WO1995004808A1 - Composition pour laver la vaisselle a la main comprenant des enzymes lipases - Google Patents

Composition pour laver la vaisselle a la main comprenant des enzymes lipases Download PDF

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Publication number
WO1995004808A1
WO1995004808A1 PCT/US1994/008415 US9408415W WO9504808A1 WO 1995004808 A1 WO1995004808 A1 WO 1995004808A1 US 9408415 W US9408415 W US 9408415W WO 9504808 A1 WO9504808 A1 WO 9504808A1
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alkyl
composition
surfactant
compositions
weight
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PCT/US1994/008415
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English (en)
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Alan Scott Goldstein
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The Procter & Gamble Company
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Priority to EP94926703A priority Critical patent/EP0712438A4/fr
Priority to AU75148/94A priority patent/AU7514894A/en
Priority to JP7506437A priority patent/JPH09501960A/ja
Publication of WO1995004808A1 publication Critical patent/WO1995004808A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0094—High foaming compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/003—Colloidal solutions, e.g. gels; Thixotropic solutions or pastes
    • 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
    • C11D3/38627—Preparations containing enzymes, e.g. protease or amylase containing lipase

Definitions

  • the formulator of a manual dishwashing detergent composition faces the challenge of deriving a formulation which meets a number of distinct consumer relevant performance demands.
  • such a composition should be effective at removing soils from dirty "dishes" when used in a manual dishwashing process.
  • the term "dishes” is used herein in a generic sense, and encompases essentially any items which may be found in a dishwashing load, including chinaware, glassware, plasticware, hollowware and cutlery, including silverware.
  • soils encountered in dishwashing will largely but not exclusively be food based. Particularly difficult soils to remove would include greasy soils, burnt on food soils, dried on food soils, highly coloured soils derived from eg : highly coloured vegetables such as beetroot and tomato, as well as non-food soils such as lipstick on the rims of glasses or nicotine stains on saucers which have been used as ashtrays.
  • the dishwashing detergent should act such as to suspend these soils in the wash solution and thus prevent their redeposition onto the dishes, or onto the surface of the sink.
  • the manual dishwashing composition should be high sudsing and the sudsing should persist throughout the washing process.
  • the sudsing is used as an indicator by the person doing the washing up that the wash solution still contains active detergent ingredients. When the sudsing subsides the sink will generally be emptied and a fresh wash solution prepared.
  • the persistence of suds throughout the washing process is measured in the industry by various suds mileage indices.
  • the manual dishwashing composition should also be mild to the skin, and particularly to the hands. That is, it should not cause skin dryness, chapping or rougness when in contact with the skin. Such skin dryness, chapping or roughness largely results from the removal of natural oils from the skin.
  • the manual dishwashing composition should desirably be effective at removing grease from plates but not natural oils from the skin.
  • compositions are formulated in a distinct way from, for example, machine dishwashing, laundry, and hard-surface cleaner compositions.
  • Manual dishwashing compositions are usually unbuilt, and may contain added levels of Ca and Mg to aid cleaning performance. Laundry and automatic dishwashing compositions typically contain high levels of builder.
  • Manual dishwashing compositions typically contain no bleaching components, which are by contrast common components of laundry, machine dishwashing and hard-surface cleaner compositions.
  • Manual dishwashing detergent typically contain high levels of high-sudsing surfactant and often suds booster.
  • Machine laundry and dishwashing compositions are desirably low foaming and typically contain lower levels of surfactant.
  • Manual dishwashing compositions are formulated to perform well at near neutral pH.
  • Machine dishwashing and laundry compositions are typically alkaline with a pH of usually 9-11
  • hard-surface cleaner compositions are often acidic with a pH of less than 6.
  • the key active component of a manual dishwashing composition is most usually a surfactant system, which will typically comprise from 5 to 80% by weight of the composition.
  • the surfactant system has a primary soil removal purpose, and also acts so as to suspend the soils in solution and prevent redeposition of these soils.
  • the surfactant system should be effective at removing and suspending greasy soils.
  • washing-up liquid is essentially just a surfactant solution with certain other minor components. This perception seems exemplified by a recent Economist Intelligence Unit market report on dishwashing products to be found in EIU, Retail Business No 409, March 1992 where level of surfactant in a product is employed essentially as an indicator of "quality" of the product.
  • Enzymes are common components of laundry and machine dishwashing compositions. Amylolytic and proteolytic enzymes are common components of such compositions. Enzymes are not commonly recognized to be of use in manual dishwashing compositions.
  • Upolytic enzymes act to hydrolyse fats or oils, which comprise esters of glycerol and fatty acids, into these glycerol and fatty acid components.
  • upolytic enzymes in laundry and machine dishwashing compositions, most particularly as a coenzyme in combination with, for example amylolytic and proteolytic enzymes.
  • lipolytic enzyme is a particularly useful component of a manual dishwashing composition containing certain surfactant systems which act such as to stabilize the enzyme when formulated in liquid compositions.
  • composition containing a surfactant system and lipolytic enzyme suitable for use in a manual dishwashing process.
  • composition is high sudsing.
  • composition is in the form of a liquid or a gel.
  • composition contains no builder salts.
  • composition contains no bleaching components.
  • said compositon contains from 5% to 80% by weight of said surfactant system, wherein the surfactant system comprises surfactant selected from nonionic, anionic, cationic, zwitterionic, ampholytic and amphoteric surfactants.
  • a 1% by weight solution of said composition has a pH of from 6 to 9.
  • Said composition can be formulated to contain no other enzyme components.
  • the first essential component of the compositions in accordance with the invention is lipolytic enzyme (lipase) which is preferably present at levels of active lipolytic enzyme of from 0.001% to 2% by weight, more preferably 0.01% to 1% by weight, most preferably from 0.05% to 0.5% by weight of the compositions.
  • lipolytic enzyme lipase
  • the lipase is preferably bacterial in origin being obtained, for example, from a lipase producing strain of Humicola sp.or Thermomyces sp. or Pseudomonas pseudoalcaligenes or Pseudomas fluorescens. Lipase from chemically or genetically modified mutants of these strains are also included herein. Mixtures of lipase from various strains are included herein, though not preferred.
  • a preferred lipase is derived from Pseudomonas pseudoalcaligenes, which is described in Granted European Patent, EP-B-0218272.
  • Another preferred lipase herein is obtained by cloning the gene from Humicola lanuginosa and expressing the gene in Aspergillus oryza, as host, as described in European Patent Application, EP-A-0258 068, which is commercially available from Novo Industri A/S, Bagsvaerd, Denmark, under the trade name Lipolase. This lipase is also described in U.S. Patent 4,810,414, Huge-Jensen et al, issued March 7, 1989.
  • Lipases herein are preferably compatible with surfactants. They are preferably stable in the present compositions and improve cleaning when they are included in the present compositions.
  • Suitable lipases include those which show a positive immunological cross- reaction with the antibody of the lipase produced by Pseudomonas flluorescens. This lipases described in Japanese Patent Application 53-20487, laid open February 24, 1987. It is available under the trade name Lipase P Amano. A method for testing immunological cross-reaction with Amano P antibody is described in U.S. Patent 4,707,291, Thorn et al, issued November 17, 1987.
  • a lipase unit is defined as the amount of lipase which produces 1 umol of titratable butyric acid per minute in a pH stat, where pH is 7.0, temperature is 30°C, and substrate is an emulsion of ributyrin and gum arabic in the presence of Ca++ and NaCI in phosphate buffer.
  • compositions of the invention contain a surfactant system at a level of from 5 % to 80 %, preferably from 10 % to 60 %, most preferably from 15 % to 50 % by weight of the composition.
  • the surfactant system is preferably formulated to be compatible with the lipolytic enzyme. In liquid or gel compositions the surfactant system is most preferably formulated such that it promotes, or at least does not degrade, the stability of the lipolytic enzyme in these compositions.
  • the surfactant system comprises surfactant selected from nonionic, anionic, cationic, zwitterionic, ampholytic and amphoteric surfactants, and any mixtures thereof.
  • the surfactant system comprises from 5% to 90% by weight, more preferably from 30% to 70% by weight of the surfactant system of anionic surfactant, and from 5% to 60% by weight, more preferably from 15% to 50% by weight of the surfactant system of nonionic surfactant.
  • the anionic surfactant may be essentially any anionic surfactant, including anionic sulfate, sulfonate or carboxylate surfactant.
  • the anionic sulfate surfactant may be any organic sulfate surfactant. It is preferably selected from the group consisting of C10-C16 a'kyl sulfate which has been ethoxylated with from about 0.5 to about 20 moles of ethylene oxide per molecule, C9-C17 acyl-N-(C ⁇
  • the anionic sulfate surfactant is a C10-C16 alkyl sulfate which has been ethoxylated with from about 0.5 to about 20, preferably from about 0.5 to about 12, moles of ethylene oxide per molecule.
  • Alkyl ethoxy sulfate surfactants comprises a primary alkyl ethoxy sulfate derived from the condensation product of a C ⁇ o-C ⁇
  • the C10-C16 alcohol itself is commercially available.
  • C12-C14 alkyl sulfate which has been ethoxylated with from about 3 to about 10 moles of ethylene oxide per molecule is preferred.
  • Blends can be made of material having different degrees of ethoxylation and/or different ethoxylate distributions arising from the specific ethoxylation techniques employed and subsequent processing steps such as distillation.
  • Anionic sulfate surfactants include the C9-C17 acyl-N-(C-
  • the counterion for the anionic sulfate surfactant component is preferably selected from calcium, sodium, potassium, magnesium, ammonium, or alkanol- ammonium, and mixtures thereof, with calcium and magnesium being preferred for cleaning and sudsing, respectively.
  • Anionic sulfonate surfactant Anionic sulfonate surfactant
  • Anionic sulfonate surfactants suitable for use herein include essentially any sulfonate surfactants including, for example, the salts (eg : alkali metal salts) of C9-C20 linear alkylbenzene sulfonates, C8-C22 primary or secondary alkane sulfonates, C8-C24 olefin sulfonates, sulfonated polycarboxylic acids, alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfonates, paraffin sulfonates, and any mixtures thereof.
  • the salts eg : alkali metal salts
  • C9-C20 linear alkylbenzene sulfonates C8-C22 primary or secondary alkane sulfonates
  • C8-C24 olefin sulfonates
  • Anionic alkyl ethoxy carboxvlate surfactant Anionic alkyl ethoxy carboxvlate surfactant
  • Alkyl ethoxy carboxylates suitable for use herein include those with the fomula RO(CH2CH2 ⁇ ) x CH2C00 _ M + wherein R is a C ⁇ o C-je alkyl group, x ranges from O to 10, and the ethoxylate distribution is such that, on a weight basis, the amount of material where x is 0 is less than about 20 %, preferably less than about 15 %, most preferably less than about 10 %, and the amount of material where x is greater than 7, is less than about 25 %, preferably less than about 15 %, most preferably less than about 10 %, the average x is from about 2 to 4 when the average R is C-
  • Alkyl polyethoxy polcarboxylate surfactants suitable for use herein include those having the formula :
  • R is a CQ to C18 alkyl group, x is from 1 to 25, R- and R2 are selected from the group consisting of hydrogen, methyl acid radical, succinic acid radical, hydroxysuccinic acid radical, and mixtures thereof, wherein at least one R ⁇ l or R2 is a succinic acid radical or hydroxysuccinic acid radical, and R3 is selected from the group consisting of hydrogen, substituted or unsubstituted hydrocarbon having between 1 and 8 carbon atoms, and mixtures thereof.
  • Secondary soap surfactants (aka “alkyl carboxyl surfactants”) useful herein are those which contain a carboxyl unit connected to a secondary carbon. It is to be understood herein that the secondary carbon can be in a ring structure, e.g. as in p-octyl benzoic acid, or as in alkyl-substituted cyclohexyl carboxylates.
  • the secondary soap surfactants should contain no ether linkages, no ester linkages and no hydroxyl groups. There should be no nitrogen atoms in the head-group (amphiphilic portion).
  • the secondary soap surfactants usually contain 11-13 total carbon atoms, although slightly more (e.g., about 14-16) can be tolerated if the soap contains a ring structure, as noted above, e.g. p-octyl benzoic acid.
  • a highly preferred class of secondary soaps useful herein comprises the secondary carboxyl materials of the formula R3 CH(R 4 )COOM, wherein R 3 is CH3(CH2) X and R 4 is CH3(CH2)y, wherein y can be O or an integer from 1 to 4, x is an integer from 4 to 10 and the sum of (x + y) is 6-10, preferably 7-9, most preferably 8.
  • Another class of secondary soaps useful herein comprises those carboxyl compounds wherein the carboxyl substituent is on a ring hydrocarbyl unit, i.e., secondary soaps of the formula R 5 -R 6 -COOM, wherein R 5 is C7- C ⁇ ⁇ o, preferably C ⁇ -Cg, alkyl or alkenyl and R 6 is a ring structure, such as benzene, cyclopentane and cyclohexane. (Note : R 5 can be in the ortho, meta or para position relative to the carboxyl on the ring.)
  • Still another class of secondary soaps comprises secondary carboxyl compounds of the formula CH3(CHR)k-(CH2) m -( CHR )n- CH(COOM)(CHR) 0 -(CH2)p-(CHR) q -CH3, wherein each R is C-1-C4 alkyl, wherein k, n, o, q are integers in the range of 0-8, provided that the total number of carbon atoms (including the carboxylate) is in the range of 10 to 18.
  • the species M can be any suitable, especially water-solubilizing, counterion, e.g., H, alkali metal, alkaline earth metal, ammonium, alkanolammonium, di- and tri- alkanolammonium, and C-
  • Sodium is convenient, as is diethanolammonium.
  • Preferred secondary soap surfactants for use herein are water-soluble members selected from the group consisting of the water-soluble salts of 2- methyl-1-undecanoic acid, 2-ethyl-1-decanoic acid, 2-propyl-1-nonanoic acid, 2- butyl-1-octanoic acid and 2-pentyl-1-heptanoic acid.
  • anionic surfactants useful for detersive purposes can also be included in the compositions hereof. These can include salts (including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts) of soap, fatty oleyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, alkyl phosphates, isethionates such as the acyl isethionates, N-acyl taurates, fatty acid amides of methyl tauride, alkyl succinates and sulfosuccinates, monoesters of sulfosuccinate (especially saturated and unsaturated ⁇ -C- j g monoesters) diesters of sulfosuccinate (especially saturated and unsaturated Cg-C 14 diesters), N-acyl sarcosinates, sulfates of alkylpolysaccharides such as the
  • 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.
  • Suitable nonionic detergent surfactants are generally disclosed in U.S. Patent 3,929,678, Laughlin et al., issued December 30, 1975, at column 13, line 14 through column 16, line 6, incorporated herein by reference. Exemplary, non- limiting classes of useful nonionic surfactants are listed below.
  • Nonionic polyhydroxv fattv acid amide surfactant Nonionic polyhydroxv fattv acid amide surfactant
  • Polyhydroxy fatty acid amides suitable for use herein are those having the structural formula :
  • R1 is H, C1-C4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl, or a mixture thereof, preferable C1-C4 alkyl, more preferably C-j or C2 alkyl, most preferably C ⁇ alkyl (i.e., methyl); and R2 is a C5-C31 hydrocarbyl, preferably straight-chain C7-C19 alkyl or alkenyl, more preferably straight-chain C9-C17 alkyl or alkenyl, most preferably straight-chain C11-C17 alkyl or alkenyl, or mixture thereof; and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof.
  • Z preferably will be derived from a reducing sugar in a reductive amination reaction; more preferably Z is a glycityl.
  • Suitable reducing sugars include glucose, fructose, maltose, lactose, galactose, mannose, and xylose.
  • high dextrose corn syrup, high fructose com syrup, and high maltose corn syrup can be utilized as well as the individual sugars listed above. These corn syrups may yield a mix of sugar components for Z. It should be understood that it is by no means intended to exclude other suitable raw materials.
  • Z preferably will be selected from the group consisting of -CH2-(CHOH) n -CH2-OH2, -CH(CH2 ⁇ H)- (CHOH) n -, -CH2OH, -CH 2 -(CHOH)2(CHOR , )(CHOH)-CH2 ⁇ H, where n is an integer from 3 to 5, inclusive, and R' is H or a cyclic or aliphatic monosaccharide, and alkoxylate derivative thereof. Most preferred are glycityls wherein n is 4, particularly -CH2-(CHOH)4-CH2 ⁇ H.
  • R ⁇ can be, for example, N-methyl, N-ethyl, N-propyl, N- isopropyl, N-butyl, N-2-hydroxy ethyl, or N-2-hydroxy propyl.
  • R2-CO-N ⁇ can be, for example, cocamide, stearamide, oleamide, lauramide, myristamide, capricamide, palmitamide, tallowamide, etc.
  • Z can be 1-deoxyglucityl, 2-deoxyfructityl, 1-deoxymaltityl, 1-deoxylactityl, 1- deoxygalactityl, 1-deoxymannityl, 1-deoxymaltotriotityl, etc.
  • the most preferred polyhydroxy fatty acid amide has the general formula :
  • R 2 is a straight chain C-
  • polyethylene, polypropylene, and polybutylene oxide condensates of alkyl phenols are suitable for use herein.
  • the polyethylene oxide condensates are preferred.
  • These compounds include the condensation products of alkyl phenols having an alkyl group containing from about 6 to about 12 carbon atoms in either a straight chain or branched chain configuration with the alkylene oxide, in a preferred embodiment, the ethylene oxide is present in an amount equal to from about 5 to about 25 moles of ethylene oxide per mole of alkyl phenol.
  • nonionic surfactants of this type include IgepalTM CO-630, marketed by the GAF Co ⁇ oration; and TritonTM ⁇ _n4, ⁇ .100, and X-102, all marketed by the Rohm & Haas Company.
  • the alkyl ethoxylate condensation products of aliphatic alcohols with from about * 1 to about 25 moles of ethylene oxide are suitable for use herein.
  • 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.
  • Particularly preferred are the condensation products of alcohols having an alkyl group containing from 10 to 20 carbon atoms with from about 2 to about 10 moles of ethylene oxide per mole of alcohol.
  • Most preferred are the condensation products of alcohols having an alkyl group containing from 10 to 14 carbon atoms with from about 6 to about 10 moles of ethylene oxide per mole of alcohol.
  • nonionic surfactants of this type include TergitolTM 15-S-9 (the condensation product of C-
  • the condensation products of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol are suitable for use herein.
  • the hydrophobic portion of these compounds preferably has a molecular weight of from about 1500 to about 1800 and exhibits water insolubility.
  • the addition of polyoxyethylene moieties of 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 about 40 moles of ethylene oxide.
  • Examples of compounds of this type include certain of the commercially-available PluronicTM surfactants, marketed by BASF.
  • the condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylenediamine are suitable for use herein.
  • 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 about 2500 to about 3000.
  • This hydrophobic moiety is condensed with ethylene oxide to the extent that the condensation product contains from about 40% to about 80% by weight of polyoxyethylene and has a molecular weight of from about 5,000 to about 11 ,000.
  • Examples of this type of nonionic surfactant include certain of the commercially available TetronicTM compounds, marketed by BASF.
  • Suitable alkylpolysaccharides for use herein are disclosed in U.S. Patent 4,565,647, Llenado, issued January 21, 1986, having a hydrophobic group containing from about 6 to about 30 carbon atoms, preferably from about 10 to about 16 carbon atoms and a polysaccharide, e.g., a polyglycoside, hydrophilic group containng from about 1.3 to about 10, preferably from about 1.3 to about 3, most preferably from about 1.3 to about 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.
  • the hydrophobic group is attached at the 2-, 3-, 4-, etc. positions thus giving a glucose or galactose as opposed to a giucoside 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 about 3 hydroxyl groups and/or the polyalkyleneoxide chain can contain up to about 10, preferably less than 5, alkyleneoxide moieties.
  • Suitable alkyl polysaccharides are octyl, nonyldecyl, undecyldodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, and octadecyl, di-, tri-, tetra-, penta-, and hexaglucosides, galatoses.
  • 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 0(C n H 2 nO)t(glycosyl) x
  • R2 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, x is from 0 to 10, preferably from about 1.3 to about 3, most preferably from about 1.3 to about 2.7, t is from 0 to 10.
  • the glycosyl is preferably derived from glucose. To prepare these compounds, the alcohol or alkylpolyethoxy alcohol is formed first and then reacted with glucose, or a source of glucose, to form the giucoside (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 predominantly the 2-position.
  • Nonionic fatty acid amide surfactant Nonionic fatty acid amide surfactant
  • Fatty acid amide surfactants suitable for use herein are those having the formula: R 6 -C -N (R 7 )2
  • R 6 is an alkyl group containing from 7 to 21, preferably from 9 to 17 carbon atoms and each R? is selected from the group consisting of hydrogen, C1-C4 alkyl, C1-C4 hydroxyalkyl, and -(C2H4 ⁇ ) x H, where x is in the range of from 1 to 3.
  • Ampholytic surfactants can be incorporated into the detergent compositions herein. 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 chain or branched.
  • One of the aliphatic substituents contains at least about 8 carbon atoms, typically from about 8 to about 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.
  • Suitable amphoteric surfactants for use herein include the alkyl amphocarboxylic acids of the formula
  • R is a C ⁇ -Ci ⁇ alkyl group
  • Rj is of the general formula
  • R 1 is a (CH2) x COOM or CH2CH2O and x is 1 or 2 and M is preferably chosen from alkali metal, alkaline earth metal, ammonium, mono-, di- , and tri-ethanolammonium, most preferably from sodium, potassium, ammonium and mixtures thereof with magnesium ions.
  • the preferred R alkyl chain length is a C-JQ to C14 alkyl group.
  • a preferred amphocarboxylic acid is produced from fatty imidazolines wherein the dicarboxylic acid functionality of the amphodicarboxylic acid is diacetic acid and/or dipropionic acid.
  • Zwitterionic surfactants can also be incorporated into the detergent compositions herein. 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 (herein incorporated by reference) for examples of zwitterionic surfactants.
  • Ampholytic, amphoteric and zwitterionic surfactants are generally used in combination with one or more anionic and/or nonionic surfactants.
  • compositions of the present invention preferebly further comprise from 1% to 20%, preferably from 2% to 20% by weight of a suds enhancing agent selected from the group consisting of amine oxides, betaines, sultaines, complex betaines, and certain nonionics.
  • a suds enhancing agent selected from the group consisting of amine oxides, betaines, sultaines, complex betaines, and certain nonionics.
  • a suds enhancing agent selected from the group consisting of amine oxides, betaines, sultaines, complex betaines, and certain nonionics.
  • Amine oxides useful in the present invention include those compounds having the formula :
  • R 3 is selected from an alkyl, hydroxyalkyl, acylamidopropoyl and alkyl phenyl group, or mixtures thereof, containing from 8 to 26 carbon atoms, preferably 8 to 16 carbon atoms;
  • R 4 is an alkylene or hydroxyalkylene group containing from 2 to 3 carbon atoms, preferably 2 carbon atoms, or mixtures thereof;
  • x is from 0 to 3, preferably 0;
  • each R 5 is an alkyl or hydyroxyalkyl group containing from 1 to 3, preferably from 1 to 2 carbon atoms, or a polyethylene oxide group containing from 1 to 3, preferable 1, ethylene oxide groups.
  • the R5 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 ⁇ o-Cl8 alkyl dimethyl amine oxides and C8-C12 alkoxy ethyl dihydroxyethyl amine oxides.
  • examples of such materials include dimethyloctylamine oxide, diethyldecylamine oxide, bis-(2-hydroxyethyl)dodecylamine oxide, dimethyldodecylamine oxide, dipropyltetradecylamine oxide, methylethylhexadecylamine oxide, dodecylamidopropyl dimethylamine oxide and dimethyl-2- hydroxyoctadecylamine oxide.
  • C ⁇ Q-C- Q alkyl dimethylamine oxide and C ⁇ o-18 acylamido alkyl dimethylamine oxide.
  • the betaines useful in the present invention are those compounds having the formula R(R')2N + R 2 COO" wherein R is a CQ-C-]Q hydrocarbyl group, preferably a C10-C16 alkyl group or C ⁇ JO-16 acylamido alkyl group, each R 1 is typically C1-C3 alkyl, preferably methyl.m and R 2 is a C1-C5 hydrocarbyl group, preferably a C1-C3 alkylene group, more preferably a C1-C2 alkylene group.
  • betaines examples include coconut acylamidopropyldimethyl betaine; hexadecyl dimethyl betaine; C «
  • Preferred betaines are C12-I8 dimethyl-ammonio hexanoate and the C- ⁇ o-18 acylamidopropane (or ethane) dimethyl (or diethyl) betaines.
  • the sultaines useful in the present invention are those compounds having the formula (R(R 1 )2N + R 2 S ⁇ 3 _ wherein R is a CQ-C- ⁇ Q hydrocarbyl group, preferably a C10-C16 alk y' 9 rou P.
  • each R 1 is typically C1-C3 alkyl, preferably methyl
  • R 2 is a C-j-C ⁇ hydrocarbyl group, preferably a C1-C3 alkylene or, preferably, hydroxyalkylene group.
  • Suitable sultaines include C12-C14 dimethylammonio-2- hydroxypropyl sulfonate, C-J2-14 amido propyl ammonio-2-hydroxypropyl sultaine, C12-14 dihydroxyethylammonio propane sulfonate, and C-
  • R is a hydrocarbon group having from 7 to 22 carbon atoms
  • A is the group (C(O))
  • n is 0 or 1
  • is hydrogen or a lower alkyl group
  • x is 2 or 3
  • y is an integer of 0 to 4
  • Q is the group -R2COOM wherein R2 is an alkylene group having from 1 to 6 carbon atoms and M is hydrogen or an ion from the groups alkali metals, alkaline earth metals, ammonium and substituted ammonium and B is hydrogen or a group Q as defined.
  • Preferred amides are C8-C20 alkyl mono- or di-C2-C3 alkanolamides, especially monoethanolamides, diethanolamides, and isopropanolamides.
  • Preferred suds enhancing agents are C10-I8 acyl amide alkyl dimethyl amine oxides, betaines, sultaines, condensation products of aliphatic alcohols with ethylene oxides, and alkylpolysaccharides, and mixtures thereof. Hydrotropes
  • a hydrotrope is typically added to the compositions of the present invention, and may be present at levels of from 0.5% to 10%, preferably from 1% to 5%, by weight.
  • Useful hydrotropes include sodium, potassium, and ammonium xylene sulfonates, sodium, potassium, and ammonium toluene sulfonate, sodium potassium and ammonium cumene sulfonate, and mixtures thereof.
  • poiycarboxylates Other compounds useful as hydrotropes herein include poiycarboxylates. Some poiycarboxylates have calcium chelating properties as well as hydrotropic properties.
  • Particularly useful hydrotropes are alkylpolyethoxy polycarboxylate surfactants of the type as previously described herein.
  • alkylpolyethoxy polycarboxylate which can be employed herein is POLY-TERGENT C, Olin Co ⁇ oration, Cheshire, CT.
  • R is a C ⁇ to C ⁇
  • x is from 1 to 2
  • M is preferably chosen from alkali metal, alkaline earth metal, ammonium, mono-, di-, and tri- ethanolammonium, most preferably from sodium, potassium, ammonium, and mixtures thereof with magnesium ions.
  • the preferred alkyl chain length (R) is a C ⁇ o to Cf4 alkyl group and the dicarboxylic acid functionally is diacetic acid and/or dipropionic acid.
  • a suitable example of an alkyl amphodicarboxylic acid is the amphoteric surfactant Miranol R 2CM Cone. manufactured by Miranol, Inc., Dayton, NJ.
  • compositions of the present invention are particularly useful when formulated to contain a lime soap dispersant compound which acts to disperse any insoluble lime soap salts which may be formed between the fatty acids produced by the lipolytic hydrolysis of fats/oils and calcium ions in the wash soluble, thereby preventing the deposition of these salts as spots or films on the articles in the wash, or as an unseemly ring around the rim of the sink.
  • Certain lime soap dispersant compounds may also provide improved product stability particularly where the product is formulated as a liquid product containing calcium ions.
  • a lime soap dispersant compound herein is defined as a compound, which has a lime soap dispersing power (LSDP), as defined hereinafter of no more than 8, preferably no more than 7, most preferably no more than 6.
  • the lime soap dispersant compound is typically present at a level of from 0.1% to 40% by weight, more preferably 1% to 20% by weight, most preferably from 2% to 10% • by weight of the compositions.
  • a lime soap dispersant is a material that prevents the precipitation of alkali metal, ammonium or amine salts of fatty acids by calcium or magnesium ions.
  • a numerical measure of the effectiveness of a lime soap dispersant is given by the lime soap dispersing power (LSDP) which is determined using the lime soap dispersion test as described in an article by H.C. Borghetty and C.A. Bergman, J. Am. Oil. Chem. Soc, volume 27, pages 88-90, (1950).
  • This lime soap dispersion test method is widely used by practitioners in this art field being referred to , for example, in the following review articles; W.N. Linfield, Surfactant Science Series, Volume 7, p3; W.N. Linfield, Tenside Surf. Det.
  • test tube The contents of the test tube are then visually inspected to check if the lime soap deposits are still intact or whether they have been dispersed into the solution.
  • the test procedure is repeated using different amounts of dispersing agent solution until the minimum amount of dispersing agent solution which will cause dispersion of the lime soap deposits is obtained.
  • the lime soap dispersing power is then obtained as:
  • a material with a lower LSDP is a more effective lime soap dispersant than one with a higher LSDP.
  • compositions containing poiyhydroxy fatty acid amide may be included in the detergent compositions herein. It has been found for compositions containing poiyhydroxy fatty acid amide that the presence of calcium greatly improves the cleaning of greasy soils. This is especially true when the compositions are used in softened water, which contains few divalent ions.
  • the calcium ions can, for example, be added as a chloride, hydroxide, oxide, formate or acetate, or nitrate salt.
  • the calcium can be added as a calcium oxide or calcium hydroxide slurry in water to neutralise the acid.
  • the calcium ions may be present in the compositions as salts.
  • the amount of calcium ions present in compositions of the invention may be dependent upon the amount of total anionic surfactant present herein.
  • the molar ratio of calcium ions to total anionic surfactant is preferably from 1 :0.1 to 1 :25, more preferably from 1:2 to 1:10, for compositions of the invention.
  • Malic or maleic acid or certain lime soap dispersant compounds may be added to a composition formulated to contain calcium to provide good product stability, and in particular to prevent the precipitation of insoluble calcium salts.
  • Malic or maleic acid may, where calcium is present, preferably be added at levels of from 0.05% to 10% of the composition and a molar ratio with calcium of from 0.01:1 to 1:10.
  • magnesium ions are preferably added to the liquid detergent compositions of the invention for improved product stability, as well as improved sudsing.
  • the magnesium can be added by neutralization of the acid with a magnesium oxide or magnesium hydroxide slurry in water. Calcium can be treated similarly. This technique minimises the addition of chloride ions, which reduces corrosive properties.
  • the neutralized surfactant salts and the hydrotrope are then added to the final mixing tank and any optional ingredients are added before adjusting the pH.
  • Liquid detergent compositions in accord with the invention will preferably be formulated such that during use in aqueous cleaning operations, the wash water will have a pH of between about 5.0 and about 8.0.
  • the liquid compositions themselves preferably have a pH in a 10% solution water at 20°C of between about 5.5 and about 8.5, most preferably between about 6.8 and about 7.8.
  • Techniques for controlling pH at recommended usage levels include the use of buffers, alkali, acids, etc., and are well known to those skilled in the art. Dilute hydrochloric acid is preferred for downward pH adjustment, and sodium hydroxide for upward pH adjustment.
  • compositions herein may additionally comprise from 0.001% to 10%, preferably from 0.005% to 8%, most preferably from 0.1% to 6%, by weight of an enzyme stabilizing system.
  • the enzyme stabilizing system can be any stabilizing system which is compatible with the enzyme of the present invention.
  • Such stabilizing systems can comprise calcium ion, boric acid, propylene glycol, short chain carboxylic acid, boronic acid, polyhydroxyl compounds and mixtures thereof such as are described in U.S.
  • chlorine bleach scavengers can be added to compositions of the present invention to prevent chlorine bleach species present in many water supplies from attacking and inactivating the enzymes, especially under alkaline conditions. While chlorine levels in water may be small, typically in the range from 0.5 ppm to 1.75 ppm, the available chlorine in the total volume of water that comes in contact with the enzyme during dishwashing is usually large; accordingly, enzyme stability in-use can be problematic.
  • Suitable chlorine scavenger anions are salts containing ammonium cations. These can be selected from the group consisting of reducing materials like sulfite, bisulfite, thiosulfite, thiosulfate, iodide, etc., antioxidants like carbamate, ascorbate, etc., organic amines such as ethylenediammetetracetic acid (EDTA) or alkali metal salt thereof and monoethanolamine (MEA), and mixtures thereof.
  • reducing materials like sulfite, bisulfite, thiosulfite, thiosulfate, iodide, etc.
  • antioxidants like carbamate, ascorbate, etc.
  • organic amines such as ethylenediammetetracetic acid (EDTA) or alkali metal salt thereof and monoethanolamine (MEA), and mixtures thereof.
  • EDTA ethylenediammetetracetic acid
  • MEA monoethanolamine
  • the detergent compositions of the present invention are liquid detergent compositions.
  • These preferred liquid detergent compositions comprise from 94% to 35% by weight, preferably from 90% to 40% by weight, most preferably from 80% to 50% by weight of a liquid carrier, e.g., water, preferably a mixture of water and a C1-C4 monohydric alcohol (e.g., ethanol, propanol, isopropanol, butanol, and mixtures thereof), with ethanol being the preferred monohydric alcohol or a mixture of water and C1-C4 dihydric alcohol (e.g.: propylene glycol).
  • a liquid carrier e.g., water, preferably a mixture of water and a C1-C4 monohydric alcohol (e.g., ethanol, propanol, isopropanol, butanol, and mixtures thereof), with ethanol being the preferred monohydric alcohol or a mixture of water and C1-C4 dihydric alcohol (e.g.: propylene glycol
  • the detergent compositions of the present invention may also be in the form of a gel.
  • Such compositions are typically formulated in polyakenyl polyether and having a molecular weight of from about 750,000 to about 4,000,000.
  • polycarboxylate polymer thickeners are the Carbopol 600 series resins available from B.F. Goodrich. Especially preferred are Carbopol 616 and 617. It is believed that these resins are more highly cross-linked than the 900 series resins and have molecular weights between about 1 ,000,000 and 4,000,000. Mixtures of polycarboxylate polymers as herein described may also be used in the present invention. Particularly preferred is a mixture of Carbopol 616 and 617 series resins.
  • the polycarboxylate polymer thickener is utilized preferably with essentially no clay thickening agent.
  • the polycarboxylate polymers of the present invention are utilized with clay in the composition of the present invention, a less desirable product, in terms of phase instability, results.
  • the polycarboxylate polymer is preferably used instead of clay as a thickening/stabilizing agent in the present compositions. If the polycarboxylate polymer is used as a thickening agent in the compositions of the present invention, it is typically present at a level of from about 0.1% to about 10%, preferably from about 0.2% to about 2% by weight.
  • the thickening agents are preferably used to provide a yield value of from about 50 to about 350 and most preferably from about 75 to about 250.
  • the yield value is an indication of the shear stress at which the gel strength is exceeded and flow is initiated. It is measured herein with a Brookfield RVT model viscometer with a T-bar B spindle at 25°utilizing a Helipath.
  • compositions herein include dyes, perfumes and opacifiers.
  • Opacifiers such as Lytron (Morton Thiokol, Inc.), a modified polystyrene latex, or ethylene glycol distearate can be added, preferably as a last step. Lytron can be added directly as a dispersion with mixing. Ethylene glycol distearate can be * added in a molten state with rapid mixing to form pearlescent crystals. Opacifiers useful herein, particularly for light duty liquids, are typically present at levels from about 0.2% to about 10%, preferably from about 0.5% to about 6% by weight.
  • soiled dishes are contacted with an effective amount, typically from about 0.5 ml. to about 20 ml. (per 25 dishes being treated), preferably from about 3 ml. to about 10 ml., of the composition of the present invention.
  • an effective amount typically from about 0.5 ml. to about 20 ml. (per 25 dishes being treated), preferably from about 3 ml. to about 10 ml., of the composition of the present invention.
  • the actual amount of liquid detergent composition used will be based on the judgement of user, and will depend upon factors such as the particular product formulation of the composition, the concentration of the composition, the number of soiled dishes to be cleaned and the degree of soiling of the dishes.
  • the process by which the soiled dishes are contacted with the effective amount of the composition of the invention may be essentially any of the processes for manual dishwashing commonly known and encompasses the dilute solution in sink process, commonly used in Northern Europe and the US ; the solution in bowl process, commonly used in Latin America and Japan, and the direct application process, commonly used in Southern Europe and developing countries.
  • a liquid detergent composition In the typical dilute solution in sink process from about 3 ml. to 15 ml., preferably from 5 ml. to 10 ml. of a liquid detergent composition is combined with from 1,000 ml. to 10,000 ml., more typically from 3,000 ml. to 5,000 ml. of water in a sink having a volumetric capacity in the range of from 5,000 ml. to 20,000 ml., more typically from 10,000 ml. to 15,000 ml.
  • the detergent composition has a surfactant concentration of from about 10 % to about 60 % by weight, preferably from about 45 % to about 50 % by weight.
  • the soiled dishes are immersed in the sink containing the detergent composition and water, where they are cleaned by contacting the soiled surface of the dish with a cloth, sponge or similar article.
  • the cloth, sponge or similar article may be immersed in the detergent composition and water mixture prior to being contacted with the dish surface and is typically contacted with the dish surface for a period of time ranging from about 1 to about 10 seconds, although the actual time will vary with each application and user.
  • the contacting of the cloth, sponge or similar article to the dish surface is preferably accompanied by a concurrent scrubbing of the dish surface.
  • a detergent composition is combined with from 50 ml. to 2,000 ml., more typically from 100 ml. to 1,000 ml. of water in a bowl having a volumetric capacity in the range of from 500 ml. to 5,000 ml., more typically from 500 ml. to 2,000 ml.
  • the detergent composition has a surfactant concentration of from about 10 % to about 60 % by weight, preferably from about 15 % to about 50 % by weight.
  • the soiled dishes are cleaned by contacting the soiled surface of the dish with a cloth, sponge or similar article.
  • the cloth, sponge or similar article may be immersed in the detergent composition and water mixture prior to being contacted with the dish surface and is typically contacted with the dish surface for a period of time ranging from about 1 to about 10 seconds, although the actual time will vary with each application and user.
  • the contacting of the cloth, sponge or similar article to the dish surface is preferably accompanied by a concurrent scrubbing of the dish surface.
  • the direct application process will typically comprise as a first step immersing the soiled dishes into a water bath without any liquid dishwashing detergent.
  • a device for absorbing liquid dishwashing detergent such as a sponge, is then placed directly into a separate quantity of undiluted liquid or gel detergent composition for a period of time typically ranging from about 1 to about 5 seconds.
  • the absorbing device, and consequently the undiluted detergent composition is then contacted individually to the surface of each of the soiled dishes to remove said soiling.
  • the absorbing device is typically contacted with each dish surface for a period of time range from 1 to 10 seconds, although the actual time of application will be dependent upon factors such as the degree of soiling of the dish.
  • the contacting of the absorbing device to the dish surface is preferably accompanied by concurrent scrubbing.
  • compositions in accord with the invention were prepared.
  • compositions were prepared by mixing all of the surfactants with the exception of the glucamide.
  • the magnesium and calcium salts were then pre- dissolved into solution together with the maleic acid and added to the surfactant mixture with the remaining components. Finally the pH was trimmed to 7.3 using hydrochloric acid and the viscosity checked.

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  • 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)
  • Dispersion Chemistry (AREA)
  • Detergent Compositions (AREA)

Abstract

L'invention concerne une composition contenant un système tensio-actif et une enzyme lipolytique, appropriée pour être utilisée dans le lavage de la vaisselle à la main. De préférence, cette composition a un pouvoir moussant élevé et se présente sous la forme d'un liquide ou d'un gel. De préférence, cette composition ne contient ni sels d'adjuvants, ni composants de blanchiment.
PCT/US1994/008415 1993-08-10 1994-07-22 Composition pour laver la vaisselle a la main comprenant des enzymes lipases WO1995004808A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP94926703A EP0712438A4 (fr) 1993-08-10 1994-07-22 Composition pour laver la vaisselle a la main comprenant des enzymes lipases
AU75148/94A AU7514894A (en) 1993-08-10 1994-07-22 Manual dishwashing composition comprising lipase enzymes
JP7506437A JPH09501960A (ja) 1993-08-10 1994-07-22 リパーゼ酵素を含んでなる手作業食器洗い用組成物

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP93870163.8 1993-08-10
EP93870163 1993-08-10

Publications (1)

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WO1995004808A1 true WO1995004808A1 (fr) 1995-02-16

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JP (1) JPH09501960A (fr)
CN (1) CN1132525A (fr)
AU (1) AU7514894A (fr)
CZ (1) CZ38896A3 (fr)
HU (1) HUT73758A (fr)
WO (1) WO1995004808A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0740697B1 (fr) * 1994-01-21 2003-04-23 Buckman Laboratories International, Inc. Enzymes pour eaux de bains recreatifs
EP3074494B1 (fr) 2013-11-27 2018-04-04 Henkel AG & Co. KGaA Stabilisation de lipase dans des détergents pour la vaisselle

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106833946A (zh) * 2015-12-04 2017-06-13 深圳市芭格美生物科技有限公司 餐具生物酶清洗液及其制备方法和应用

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US4707291A (en) * 1985-06-11 1987-11-17 Lever Brothers Company Enzymatic detergent composition
US4950417A (en) * 1989-05-01 1990-08-21 Miles Inc. Detergent formulations containing alkaline lipase derived from Pseudomonas plantarii
US5089163A (en) * 1989-01-30 1992-02-18 Lever Brothers Company, Division Of Conopco, Inc. Enzymatic liquid detergent composition

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US3697451A (en) * 1969-01-02 1972-10-10 Witco Chemical Corp Stable enzyme containing liquid detergent
GB8629538D0 (en) * 1986-12-10 1987-01-21 Unilever Plc Enzymatic dishwashing & rinsing composition
US5069810A (en) * 1989-03-16 1991-12-03 Olin Corporation Cleaning composition comprising microbial lipase SD2 and sodium dodecylbenzene sulfonate
US5811382A (en) * 1991-12-20 1998-09-22 Novo Nordisk A/S Detergent compositions

Patent Citations (3)

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Publication number Priority date Publication date Assignee Title
US4707291A (en) * 1985-06-11 1987-11-17 Lever Brothers Company Enzymatic detergent composition
US5089163A (en) * 1989-01-30 1992-02-18 Lever Brothers Company, Division Of Conopco, Inc. Enzymatic liquid detergent composition
US4950417A (en) * 1989-05-01 1990-08-21 Miles Inc. Detergent formulations containing alkaline lipase derived from Pseudomonas plantarii

Non-Patent Citations (1)

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Title
See also references of EP0712438A4 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0740697B1 (fr) * 1994-01-21 2003-04-23 Buckman Laboratories International, Inc. Enzymes pour eaux de bains recreatifs
EP3074494B1 (fr) 2013-11-27 2018-04-04 Henkel AG & Co. KGaA Stabilisation de lipase dans des détergents pour la vaisselle

Also Published As

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CN1132525A (zh) 1996-10-02
EP0712438A1 (fr) 1996-05-22
HU9600311D0 (en) 1996-04-29
CZ38896A3 (en) 1996-08-14
EP0712438A4 (fr) 1999-04-14
AU7514894A (en) 1995-02-28
JPH09501960A (ja) 1997-02-25
HUT73758A (en) 1996-09-30

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