WO1996012004A1 - Compositions detergentes pour lessive comprenant une enzyme lipolytique et des amines - Google Patents

Compositions detergentes pour lessive comprenant une enzyme lipolytique et des amines Download PDF

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Publication number
WO1996012004A1
WO1996012004A1 PCT/US1995/012469 US9512469W WO9612004A1 WO 1996012004 A1 WO1996012004 A1 WO 1996012004A1 US 9512469 W US9512469 W US 9512469W WO 9612004 A1 WO9612004 A1 WO 9612004A1
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Prior art keywords
alkyl
detergent composition
amine
lipase
detergent compositions
Prior art date
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PCT/US1995/012469
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English (en)
Inventor
Dimitris Lappas
Rajan Keshav Panandiker
Thomas Wilhelm Horner
Robert Walter Boswell
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The Procter & Gamble Company
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First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=26788456&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=WO1996012004(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Priority claimed from PCT/US1994/011779 external-priority patent/WO1996012000A1/fr
Priority to DE69526360T priority Critical patent/DE69526360T2/de
Priority to CA002202505A priority patent/CA2202505C/fr
Priority to AU36869/95A priority patent/AU3686995A/en
Priority to US08/817,154 priority patent/US5935271A/en
Application filed by The Procter & Gamble Company filed Critical The Procter & Gamble Company
Priority to CZ971109A priority patent/CZ110997A3/cs
Priority to EP95934562A priority patent/EP0785981B1/fr
Priority to BR9509349A priority patent/BR9509349A/pt
Priority to JP8513248A priority patent/JPH10509468A/ja
Priority to AT95934562T priority patent/ATE215984T1/de
Publication of WO1996012004A1 publication Critical patent/WO1996012004A1/fr
Priority to MXPA/A/1997/002728A priority patent/MXPA97002728A/xx

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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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/65—Mixtures of anionic with cationic compounds
    • 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
    • C11D1/86—Mixtures of anionic, cationic, and non-ionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0026—Low foaming or foam regulating compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/30—Amines; Substituted amines ; Quaternized amines
    • 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
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/32—Amides; Substituted amides
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • 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
    • 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
    • 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
    • C11D1/38—Cationic compounds
    • C11D1/52—Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
    • C11D1/525—Carboxylic amides (R1-CO-NR2R3), where R1, R2 or R3 contain two or more hydroxy groups per alkyl group, e.g. R3 being a reducing sugar rest
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/52—Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
    • C11D1/526—Carboxylic amides (R1-CO-NR2R3), where R1, R2 or R3 are polyalkoxylated
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/52—Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
    • C11D1/528—Carboxylic amides (R1-CO-NR2R3), where at least one of the chains R1, R2 or R3 is interrupted by a functional group, e.g. a -NH-, -NR-, -CO-, or -CON- group
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/75—Amino oxides

Definitions

  • the present invention relates to laundry detergent compositions containing a lipolytic enzyme (lipase) and specially selected primary and/or tertiary amines.
  • the compositions provide enhanced cleaning of grease/oil soils and stains, particulary when used in a pre-treat laundering process for cleaning fabrics stained with grease/oil soils.
  • lipase in detergent compositions for improved cleaning performance is known, e.g. enhancement of removal of triglycerides containing soils and stains from fabrics.
  • Examples are US Patent 4,769,173; US Patent 5,069,809; PCT application WO94/03578.
  • USP 4,769,173 is disclosed a certain class of lipases consisting of fungal upases ex Humicola lanuginosa together with strong bleaching agents in detergent compositions.
  • An example of a fungal lipase in this patent is the lipase ex Humicola lanuginosa, available from Amano under the tradename Amano-CE.
  • USP 5,069,809 is disclosed the combination of strong bleaching agents with a lipase enzyme produced by cloning the gene encoding the lipase produced by Humicola lanuginosa and expressing the gene in Aspergillus oryzae as host for use in detergent compositions.
  • WO 94/03578 is disclosed an enzymatic detergent composition containing 10 to 20 000 LU (Lipolytic units) per gram of detergent composition of a lipase showing a substantial lipolytic activity during the main cycle of a wash process.
  • This lipase is selected in particular on its inactivation behaviour with Diisopropyl Fluoro Phosphate (DFP) .
  • DFP Diisopropyl Fluoro Phosphate
  • lipase enzymes only the lipase derived from Humicola lanuginosa and produced in Aspergillus oryzae as host has so far found wide-spread application as additive for fabric washing products. It is available under the tradename Lipolase®, from Novo Nordisk.
  • WO 92/05249 describes the D96L variant of the native Humicola lanuginosa lipase improves the lard stain removal efficiency by a factor 4.4 over the wild-type lipase (enzymes compared in an amount ranging from 0.075 to 2.5 mg protein per liter) .
  • lipase to clean soils and stains from fabrics present in the typical load of laundry is of high importance in the evaluation of detergent performance.
  • the relative ability of lipase to meet various performance criteria is among other depending on the presence of cosurfactants.
  • a surfactant system comprising a cosurfactant selected from the group of primary or tertiary amines.
  • liquid detergent compositions containing a lipolytic enzyme and a specially selected primary of tertiary amine show synergistic removal of greasy/oily soils particularly when the detergent composition is used in a pre-treatment application to greasy/oily soil stains on fabrics prior to and in conjunction with a normal wash process of the fabrics.
  • An essential ingredient in the present laundry detergent compositions is a performance-enhancing amount, preferably from about 0.0001 to 1.0% on an active basis, of a detergent-compatible lipase (lipolytic enzyme) .
  • a detergent-compatible lipase lipolytic enzyme
  • compatibility with the other ingredients of the composition particularly detergent surfactants and any detergency builders.
  • Liquid detergent compositions, particularly heavy duty liquids, are preferred herein.
  • Any lipase suitable for use in a laundry detergent composition can be used herein.
  • Suitable upases for use herein include those of bacterial and fungal origin. Lipase from chemically or genetically modified mutants are included herein.
  • Suitable bacterial upases include those produced by Pseudomonas, such as Pseudomonas stutzeri ATCC 19.154, as disclosed in British Patent 1,372,034, incorporated herein by reference. Suitable upases include those which show a positive immunological cross-reaction with the antibody of the lipase produced by the microorganism Pseudomonas fluorescens IAM 1057. This lipase and a method for its purificatioh have been described in Japanese Patent Application 53-20487, laid open on February 24, 1978, which is incorporated herein by reference.
  • This lipase is available under the trade name Lipase P "Amano, " hereinafter referred to as "Amano-P.”
  • Mano-P Lipase P
  • Such upases should show a positive immunological cross reaction with Amano-P antibody, using the standard and well-known immunodiffusion procedure according to Ouchterlony (Acta. Med. Scan., 133, pages 76-79 (1950)).
  • These lipases, and a method for their immunological cross-reaction with Amano-P are also described in U.S. Patent 4,707,291, Thorn et al., issued November 17, 1987, incorporated herein by reference.
  • Typical examples thereof are the Amano-P lipase, the lipase ex Pseudomonas fragi FERM P 1339 (available under the trade name Amano-B) , lipase ex Pseudomonas nitroreducens var. lipolyticum FERM P 1338 (available under the trade name Amano-CES) , lipases ex Chromobacter viscosum, e.g., Chromobacter viscosum var. lipolyticum NRRLB 3673, and further Chromobacter viscosum lipases, and lipases ex Pseudomonas gladioli.
  • Other lipases of interest are Amano AKG and Bacillis Sp lipase.
  • Suitable fungal lipases include those producible by Humicola lanuginosa and Thermomyces lanuginosus. Most preferred is lipases obtained by cloning the gene from Humicola lanuginosa and expressing the gene in Aspergillus oryzae as described in European Patent Application 0 258 068, incorporated herein by reference, commercially available under the trade name LipolaseTM.
  • Highly preferred lipases are the D96L lipolytic enzyme variant of the native lipase derived from Humicola lanuginosa as described in US Serial No. 08/341,826.
  • the Humicola lanuginosa strain DSM 4106 is used. This enzyme is incorporated into the composition in accordance with the invention at a level of from 50LU to 8500LU per liter wash solution.
  • the variant D96L is present at a level of from 100LU to 7500LU per liter of wash solution. More preferably at a level of from 150 LU to 5000 LU per liter of wash solution.
  • D96L lipolytic enzyme variant is meant the lipase variant as described in patent application WO 92/05249 viz. wherein the native lipase ex Humicola lanuginosa aspartic acid (D) residue at position 96 is changed to Leucine (L) . According to the nomenclature said substitution of aspartic acid to Leucine in position 96 is shown as : D96L.
  • D96L lipolytic enzyme variant is particularly preferred because of the good odor characteristics associated with the combined use of amines.
  • lipase units per gram (LU/g) of lipase can be used in these compositions.
  • a lipase unit is that amount of lipase which produces 1 ⁇ mol 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 tributyrin, and gum arabic, in the presence of Ca ++ and NaCl in phosphate buffer.
  • the amines as used herein refer to primary or tertiary amines which is believed to form a mixed micelle with the anionic surfactant and where the carbon chain length of the alkyl group is equal or greater than Cg.
  • Suitable primary amines for use herein include amines according to the formula R ⁇ NH2 wherein R * L is a C5-C12 preferably alkyl chain or R4X(CH2) n .
  • x is _ 0-,- C(0)NH- or -NH- R4 is a Cg-C]_2 alkyl chain n is between 1 to 5, preferably 3.
  • R- ⁇ alkyl chains may be straight or branched and may be interrupted with up to 12, preferably less than 5 ethylene oxide moieties.
  • Preferred amines according to the formula herein above are n-alkyl amines.
  • Suitable amines for use herein may be selected from 1-hexylamine, 1-octylamine, 1-decylamine and laurylamine.
  • Other preferred primary amines include C8-C10 oxypropylamine, octyloxypropylamine, 2-ethylhexyl- oxypropylamine, lauryl a ido propylamine and amido propyla ine.
  • Suitable tertiary amines for use herein include tertiary amines having the formula R1R2R3N wherein Rl and R2 are C ⁇ -Cg alkylchains or
  • R3 is either a Cg-C ⁇ , preferably Cg-Cio alkyl chain, or R3 is R4X(CH2 )n . whereby X is -0-, -C(0)NH- or -NH- ⁇ 4 is a C4- C12 n i- 5 between 1 to 5, preferably 2-3. R5 is H or C ⁇ -C2 alkyl and x is between 1 to 6 .
  • R3 and R4 may be linear or branched ; R3 alkyl chains may be interrupted with up to 12, preferably less than 5, ethylene oxide moieties.
  • Preferred tertiary amines are R1R2R3N where Rl is a C6- C12 alkyl chain, R2 and R3 are C1-C3 alkyl or
  • R ⁇ is Cg-Ci ⁇ alkyl
  • n is 2-4, preferably n is 3
  • R2 and R3 is C1-C
  • Most preferred amines of the present invention include 1-octylamine, 1-hexylamine, 1-decylamine, l-dodecylamine,C8- lOoxypropylamine, N coco l-3diaminopropane, coconutalkyldimethylamine, lauryldimethylamine, lauryl bis (hydroxyethyl)amine, coco bis (hydroxyehtyl)amine, lauryl amine 2 moles propoxylated, octyl amine 2 moles propoxylated, lauryl amidopropyldimethylamine, C8-10 amidopropyldimethylamine and CIO amidopropyldimethylamine.
  • the most preferred amines for use in the compositions herein are 1-hexylamine, 1-octylamine, 1-decylamine, 1- dodecylamine. Especially desirable are n- dodecyldimethylamine and bishydroxyethylcoconutalkylamine and oleylamine 7 times ethoxylated, lauryl amido propylamine and cocoamido propylamine.
  • the present invention also provides a process for laundering fabrics soiled with greasy/oily stains or soil. Such a process employs contacting these fabrics with an aqueous washing solution formed from an effective amount of the detergent compositions hereinbefore described. Contacting of fabrics with washing solution will generally occur under conditions of agitation.
  • Agitation is preferably provided in a washing machine for good cleaning. Washing is preferably followed by drying the wet fabric in a conventional clothes dryer.
  • An effective amount of the liquid or granular detergent composition in the aqueous wash solution in the washing machine is preferably from about 500 to about 7000 ppm, more preferably from about 1000 to 3000 ppm.
  • the detergent compositions herein may also be used to pretreat fabrics containing greasy/oily soils or stains prior to washing such fabrics using conventional aqueous washing solutions. Such pretreatment involves the application of highly concentrated forms of the detergent compositions herein directly onto the greasy or oily stains or soils found on the fabric to be cleaned. For compositions herein in liquid form, this will generally involve the direct application of the composition as is to the stain/soil on the fabric.
  • Pretreatment of greasy/oily stains or soils will generally occur for a period of from about 30 seconds to 24 hours prior to washing the pretreated soiled/stained substrate in conventional manner. More preferably, pretreatment times will range from about 1 to 180 minutes.
  • Detergent ingredients
  • the liquid detergent composition may comprise one or more of a surfactant selected from a wide range of surfactants.
  • Preferred anionic surfactants include the alkyl sulfate surfactants hereof are water soluble salts or acids of the formula ROSO3M wherein R preferably is a 10-C2 hydrocarbyl, preferably an alkyl or hydroxyalkyl having a c 10 ⁇ c 18 alkyl component, more preferably a Ci2 ⁇ c l5 alkyl or hydroxyalkyl, and M is H or a cation, e.g., an alkali metal cation (e.g. sodium, potassium, lithium), or ammonium or substituted ammonium (e.g.
  • R preferably is a 10-C2 hydrocarbyl, preferably an alkyl or hydroxyalkyl having a c 10 ⁇ c 18 alkyl component, more preferably a Ci2 ⁇ c l5 alkyl or hydroxyalkyl
  • M is H or a cation, e.g., an alkali metal cation (e.g. sodium, potassium,
  • methyl-, dimethyl-, and trimethyl ammonium cations and quaternary ammonium cations such as tetramethyl-ammonium and dimethyl piperdinium cations and quaternary ammonium cations derived from alkylamines such as ethylamine, diethylamine, triethylamine, and mixtures thereof, and the like) .
  • alkyl alkoxylated sulfate surfactants hereof are water soluble salts or acids of the formula R0(A) m S03M wherein R is an unsubstituted C10-C24 alkyl or hydroxyalkyl group having a c 10 ⁇ c 24 alkyl component, preferably a Ci2 ⁇ c 18 alkyl or hydroxyalkyl, more preferably C 2 ⁇ c 15 alkyl or hydroxyalkyl, A is an ethoxy or propoxy unit, m is greater than zero, typically between about 0.5 and about 6, more preferably between about 0.5 and about 3, and M is H or a cation which can be, for example, a metal cation (e.g., sodium, potassium, lithium, calcium, magnesium, etc.), ammonium or substituted-ammonium cation.
  • R is an unsubstituted C10-C24 alkyl or hydroxyalkyl group having a c 10 ⁇ c 24 alkyl component,
  • Alkyl ethoxylated sulfates as well as alkyl propoxylated sulfates are contemplated herein.
  • Specific examples of substituted ammonium cations include methyl-, dimethyl, trimethyl-ammonium cations and quaternary ammonium cations such as tetramethyl-ammonium and dimethyl piperdinium cations and those derived from alkylamines such as ethylamine, diethylamine, triethylamine, mixtures thereof, and the like.
  • Exemplary surfactants are i2 -C 15 alkyl polyethoxylate (1.0) sulfate , C 1 2" c 15 alkyl polyethoxylate (2.25) sulfate (C 12 -C 15 E(2.25.M) , C 12 - Ci5 alkyl polyethoxylate (3.0) sulfate (C12-C15E(3.0)M) , and c 12" c 15 alkyl polyethoxylate (4.0) sulfate (C12-C15E(4.0)M) , wherein M is conveniently selected from sodium and potassium.
  • alkyl ester sulfonate surfactants including linear esters of C ⁇ - C20 carboxylic acids (i.e., fatty acids) which are sulfonated with gaseous SO3 according to "The Journal of the American Oil Chemists Society", 52 (1975), pp. 323-329.
  • Suitable starting materials would include natural fatty substances as derived from tallow, palm oil, etc.
  • alkyl ester sulfonate surfactant especially for laundry applications, comprise alkyl ester sulfonate surfactants of the structural formula :
  • R 3 is a Cg-C20 hydrocarbyl, preferably an alkyl, or combination thereof
  • R 4 is a Ci-C ⁇ hydrocarbyl, preferably an alkyl, or combination thereof
  • M is a cation which forms a water soluble salt with the alkyl ester sulfonate.
  • Suitable salt-forming cations include metals such as sodium, potassium, and lithium, and substituted or unsubstituted ammonium cations, such as monoethanolamine, diethanolamine, and triethanolamine.
  • R 3 is C ⁇ o ⁇ c 16 alkyl
  • R 4 is methyl, ethyl or isopropyl.
  • the methyl ester sulfonates wherein R 3 is C ⁇ o ⁇ c 16 alkyl.
  • 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, 9-C20 linear alkylbenzenesulfonates, C8 -( --22 primary of secondary alkanesulfonates, Cg-C24 olefinsulfonates, sulfonated polycarboxylic acids prepared by sulfonation of the pyrolyzed product of alkaline earth metal citrates, e.g., as described in British patent specification No.
  • Cg- C2 alkylpolyglycolethersulfates (containing up to 10 moles of ethylene oxide) ; alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, paraffin sulfonates, alkyl phosphates, isethionates such as the acyl isethionates, N-acyl taurates, alkyl succinamates and sulfosuccinates, monoesters of sulfosuccinates (especially saturated and unsaturated Ci2 ⁇ c 18 monoesters) and diesters of sulfosuccinates (especially saturated and unsaturated Cg- C12 diesters) , sulfates of alkylpolysaccharides such as the sulfates of alkylpolyglu
  • Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tall oil. Further examples are described in "Surface-Active Agents and Detergents" (Vol. I and II by Schwartz, Perry and Berch). A variety of such surfactants are also generally disclosed in U.S. Patent 3,929,678, issued December 30, 1975 to Laughlin, et al. at Column 23, line 58 through Column 29, line 23 (herein incorporated by reference) .
  • the laundry detergent compositions of the present invention typically comprise from about 1% to about 40%, preferably from about 5% to about 25% by weight of such anionic surfactants.
  • One class of nonionic surfactants useful in the present invention are condensates of ethylene oxide with a hydrophobic moiety to provide a surfactant having an average hydrophilic-lipophilic balance (HLB) in the range from 8 to 17, preferably from 9.5 to 14, more preferably from 12 to 14.
  • HLB hydrophilic-lipophilic balance
  • the hydrophobic (lipophilic) moiety may be aliphatic or aromatic in nature and the length of the polyoxyethylene 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.
  • Especially preferred nonionic surfactants of this type are the C9-C15 primary alcohol ethoxylates containing 3-12 moles of ethylene oxide per mole of alcohol, particularly the 2 _c l5 primary alcohols containing 5-8 moles of ethylene oxide per mole of alcohol.
  • Another class of nonionic surfactants comprises alkyl polyglucoside compounds of general formula
  • Z is a moiety derived from glucose; R is a saturated hydrophobic alkyl group that contains from 12 to 18 carbon atoms; t is from 0 to 10 and n is 2 or 3; x is from 1.3 to 4, the compounds including less than 10% unreacted fatty alcohol and less than 50% short chain alkyl polyglucosides.
  • Compounds of this type and their use in detergent are disclosed in EP-B 0 070 077, 0 075 996 and 0 094 118.
  • nonionic surfactants are poly hydroxy fatty acid amide surfactants of the formula
  • R 1 is H, or R 1 is C -4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl or a mixture thereof
  • R 2 is C5-31 hydrocarbyl
  • Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative thereof.
  • R is methyl
  • R 2 is a straight Cn_i5 alkyl or alkenyl chain such as coconut alkyl or mixtures thereof
  • Z is derived from a reducing sugar such as glucose, fructose, maltose, lactose, in a reductive amination reaction.
  • compositions of the present invention may comprise amine oxide in accordance with the general formula I:
  • the structure (I) provides one long-chain moiety R (EO) (PO) (BO) and two x y z short chain moieties, CH R' .
  • R' is preferably selected from hydrogen, methyl and -CH2OH.
  • R 1 is a primary or branched hydrocarbyl moiety which can be saturated or unsaturated, preferably, R is a primary alkyl moiety.
  • R is a hydrocarbyl moiety having chainlength of from about 8 to about 18.
  • the invention also encompasses amine oxides wherein x+y+z is different from zero, specifically x+y+z is from about 1 to about 10, R is a primary alkyl group containing 8 to about 24 carbons, preferably from about 12 to about 16 carbon atoms; in these embodiments y + z is preferably 0 and x is preferably from about 1 to about 6, more preferably from about 2 to about 4; EO represents ethyleneoxy; PO represents propyleneoxy; and BO represents butyleneoxy.
  • amine oxides can be prepared by conventional synthetic methods, e.g., by the reaction of alkylethoxysulfates with dimethylamine followed by oxidation of the ethoxylated amine with hydrogen peroxide.
  • Highly preferred amine oxides herein are solids at ambient temperature, more preferably they have melting- points in the range 30°C to 90°C.
  • Amine oxides suitable for use herein are made commercially by a number of suppliers, including Akzo Che ie, Ethyl Corp., and Procter & Gamble. See McCutcheon's compilation and Kirk-Othmer review article for alternate amine oxide manufacturers.
  • Preferred commercially available amine oxides are the solid, dihydrate ADMOX 16 and ADMOX 18, ADMOX 12 and especially ADMOX 14 from Ethyl Corp.
  • Preferred embodiments include hexadecyldimethylamine oxide dihydrate, dodecyldimethylamine oxide dihydrate, octadecyldimethylamine oxide dihydrate, hexadecyltris
  • R * CH OH, such as hexadecylbis (2- hydroxyethyl)amine oxide, tallowbis (2- hydroxyethyl)amine oxide, stearylbis(2-hydroxyethyl)amine oxide and oleylbis(2- hydroxyethyl) amine oxide, dodecyldimethylamine oxide dihydrate.
  • the laundry detergent compositions of the present invention typically comprise nonionic surfactants in the weight ratio of anionic surfactant to nonionic surfactant from 6:1 to 1:3, preferably from 5:1 to 2:1.
  • 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 is an alkyl or alkyl benzyl group having from about 8 to about 18 carbon atoms in the alkyl chain
  • each R 3 is selected from the group consisting of -CH2CH2-, CH 2 CH(CH 3 )-, -CH2CH(CH2 ⁇ H)-, -CH 2 CH 2 CH2-, and mixtures thereof
  • each R 4 is selected from the group consisting of c l ⁇ c 4 alkyl, C1-C4 hydroxyalkyl, benzyl ring structures formed by joining the two R 4 groups, -CH2CHOH- CHOHCOR ⁇ CHOHCH2 ⁇ H wherein R*- 5 is any hexose or hexose polymer having a molecular weight less than about 1000, and hydrogen when y is not 0;
  • R ⁇ is the same as R 4 or is an alkyl chain wherein the total number of carbon atoms of R 2 plus R ⁇ is not more than about 18; each y is from 0 to about 10
  • Preferred cationic surfactants are the water-soluble quaternary ammonium compounds useful in the present composition having the formula :
  • R- ⁇ is Cg-C ⁇ g alkyl
  • each of R2/ 3 and R4 is independently C1-C4 alkyl, C1-C hydroxy alkyl, benzyl, and -(C2H4 ⁇ ) x H where x has a value from 1 to 5, and X is an anion.
  • R2, R3 or R4 should be benzyl.
  • the preferred alkyl chain length for R]_ is i2 ⁇ c 15 particularly where the alkyl group is a mixture of chain lengths derived from coconut or palm kernel fat or is derived synthetically by olefin build up or 0X0 alcohols synthesis.
  • Preferred groups for R2R3 and R4 are methyl and hydroxyethyl groups and the anion X may be selected from halide, methosulphate, acetate and phosphate ions.
  • Suitable quaternary ammonium compounds of formulae (i) for use herein are : coconut trimethyl ammonium chloride or bromide; coconut methyl dihydroxyethyl ammonium chloride or bromide; decyl triethyl ammonium chloride; decyl dimethyl hydroxyethyl ammonium chloride or bromide; c 12-15 dimethyl hydroxyethyl ammonium chloride or bromide; coconut dimethyl hydroxyethyl ammonium chloride or bromide; myristyl trimethyl ammonium methyl sulphate; lauryl dimethyl benzyl ammonium chloride or bromide; lauryl dimethyl (ethenoxy) 4 ammonium chloride or bromide; choline esters (compounds of formula (i) wherein R_ is -
  • CH2 ⁇ 0-C(0)-C12-14 alkyl and R2R3R are methyl
  • Other cationic surfactants useful herein are also described in U.S. Patent 4,228,044, Cambre, issued October 14, 1980.
  • the laundry detergent compositions of the present invention typically comprise from 0.5% to about 5%, preferably from about 1% to about 3% by weight of such cationic surfactants.
  • compositions according to the present invention may further comprise a builder system.
  • a builder system Any conventional builder system is suitable for use herein including aluminosilicate materials, silicates, polycarboxylates and fatty acids, materials such as ethylenediamine tetraacetate, metal ion sequestrants such as a inopolyphosphonates, particularly ethylenediamine tetramethylene phosphonic acid and diethylene triamine pentamethylenephosphonic acid.
  • phosphate builders can also be used herein.
  • Suitable polycarboxylates builders for use herein include citric acid, preferably in the form of a water- soluble salt, derivatives of succinic acid of the formula R- CH(COOH)CH2 (COOH) wherein R is C10-20 alkyl or alkenyl, preferably C12-16, or wherein R can be substituted with hydroxyl, sulfo sulfoxyl or sulfone substituents.
  • Specific examples include lauryl succinate , myristyl succinate, palmityl succinate 2-dodecenylsuccinate, 2-tetradecenyl succinate.
  • Succinate builders are preferably used in the form of their water-soluble salts, including sodium, potassium, ammonium and alkanolammonium salts.
  • polycarboxylates are oxodisuccinates and mixtures of tartrate monosuccinic and tartrate disuccinic acid such as described in US 4,663,071.
  • suitable fatty acid builders for use herein are saturated or unsaturated C10-18 fatty acids, as well as the corresponding soaps.
  • Preferred saturated species have from 12 to 16 carbon atoms in the alkyl chain.
  • the preferred unsaturated fatty acid is oleic acid.
  • Other preferred builder system for liquid compositions is based on dodecenyl succinic acid and citric acid.
  • Detergency builder salts are normally included in amounts of from 3% to 50% by weight of the composition preferably from 5% to 30% and most usually from 5% to 25% by weight.
  • Preferred detergent compositions of the present invention may further comprise one or more enzymes which provide cleaning performance and/or fabric care benefits.
  • Said enzymes include enzymes selected from cellulases, hemicellulases, peroxidases, proteases, gluco-amylases, amylases, lipases, cutinases, pectinases, xylanases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases, pentosanases, malanases, ⁇ -glucanases, arabinosidases or mixtures thereof.
  • a preferred combination is a detergent composition having a cocktail of conventional applicable enzymes like protease, amylase, lipase, cutinase and/or cellulase in conjunction with the lipolytic enzyme variant D96L at a level of from 50 LU to 8500 LU per liter wash solution.
  • the cellulases usable in the present invention include both bacterial or fungal cellulase. Preferably, they will have a pH optimum of between 5 and 9.5. Suitable cellulases are disclosed in U.S. Patent 4,435,307, Barbesgoard et al, which discloses fungal cellulase produced from Humicola insolens. Suitable cellulases are also disclosed in GB-A- 2.075.028; GB-A-2.095.275 and DE-OS-2.247.832.
  • cellulases examples include cellulases produced by a strain of Humicola insolens (Humicola grisea var. thermoidea) , particularly the Humicola strain DSM 1800.
  • suitable cellulases are cellulases originated from Humicola insolens having a molecular weight of about 50KDa, an isoelectric point of 5.5 and containing 415 amino acids.
  • Especially suitable cellulases are the cellulases having color care benefits. Examples of such cellulases are cellulases described in European patent application No. 91202879.2, filed November 6, 1991 (Novo).
  • Peroxidase enzymes are used in combination with oxygen sources, e.g. percarbonate, perborate, persulfate, hydrogen peroxide, etc. They are used for "solution bleaching", i.e. to prevent transfer of dyes or pigments removed from substrates during wash operations to other substrates in the wash solution.
  • Peroxidase enzymes are known in the art, and include, for example, horseradish peroxidase, ligninase, and haloperoxidase such as chloro- and bromo-peroxidase.
  • Peroxidase-containing detergent compositions are disclosed, for example, in PCT International Application WO 89/099813 and in European Patent application EP No. 91202882.6, filed on November 6, 1991.
  • Said cellulases and/or peroxidases are normally incorporated in the detergent composition at levels from 0.0001% to 2% of active enzyme by weight of the detergent composition.
  • protease enzymes include those sold under the tradenames Alcalase, Savinase, Primase, Durazym, and Esperase by Novo Nordisk A/S (Denmark) , those sold under the tradename Maxatase, Maxacal and Maxapem by Gist-Brocades, those sold by Genencor International, and those sold under the tradename Opticlean and Optimase by Solvay Enzymes. Also proteases described in our co-pending application USSN 08/136,797 can be included in the detergent composition of the invention. Protease enzyme may be incorporated into the compositions in accordance with the invention at a level of from 0.0001% to 2% active enzyme by weight of the composition.
  • a preferred protease herein referred to as "Protease D” is a carbonyl hydrolase variant having an amino acid sequence not found in nature, which is derived from a precursor carbonyl hydrolase by substituting a different amino acid for the amino acid residue at a position in said carbonyl hydrolase equivalent to position +76, preferably also in combination with one or more amino acid residue positions equivalent to those selected from the group consisting of +99, +101, +103, +104, +107, +123, +27, +105, +109, +126, +128, +135, +156, +166, +195, +197, +204, +206, +210, +216, +217, +218, +222, +260, +265, and/or +274 according to the numbering of Bacill us amyloliquefaciens subtilisin, as described in the concurrently filed patent application of A. Baeck et al. entitled “Protease-Containing Cleaning Compositions" having U.S. Serial No. 08/3
  • cutinases [EC 3.1.1.50] which can be considered as a special kind of lipase, namely lipases which do not require interfacial activation. Addition of cutinases to detergent compositions have been described in e.g. WO-A- 88/09367 (Genencor) .
  • the lipases and/or cutinases are normally incorporated in the detergent composition at levels from 0.0001% to 2% of active enzyme by weight of the detergent composition.
  • Amylases (& and/or ⁇ ) can be included for removal of carbohydrate-based stains. Suitable amylases are Termamyl R (Novo Nordisk) , Fungamyl R and BAN R (Novo Nordisk) .
  • the above-mentioned enzymes may be of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin.
  • Said enzymes are normally incorporated in the detergent composition at levels from 0.0001% to 2% of active enzyme by weight of the detergent composition.
  • Other suitable detergent ingredients that can be added are enzyme oxidation scavengers which are described in Copending European Patent application 92870018.6 filed on January 31, 1992. Examples of such enzyme oxidation scavengers are ethoxylated tetraethylene polyamines.
  • a preferred component to be used in the detergent compositions of the present invention comprise soil-release agents.
  • Soil release agents useful in compositions of the present invention are conventionally copolymers or terpolymers of terephthalic acid with ethylene glycol and/or propylene glycol units in various arrangements. Examples of such polymers are disclosed in the commonly assigned US Patent Nos. 4116885 and 4711730 and European Published Patent Application No. 0 272 033. A particular preferred polymer in accordance with EP-A-0 272 033 has the formula
  • modified polyesters as random copolymers of dimethyl terephtalate, dimethyl sulfoisophtalate, ethylene glycol and 1-2 propane diol, the end groups consisting primarily of sulphobenzoate and secondarily of mono esters of ethylene glycol and/or propane-diol.
  • the target is to obtain a polymer capped at both end by sulphobenzoate groups, "primarily", in the present context most of said copolymers herein will be end- capped by sulphobenzoate groups.
  • some copolymers will be less than fully capped, and therefore their end groups may consist of monoester of ethylene glycol and/or propane 1-2 diol, thereof consist “secondarily” of such species.
  • the selected polyesters herein contain about 46% by weight of dimethyl terephtalic acid, about 16% by weight of propane -1.2 diol, about 10% by weight ethylene glycol about 13% by weight of dimethyl sulfobenzoid acid and about 15% by weight of sulfoisophtalic acid, and have a molecular weight of about 3.000.
  • the polyesters and their method of preparation are described in detail in EPA 311 342.
  • Particularly suitable soil-release polymers include oligomeric esters such as described in US Patent Application No. 08/355 938 filed December 14, 1994. Said esters comprise
  • detergent compositions may be employed, such as soil-suspending agents, abrasives, bactericides, tarnish inhibitors, coloring agents, foam control agents, corrosion inhibitors and perfumes.
  • the liquid compositions according to the present invention are in "concentrated form"; in such case, the liquid detergent compositions according to the present invention will contain a lower amount of water, compared to conventional liquid detergents.
  • the level of water is less than 50%, preferably less than 30% by weight of the detergent compositons.
  • Said concentrated products provide advantages to the consumer, who has a product which can be used in lower amounts and to the producer, who has lower shipping costs.
  • liquid compositions are especially effective when applied directly to soils and stains in a pretreatment step.
  • the detergent compositions of the present invention can also be used as detergent additive products. Such additive products are intended to supplement or boost the performance of conventional detergent compositions.
  • the detergent compositions according to the present invention include compositions which are to be used for cleaning of substrates, such as fabrics, fibers, hard surfaces, skin etc., for example hard surface cleaning compositions (with or without abrasives), laundry detergent compositions, automatic and non-automatic dishwashing compositions.
  • Amylase (300KNU/g) 0, 1 0.1 0.1 0, 0 1 Lipase D96/L (lOOKNU/g) 0.15 0.15 0.15 0.15 0 15 Protease (34g/l) 0.5 0.5 0.5 0.5 0.5 0, 5 Endo-A (5000 CEVU/g) 0.05 0.05 0.05 0.05 0.5 Carezyme (5000 CEVU/g) 0.09 0.09 0.09 0.09 0.9 Terephthalate-based polymer 0.15 0.15 Oligomeric ester (Formula A) 0.07 0.07 0.07 Boric acid 2.4 2.4 2.8 2.8 2.4 2.4
  • Tetraethylenepenta ine 1.18 1.18 1.00 ethoxylated (15-18) Water, perfume, enzymes, to 100% to 100% to 100% soil release polymers suds suppressor & other optional ingredients
  • Tetraethylenepentamine 1.18 1.18 1.18 1.18 ethoxylated (15-18) Water, perfume, to 100% to 100% to 100% to 100% to 100% enzymes, soil release polymers suds suppressor & other optional ingredients

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  • Engineering & Computer Science (AREA)
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Abstract

L'invention porte sur des compositions détergentes pour lessive comprenant une enzyme lipolytique (lipase) et des amines primaires et/ou tertiaires spécialement sélectionnées. Lesdites compositions assurent un meilleur nettoyage des salissures et taches de graisse et d'huile notamment lorsqu'on les utilise pour un prétraitement de tissus comportant des salissures graisseuses ou huileuses avant le lavage.
PCT/US1995/012469 1994-10-13 1995-09-29 Compositions detergentes pour lessive comprenant une enzyme lipolytique et des amines WO1996012004A1 (fr)

Priority Applications (10)

Application Number Priority Date Filing Date Title
AT95934562T ATE215984T1 (de) 1994-10-13 1995-09-29 Textilwaschmittel enthaltend lipolytisches enzym und aminverbindungen
JP8513248A JPH10509468A (ja) 1994-10-13 1995-09-29 脂肪分解酵素及びアミンを含有した洗濯洗剤組成物
CA002202505A CA2202505C (fr) 1994-10-13 1995-09-29 Compositions detergentes pour lessive comprenant une enzyme lipolytique et des amines
AU36869/95A AU3686995A (en) 1994-10-13 1995-09-29 Laundry detergent compositions containing lipolytic enzyme and amines
US08/817,154 US5935271A (en) 1994-10-13 1995-09-29 Laundry detergent compositions containing lipolytic enzyme and amines
DE69526360T DE69526360T2 (de) 1994-10-13 1995-09-29 Textilwaschmittel enthaltend lipolytisches enzym und aminverbindungen
CZ971109A CZ110997A3 (en) 1994-10-13 1995-09-29 Detergents containing lipolitic enzyme and amines
EP95934562A EP0785981B1 (fr) 1994-10-13 1995-09-29 Compositions detergentes pour lessive comprenant une enzyme lipolytique et des amines
BR9509349A BR9509349A (pt) 1994-10-13 1995-09-29 Composições detergentes para lavagem de roupas contendo enzimas lipolíticas a aminas
MXPA/A/1997/002728A MXPA97002728A (en) 1994-10-13 1997-04-14 Detergent compositions for laundry quecontain lipolitic enzyme and ami

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
PCT/US1994/011779 WO1996012000A1 (fr) 1994-10-13 1994-10-13 Composition detergente contenant des amines et des tensioactifs anioniques
USPCT/US94/11779 1994-10-13
USPCT/US95/07824 1995-06-20
PCT/US1995/007824 WO1997000929A1 (fr) 1994-10-13 1995-06-20 Composition detergente contenant des amines et des tensio-actifs anioniques

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PCT/US1995/012469 WO1996012004A1 (fr) 1994-10-13 1995-09-29 Compositions detergentes pour lessive comprenant une enzyme lipolytique et des amines

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* Cited by examiner, † Cited by third party
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WO1997019155A1 (fr) * 1995-11-17 1997-05-29 The Procter & Gamble Company Compositions detergentes lessivielles contenant une enzyme lipolytique et des composes d'ammonium quaternaire selectionnes
WO1997035948A2 (fr) * 1996-03-26 1997-10-02 Basf Aktiengesellschaft Renforçateur du pouvoir lavant de detergents
WO1997043377A1 (fr) * 1996-05-15 1997-11-20 The Procter & Gamble Company Compositions de detergence comprenant une enzyme lipolytique specifique ainsi qu'un tensioactif a base de polyglucoside d'alkyle
WO1997043375A1 (fr) * 1996-05-15 1997-11-20 The Procter & Gamble Company Compositions detergentes comprenant une enzyme lipolytique et un systeme tensio-actif specifique
WO1997043380A1 (fr) * 1996-05-15 1997-11-20 The Procter & Gamble Company Compositions detergentes comprenant une enzyme lipolytique specifique et une zeolite map
WO1997043379A1 (fr) * 1996-05-15 1997-11-20 The Procter & Gamble Company Compositions detergentes comprenant une enzyme lipolytique specifique et un dispersant a base de savon de chaux
WO1997043376A1 (fr) * 1996-05-15 1997-11-20 The Procter & Gamble Company Compositions detergentes comportant des enzymes lipolytiques
WO1997043374A1 (fr) * 1996-05-15 1997-11-20 The Procter & Gamble Company Compositions detergentes contenant un enzyme lipolytique specifique et un polymere facilitant le lavage
EP0791046B1 (fr) * 1994-11-18 2000-04-05 THE PROCTER & GAMBLE COMPANY Compositions de detergents contenant de la lipase et de la prote ase
DE19850012A1 (de) * 1998-10-30 2000-05-04 Aladin Ges Fuer Innovative Mik Rohrreiniger
US6506716B1 (en) * 1997-07-29 2003-01-14 The Procter & Gamble Company Aqueous, gel laundry detergent composition
WO2006041704A1 (fr) * 2004-10-04 2006-04-20 Akzo Nobel N.V. Composition detergente liquide pour lavages delicats
US7319112B2 (en) 2000-07-14 2008-01-15 The Procter & Gamble Co. Non-halogenated antibacterial agents and processes for making same
US7572761B2 (en) 2005-11-14 2009-08-11 Evonik Degussa Gmbh Process for cleaning and softening fabrics
EP2389429A2 (fr) * 2009-01-20 2011-11-30 Ecolab INC. Compositions enzymatiques antimicrobiennes aqueuses stables
EP3858965A1 (fr) 2020-01-28 2021-08-04 The Procter & Gamble Company Produit de nettoyage
US11753604B2 (en) 2020-01-28 2023-09-12 The Procter & Gamble Company Cleaning product

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US5827813A (en) * 1997-02-28 1998-10-27 Procter & Gamble Company Detergent compositions having color care agents
EP1354872A1 (fr) 2002-04-17 2003-10-22 Kao Corporation Sels d'amines d'esters d'acide sulfurique, sels d'amines d'acides sulfuriques, leur préparation et compositions adoucissantes
ES2670044T3 (es) 2015-06-04 2018-05-29 The Procter & Gamble Company Composición detergente líquida para lavado de vajillas a mano
CN106635496A (zh) * 2016-12-12 2017-05-10 广州立白企业集团有限公司 烷氧基烷基胺类化合物在洗涤剂中的应用及洗涤剂组合物

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US3755085A (en) * 1970-09-30 1973-08-28 Procter & Gamble Prevention of enzyme deactivation by chlorine
EP0171006A2 (fr) * 1984-08-04 1986-02-12 Henkel Kommanditgesellschaft auf Aktien Agent de nettoyage de la vaisselle
WO1986007603A1 (fr) * 1985-06-22 1986-12-31 Henkel Kommanditgesellschaft Auf Aktien Agent de lavage pour basses temperatures de lavage
WO1992005249A1 (fr) * 1990-09-13 1992-04-02 Novo Nordisk A/S Variantes lipasiques
EP0588413A1 (fr) * 1992-09-15 1994-03-23 Unilever N.V. Composition détergente

Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0791046B1 (fr) * 1994-11-18 2000-04-05 THE PROCTER & GAMBLE COMPANY Compositions de detergents contenant de la lipase et de la prote ase
WO1997019155A1 (fr) * 1995-11-17 1997-05-29 The Procter & Gamble Company Compositions detergentes lessivielles contenant une enzyme lipolytique et des composes d'ammonium quaternaire selectionnes
WO1997035948A2 (fr) * 1996-03-26 1997-10-02 Basf Aktiengesellschaft Renforçateur du pouvoir lavant de detergents
WO1997035948A3 (fr) * 1996-03-26 1997-11-20 Basf Ag Renforçateur du pouvoir lavant de detergents
US6180590B1 (en) 1996-03-26 2001-01-30 Basf Aktiengesellschaft Washing power enhancer for detergents
WO1997043377A1 (fr) * 1996-05-15 1997-11-20 The Procter & Gamble Company Compositions de detergence comprenant une enzyme lipolytique specifique ainsi qu'un tensioactif a base de polyglucoside d'alkyle
WO1997043375A1 (fr) * 1996-05-15 1997-11-20 The Procter & Gamble Company Compositions detergentes comprenant une enzyme lipolytique et un systeme tensio-actif specifique
WO1997043380A1 (fr) * 1996-05-15 1997-11-20 The Procter & Gamble Company Compositions detergentes comprenant une enzyme lipolytique specifique et une zeolite map
WO1997043379A1 (fr) * 1996-05-15 1997-11-20 The Procter & Gamble Company Compositions detergentes comprenant une enzyme lipolytique specifique et un dispersant a base de savon de chaux
WO1997043376A1 (fr) * 1996-05-15 1997-11-20 The Procter & Gamble Company Compositions detergentes comportant des enzymes lipolytiques
WO1997043374A1 (fr) * 1996-05-15 1997-11-20 The Procter & Gamble Company Compositions detergentes contenant un enzyme lipolytique specifique et un polymere facilitant le lavage
US6506716B1 (en) * 1997-07-29 2003-01-14 The Procter & Gamble Company Aqueous, gel laundry detergent composition
DE19850012A1 (de) * 1998-10-30 2000-05-04 Aladin Ges Fuer Innovative Mik Rohrreiniger
US7319112B2 (en) 2000-07-14 2008-01-15 The Procter & Gamble Co. Non-halogenated antibacterial agents and processes for making same
WO2006041704A1 (fr) * 2004-10-04 2006-04-20 Akzo Nobel N.V. Composition detergente liquide pour lavages delicats
US7572761B2 (en) 2005-11-14 2009-08-11 Evonik Degussa Gmbh Process for cleaning and softening fabrics
EP2389429A2 (fr) * 2009-01-20 2011-11-30 Ecolab INC. Compositions enzymatiques antimicrobiennes aqueuses stables
EP2389429A4 (fr) * 2009-01-20 2013-04-24 Ecolab Inc Compositions enzymatiques antimicrobiennes aqueuses stables
EP3858965A1 (fr) 2020-01-28 2021-08-04 The Procter & Gamble Company Produit de nettoyage
US11753604B2 (en) 2020-01-28 2023-09-12 The Procter & Gamble Company Cleaning product

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EP0785981B1 (fr) 2002-04-10
CN1168691A (zh) 1997-12-24
MX9702728A (es) 1997-07-31
DE69526360T2 (de) 2002-11-28
WO1997000929A1 (fr) 1997-01-09
ATE215984T1 (de) 2002-04-15
DE69526360D1 (de) 2002-05-16

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