en) 2000-01-11
ES2173173T3 (es) 2002-10-16
PH11994049605B1 (en) 2001-06-19
CA2176697A1 (en) 1995-06-29
EP0736085A4 (de) 1997-03-19
DE69429930T3 (de) 2010-07-08
DE69429930T2 (de) 2002-11-07
EP0736085A1 (de) 1996-10-09
CN1138346A (zh) 1996-12-18

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Effective date: 20021111

Opponent name: UNILEVER N.V.

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R26 Opposition filed (corrected)

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Opponent name: UNILEVER N.V.

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Opponent name: HENKEL AG & CO. KGAA

Opponent name: UNILEVER N.V.

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