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WO1997043377A1 - Compositions de detergence comprenant une enzyme lipolytique specifique ainsi qu'un tensioactif a base de polyglucoside d'alkyle - Google Patents

Compositions de detergence comprenant une enzyme lipolytique specifique ainsi qu'un tensioactif a base de polyglucoside d'alkyle Download PDF

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Publication number
WO1997043377A1
WO1997043377A1 PCT/US1996/007088 US9607088W WO9743377A1 WO 1997043377 A1 WO1997043377 A1 WO 1997043377A1 US 9607088 W US9607088 W US 9607088W WO 9743377 A1 WO9743377 A1 WO 9743377A1
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WO
WIPO (PCT)
Prior art keywords
alkyl
detergent composition
detergent
composition according
lipolytic enzyme
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PCT/US1996/007088
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English (en)
Inventor
Andre Cesar Baeck
Chandrika Kasturi
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The Procter & Gamble Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by The Procter & Gamble Company filed Critical The Procter & Gamble Company
Priority to PCT/US1996/007088 priority Critical patent/WO1997043377A1/fr
Priority to BR9612608A priority patent/BR9612608A/pt
Priority to AU58618/96A priority patent/AU5861896A/en
Priority to EP96920251A priority patent/EP0912683A1/fr
Publication of WO1997043377A1 publication Critical patent/WO1997043377A1/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
    • C11D3/16—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
    • C11D1/66—Non-ionic compounds
    • C11D1/662—Carbohydrates or derivatives

Definitions

  • the present invention relates to detergent compositions comprising a specific lipolytic enzyme and an alkyl poly glucoside surfactant.
  • lipolytic enzyme e.g. lipase
  • detergent compositions for improved cleaning performance e.g. enhancement of removal of triglycerides containing soils and stains from fabrics.
  • lipolytic enzyme e.g. lipase
  • examples are US Patent 4,769,173, Cornelissen et al. issued August 29, 1989; US Patent 5,069,809, Lagerwaard et al., issued December 3, 1991; PCT application WO94/03578 and HAPPI (Household & Personal Products Industry) No. 28/1991.
  • 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 In spite of the large number of publications on lipase enzymes only the lipase derived from Humicola lanuginosa strain DSM 4106 and produced in Aspergillus oryzae as host has so far found wide-spread application as additive for fabric washing products. It is available from Novo Nordisk under the tradename Lipolase (TM) . Gormsen and Malmos describe in HAPPI this enzyme with trademark "Lipolase" as being the first detergent lipase with a commercially relevant cost performance based on the use of recombinant DNA technology on an industrial scale.
  • TM Lipolase
  • Lipolase is the most effective during the drying step rather than the washing process itself. During the drying of the fabric, the conditions like water level are more favourable for lipolytic hydrolysis than during the actual wash cycle.
  • 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 variant D96L
  • D96L lipase variant
  • 0.001-lOOmg 5-500.000 LU/1 lipase variant per liter of wash liquor.
  • lipolytic enzyme deactivation occurs in detergent formulations. The loss of activity of the enzyme is among others depending on the presence of adjunct detergent ingredients.
  • One type of adjunct detergent ingredients is the surfactants.
  • detersive surfactants are known in the literature and in commercial practice. They perform a dual function within the detergent matrix. First, surfactant molecules reduce the interfacial tension between the soil and aqueous phase and thereby gradually remove the stain from the surface by a roll-up, emulsification or solubilisation mechanism. Anionic surfactants are particularly suitable for this function. Secondly, surfactant molecules keep the soil in suspension and prevent redeposition onto the surface. Alkyl poly glucoside nonionic and anionic surfactants traditionally serve that purpose.
  • Alkyl polyglucoside surfactants have been disclosed in U.S. Pat.Nos. 3,598,865; 3,721,633 and 3,772,269. These patents also disclose processes for making alkyl polyglucoside surfactants and built liquid detergent compositions containing these surfactants.
  • U.S. Pat.No. 3,219,656 discloses alkyl monoglucosides and suggests their utility as foam stabilizers for other surfactants.
  • Various polyglucoside surfactant structures and processes for making them are disclosed in U.S. Pat.Nos. 2,974,134; 3,640,998; 3,839,318; 3,314,936; 3,346,558; 4,011,389 and 4,223,129.
  • Alkyl polyglucoside surfactants have also been disclosed in combination with several cosurfactants in cleaning compositions.
  • U.S. Pat.No. 4,396,520 discloses a detergent composition containing an alkyl polysaccharide surfactant and a calcium sensitive anionic detergent cosurfactant.
  • U.S. Pat.No. 4,565,647 discloses a foaming composition containing an alkyl polysaccharide surfactant and a sulfate, sulfonate, and/or carboxylate cosurfactant.
  • 4,599,188 discloses a foaming composition containing an alkyl polysaccharide surfactant, a sulfate, sulfonate and/or carboxylate cosurfactant, and an amide and/or amine oxide auxiliary foam booster.
  • U.S. Pat.No. 4,732,704 discloses a manual dishwashing detergent composition containing an alkyl monoglucoside surfactant, an anionic surfactant of the sulfate or sulfonate type, and a fatty acid alkanol amide.
  • U.S. Pat. No. 4,839,098 discloses a manual dishwashing detergent composition containing an alkyl polyglucoside surfactant and a dialkyl sulfosuccinate.
  • Alkyl poly glucoside surfactants are also described in WO 92/19711, WO 92/08439, DE 4 029 035, JP 3 163 198, JO 3 174 796, EP 216 301, EP 280 143, WO91/13096, and WO 92/19711.
  • the overall performance of a detergent is judged by not only its ability to remove soils ans stains, e.g. greasy/oily soils, but also its ability to prevent redeposition of the soils, or the breakdown products of the soils or of any insoluble salt, on the article washed. Redeposition effects results in the articles being coated in an unseemly film, appearing streaked or being covered in visible spots which remain intact at the end of the wash process.
  • detergent compositions including laundry, dishwashing and hard surface cleaner, containing a specific lipolytic enzyme and an alkyl poly glucoside surfactant.
  • alkyl poly glucoside surfactants of the type disclosed hereinafter provide a stabilising and/or performance boosting function for the specific lipolytic enzyme.
  • the present invention relates to detergent compositions comprising a specific lipolytic enzyme and an alkyl poly glucoside surfactant.
  • An essential component of the detergent composition according to the invention is a specific lipolytic enzyme.
  • lipolytic enzyme is intended to indicate an enzyme exhibiting a lipid degrading capability, such as a capability of degrading a triglyceride, a phospholipid, a wax-ester or cutin.
  • the lipolytic enzyme may, e.g., be a lipase, a phospholipase, an esterase or a cutinase.
  • the specific lipolytic enzymes suitable for the present invention are those lipolytic enzymes which provide a significantly improved whiteness maintenance performance when compared to an identical hydrolytic activity (same amount of LU per liter of wash solution) of the LipolaseTM enzyme.
  • the significant whiteness maintenance performance as used herein can be visually evaluated by expert graders using the 0->4 panel score units (PSU) Scheffe scale (0 stands for no difference and 4 represents a very large difference) .
  • the specific lipolytic enzyme suitable for the present invention is incorporated into the detergent composition in accordance with the invention at a level of from 50 LU to 8500 LU per liter wash solution.
  • said lipolytic enzyme is present at a level of from 100 LU to 7500 LU per liter of wash solution. More preferably at a level of from 150 LU to 5000 LU per liter of wash solution.
  • Suitable specific lipolytic enzymes for use herein include those of bacterial and fungal origin.
  • the lipolytic enzymes from chemically or genetically modified mutants are included herein.
  • Preferred lipolytic enzymes include variants of lipolytic enzymes producible by Humicola lanuginosa and Thermomyces lanuginosus, or by cloning and expressing the gene responsible for producing said variants into a host organism, e.g. Aspergillus oryzae as described in European Patent Application 0 258 068, incorporated herein by reference.
  • Highly preferred lipolytic enzymes are variants 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.
  • An example of said variants is D96L lipolytic enzyme.
  • 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 the aspartic acid (D) residue at position 96 is changed to Leucine (L) . According to this nomenclature said substitution of aspartic acid to Leucine in position 96 is shown as : D96L.
  • a substrate for D96L was prepared by emulsifying glycerine tributyrate (Merck) using gum-arabic as emulsifier. Lipase activity was assayed at pH 7 using pH stat. method.
  • One unit of lipase activity is defined as the amount needed to liberate one micromole fatty acid per minute.
  • the detergent compositions according to the present invention comprise an alkyl poly glucoside surfactant of the formula :
  • R is on the average a C ⁇ Q to c 16' preferably C ⁇ 2 to C14, alkyl
  • G is a moiety derived from a reducing saccharide containing fron 5 to 6 carbons atoms, preferably a glucose unit
  • x is on the average from 1.0 to 3.0 preferably from about 1.1 to 1.5, and represent the average degree, of polymerisation of the alkyl polysaccharide surfactant.
  • x can only assume integral values.
  • the physical sample can be characterized by the average value of x, which can assume non-integral values. In the specification, the values of x are to be understood to be average values.
  • the polysaccharide hydrophilic portion of the surfactant contains from about 1 to about 3, preferably from 1.1. to about 1.5, saccharide units on the average.
  • the saccharide unit may be galactoside, glucoside, lactoside, fructoside, glucosyl, fructosyl, lactosyl and/or galactosyl units. Mixtures of these saccharide moieties may be used in the alkyl polysaccharide surfactant.
  • Glucoside is the preferred saccharide moiety.
  • Other saccharide moieties will act similarly, but because glucoside is the preferred saccharide moiety, the remaining disclosure will focus on the alkyl polyglucoside surfactant.
  • the hydrophobic group on the alkyl polysaccharide is an alkyl group, either saturated or unsaturated, branched or unbranched, containing from about 10 to about 16 carbon atoms on the average.
  • the alkyl group is primarily a straight chain saturated C ⁇ 2 to C ⁇ 4 alkyl group.
  • Any reducing saccharide containing 5 or 6 carbon atoms can be used, e.g., glucose, galactose and galactosyl moieties can be substituted for the glucosyl moieties (optionally the hydrophobic group is attached at the 2-, 3-, 4-, etc. positions thus giving a glucose or galactose as opposed to a glucoside or galactoside) .
  • the intersaccharide bonds can be, e.g., between the one position of the additional saccharide units and the 2- , 3-, 4-, and/or 6- positions on the preceding saccharide units.
  • the preferred alkylpolyglycosides have the formula
  • R 2 is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups contain from about 10 to about 18, preferably from about 12 to about 14, carbon atoms; n is 2 or 3, preferably 2; t is from 0 to about 10, preferably 0; and x is 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.
  • 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 glucoside
  • the additional glycosyl units can then be attached between their 1-position and the preceding glycosyl units 2-, 3-, 4- and/or 6-position, preferably predominately the 2-position.
  • Said alkyl poly glucoside surfactants are comprised within the detergent compositions of the present invention at a level from 0.1 to 10%, preferably from 1 to 6%, more preferably from 2 to 5% by weight of total composition.
  • the objective of the washing process of soiled fabrics is to clean these, i.e. to remove soils and stains from the soiled clothes.
  • the removed soils appear in the wash solution, they can redeposit onto the fabrics being washed.
  • the redeposition of soil has a strong negative impact on the whiteness of the fabric. But also the brightness and freshness of colored fabrics is reduced by such redeposition.
  • Whiteness maintenance is the monitoring of the whiteness of wash & wear fabrics over a number of washing cycles.
  • a good performing detergent has a good whiteness maintenance profile, i.e. it ensures that the whiteness of washed fabrics is maintained at a high level during the complete life cycle of wearing & washing by preventing as much as possible the redeposition onto white fabrics of removed soils.
  • the detergent compositions of the invention may also contain additional detergent components.
  • additional detergent components The precise nature of these additional components, and levels of incorporation thereof will depend on the physical form of the composition, and the nature of the cleaning operation for which it is to be used.
  • the cleaning compositions according to the invention can be liquid, paste, gels, bars, tablets, powder or granular forms. Granular compositions can also be in
  • liquid compositions can also be in a “concentrated” form.
  • compositions of the invention may for example, be formulated as hard surface cleaner, hand and machine dishwashing compositions, hand and machine laundry detergent compositions including laundry additive compositions and compositions suitable for use in the soaking and/or pretreatment of stained fabrics, rinse added fabric softener compositions.
  • compositions of the invention When formulated as compositions for use in manual dishwashing methods the compositions of the invention preferably contain a surfactant and preferably other detergent compounds selected from organic polymeric compounds, suds enhancing agents, group II metal ions, solvents, hydrotropes and additional enzymes.
  • a surfactant preferably other detergent compounds selected from organic polymeric compounds, suds enhancing agents, group II metal ions, solvents, hydrotropes and additional enzymes.
  • compositions suitable for use in a laundry machine washing method preferably contain both a surfactant and a builder compound and additionally one or more detergent components preferably selected from organic polymeric compounds, bleaching agents, additional enzymes, suds suppressors, dispersants, lime-soap dispersants, soil release polymer, soil suspension and anti-redeposition agents and corrosion inhibitors.
  • Laundry compositions can also contain softening agents, as additional detergent components.
  • compositions of the invention can also be used as detergent additive products. Such additive products are intended to supplement or boost the performance of conventional detergent compositions. If needed the density of the granular laundry detergent compositions herein ranges from 400 to 1200 g/litre, preferably 600 to 950 g/litre of composition measured at 20°C.
  • the "compact" form of the granular laundry detergent compositions herein is best reflected by density and, in terms of composition, by the amount of inorganic filler salt; inorganic filler salts are conventional ingredients of detergent compositions in powder form; in conventional detergent compositions, the filler salts are present in substantial amounts, typically 17-35% by weight of the total composition. In the compact compositions, the filler salt is present in amounts not exceeding 15% of the total composition, preferably not exceeding 10%, most preferably not exceeding 5% by weight of the composition.
  • the inorganic filler salts are selected from the alkali and alkaline-earth-metal salts of sulphates and chlorides.
  • a preferred filler salt is sodium sulphate.
  • Liquid detergent compositions according to the present invention can also be in a "concentrated form", in such case, the liquid detergent compositions according the present invention will contain a lower amount of water, compared to conventional liquid detergents.
  • the water content of the concentrated liquid detergent is preferably less than 40%, more preferably less than 30%, most preferably less than 20% by weight of the detergent composition.
  • the detergent compositions according to the present invention can additionally comprise a surfactant system wherein the surfactant can be selected from other nonionic and/or anionic and/or cationic and/or ampholytic and/or zwitterionic and/or semi-polar surfactants.
  • the surfactant is typically present at a level of from 0.1% to 60% by weight. More preferred levels of incorporation are 1% to 35% by weight, most preferably from 1% to 25% by weight of detergent compositions in accord with the invention.
  • Preferred surfactant systems to be used according to the present invention comprise as a surfactant one or more of the nonionic and/or anionic surfactants described herein.
  • Polyethylene, polypropylene, and polybytylene oxide condensates of alkyl phenols are suitable for use as the nonionic surfactant of the surfactant systems of the present invention, with the polyethylene oxide condensates being preferred.
  • These compounds include the condensation products of alkyl phenols having an alkyl group containing from about 6 to about 14 carbon atoms, preferably from about 8 to about 14 carbon atoms, in either a straight- chain or branched-chain configuration with the alkylene oxide.
  • the ethylene oxide is present in an amount equal to from about 2 to about 25 moles, more preferably from about 3 to about 15 moles, of ethylene oxide per mole of alkyl phenol.
  • nonionic surfactants of this type include IgepalTM CO-630, marketed by the GAF Corporation; and TritonTM X-45, X-114, X-100 and X-102, all marketed by the Rohm & Haas Company. These surfactants are commonly referred to as alkylphenol alkoxylates (e.g., alkyl phenol ethoxylates) .
  • alkylphenol alkoxylates e.g., alkyl phenol ethoxylates
  • the condensation products of primary and secondary aliphatic alcohols with from about 1 to about 25 moles of ethylene oxide are suitable for use as the nonionic surfactant of the nonionic surfactant systems of the present invention.
  • the alkyl chain of the aliphatic alcohol can either be straight or branched, primary or secondary, and generally contains from about 8 to about 22 carbon atoms.
  • About 2 to about 7 moles of ethylene oxide and most preferably from 2 to 5 moles of ethylene oxide per mole of alcohol are present in said condensation products.
  • nonionic surfactants of this type include TergitolTM 15-S-9 (the condensation product of linear alcohol with 9 moles ethylene oxide) , TergitolTM 24- L-6 NMW (the condensation product of Ci2 ⁇ c 14 primary alcohol with 6 moles ethylene oxide with a narrow molecular weight distribytion) , both marketed by Union Carbide Corporation; NeodolTM 45-9 (the condensation product of C14-C15 linear alcohol with 9 moles of ethylene oxide) ,
  • NeodolTM 23-3 (the condensation product of Ci2 -C 13 linear alcohol with 3.0 moles of ethylene oxide), NeodolTM 45-7
  • NeodolTM 45-5 (the condensation product of C14-C15 linear alcohol with 5 moles of ethylene oxide) marketed by Shell Chemical Company
  • KyroTM EOB the condensation product of C13-C15 alcohol with 9 moles ethylene oxide
  • Genapol LA 030 or 050 (the condensation product of C ] _2 ⁇ C14 alcohol with 3 or 5 moles of ethylene oxide) marketed by Hoechst.
  • Preferred range of HLB in these products is from 8-11 and most preferred from 8-10.
  • the condensation products of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol are also suitable for use as the additional nonionic surfactant systems of the present invention.
  • the hydrophobic portion of these compounds will preferably have a molecular weight of from about 1500 to about 1800 and will exhibit water insolubility.
  • the addition of polyoxyethylene moieties to this hydrophobic portion tends to increase the water solubility of the molecule as a whole, and the liquid character of the product is retained up to the point where the polyoxyethylene content is about 50% of the total weight of the condensation product, which corresponds to condensation with up to about 40 moles of ethylene oxide.
  • Examples of compounds of this type include certain of the commercially- available PluronicTM surfactants, marketed by BASF.
  • nonionic surfactant of the nonionic surfactant system of the present invention are the condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylenediamine.
  • the hydrophobic moiety of these products consists of the reaction product of ethylenediamine and excess propylene oxide, and generally has a molecular weight of from 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.
  • this type of nonionic surfactant include certain of the commercially available TetronicTM compounds, marketed by BASF.
  • nonionic surfactant of the surfactant systems of the present invention are polyethylene oxide condensates of alkyl phenols, condensation products of primary and secondary aliphatic alcohols with from about 1 to about 25 moles of ethylene oxide, alkylpolysaccharides, and mixtures thereof. Most preferred are C8-C14 alkyl phenol ethoxylates having from 3 to 15 ethoxy groups and alcohol ethoxylates (preferably Cio avg.) having from 2 to 10 ethoxy groups, and mixtures thereof. Highly preferred nonionic surfactants are polyhydroxy fatty acid amide surfactants of the formula.
  • R 1 is H, or R 1 is C ⁇ -q 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 1 is methyl
  • R 2 is a straight C ⁇ _ ⁇ __i5 alkyl or C ⁇ g_i8 alkyl or alkenyl chain such as coconut alkyl or mixtures thereof
  • Z is derived from a reducing sugar such as glucose, fructose, maltose, lactose, in a reductive amination reaction.
  • the nonionic surfactant systems of the present invention act to improve the greasy/oily stain removal properties of such detergent compositions across a broad range of cleaning conditions.
  • Suitable anionic surfactants to be used are linear alkyl benzene sulfonate, alkyl ester sulfonate surfactants including linear esters of Cg-C20 carboxylic acids (i.e., fatty acids) which are sulfonated with gaseous SO 3 according to "The Journal of the American Oil Chemists Society", 52 (1975), pp. 323-329. Suitable starting materials would include natural fatty substances as derived from tallow, palm oil, etc.
  • the preferred alkyl ester sulfonate surfactant, especially for laundry applications comprise alkyl ester sulfonate surfactants of the structural formula : 0
  • R 3 is a Cg-C20 hydrocarbyl, preferably an alkyl, or combination thereof
  • R ⁇ is a C ⁇ -Cg 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.
  • alkyl sulfate surfactants which are water soluble salts or acids of the formula ROSO3M wherein R preferably is a C ⁇ o ⁇ c 24 hydrocarbyl, preferably an alkyl or hydroxyalkyl having a c 10 ⁇ c 20 alkyl component, more preferably a Ci2 -C ⁇ g alkyl or hydroxyalkyl, and M is H or a cation, e.g., an alkali metal cation (e.g. sodium, potassium, lithium), or ammonium or substituted ammonium (e.g.
  • R preferably is a C ⁇ o ⁇ c 24 hydrocarbyl, preferably an alkyl or hydroxyalkyl having a c 10 ⁇ c 20 alkyl component, more preferably a Ci2 -C ⁇ g alkyl or hydroxyalkyl
  • M is H or a cation, e.g., an alkali metal cation (e.g. sodium, potassium, lithium),
  • alkylamines such as ethylamine, diethylamine, triethylamine, and mixtures thereof, and the like.
  • alkyl chains of C ⁇ -C ⁇ g are preferred for lower wash temperatures (e.g. below about 50°C) and C ⁇ g-ig alkyl chains are preferred for higher wash temperatures (e.g. above about 50°C) .
  • Other anionic surfactants useful for detersive purposes can also be included in the detergent compositions of the present invention.
  • salts including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts
  • soap Cg-C22 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.
  • alkylpolyglycolethersulfates (containing up to 10 moles of ethylene oxide) ; alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, paraffin sulfonates, alkyl phosphates, isethionates such as the acyl isethionates, N-acyl taurates, alkyl succinamates and sulfosuccinates, monoesters of sulfosuccinates (especially saturated and unsaturated C ⁇ -Cig monoesters) and diesters of sulfosuccinates (especially saturated and unsaturated Cs-Ci2 diesters) , acyl sarcosinates, sulfates of alkylpolysaccharides such
  • alkyl alkoxylated sulfate surfactants hereof are water soluble salts or acids of the formula R0(A) m S03M wherein R is an unsubstituted CIQ -C 24 alkyl or hydroxyalkyl group having a C ⁇ o ⁇ C24 alkyl component, preferably a Ci2 _c 2 0 alkyl or hydroxyalkyl, more preferably Ci2 ⁇ Cl8 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 CIQ -C 24 alkyl or hydroxyalkyl group having a C ⁇ o ⁇ C24 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 c 12 ⁇ c 18 alkyl polyethoxylate (1.0) sulfate (Ci2 -c ⁇ gE(1.0)M) , Ci2 _ Cl8 alkyl polyethoxylate (2.25) sulfate (C 1 2"C 1 gE(2.25)M) , C 12 - C 18 alkyl polyethoxylate (3.0) sulfate (C 12 -C 18 E(3.0)M) , and c i2 ⁇ c 18 alkyl polyethoxylate (4.0) sulfate (C ⁇ 2 ⁇ C ⁇ gE(4.0)M), wherein M is conveniently selected from sodium and potassium.
  • the detergent compositions of the present invention typically comprise from about 1% to about 40%, preferably from about 3% to about 20% by weight of such anionic surfactants.
  • the detergent compositions of the present invention may also contain cationic, ampholytic, zwitterionic, and semi-polar surfactants, as well as the nonionic and/or anionic surfactants other than those already described herein.
  • Cationic detersive surfactants suitable for use in the detergent compositions of the present invention are those having one long-chain hydrocarbyl group. Examples of such cationic surfactants include the ammonium surfactants such as alkyltrimethylammonium 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 )-, -CH 2 CH(CH 2 OH)-, -CH 2 CH 2 CH 2 -, and mixtures thereof
  • each R 4 is selected from the group consisting of C1-C4 alkyl, C1-C4 hydroxyalkyl, benzyl ring structures formed by joining the two R 4 groups, -CH2CHOH- CHOHCOR 6 CHOHCH2 ⁇ H wherein R 6 is any hexose or hexose polymer having a molecular weight less than about 1000, and hydrogen when y is not 0
  • R 5 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 and
  • Highly preferred cationic surfactants are the water- soluble quaternary ammonium compounds useful in the present composition having the formula :
  • each of R 2 , R3 and R4 is independently C1-C4 alkyl, C1-C4 hydroxy alkyl, benzyl, and -(C2H4Q) X H where x has a value from 2 to 5, and X is an anion.
  • R2, R3 or R4 should be benzyl.
  • the preferred alkyl chain length for R is C12-C15 particularly where the alkyl group is a mixture of chain lengths derived from coconut or palm kernel fat or is derived synthetically by olefin byild up or OXO alcohols synthesis.
  • 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
  • Quaternary ammonium surfactants suitable for the present invention have the formula (I) :
  • Rl is a short chainlength alkyl (C6-C10) or alkylamidoalkyl of the formula (II) :
  • Formula II y is 2-4, preferably 3. whereby R2 is H or a C1-C3 alkyl, whereby x is 0-4, preferably 0-2, most preferably 0, whereby R3, R4 and R5 are either the same or different and can be either a short chain alkyl (C1-C3) or alkoxylated alkyl of the formula III,
  • X ⁇ is a counterion, preferably a halide, e.g. chloride or methylsulfate.
  • R6 is C ⁇ -C4 and z is 1 or 2.
  • the detergent compositions of the present invention typically comprise from 0.2% to about 25%, preferably from about 1% to about 8% by weight of such cationic surfactants.
  • Ampholytic surfactants are also suitable for use in the detergent compositions of the present invention. These surfactants can be broadly described as aliphatic derivatives of secondary or tertiary amines, or aliphatic derivatives of heterocyclic secondary and tertiary amines in which the aliphatic radical can be straight- or branched-chain.
  • One of the aliphatic substituents contains at least 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.
  • the detergent compositions of the present invention typically comprise from 0.2% to about 15%, preferably from about 1% to about 10% by weight of such ampholytic surfactants.
  • Zwitterionic surfactants are also suitable for use in detergent compositions. These surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. See U.S. Patent No. 3,929,678 to Laughlin et al., issued December 30, 1975 at column 19, line 38 through column 22, line 48, for examples of zwitterionic surfactants.
  • the detergent compositions of the present invention typically comprise from 0.2% to about 15%, preferably from about 1% to about 10% by weight of such zwitterionic surfactants.
  • Semi-polar nonionic surfactants are a special category of nonionic I surfactants which include water-soluble amine oxides containing one alkyl moiety of from about 10 to about 18 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from about 1 to about 3 carbon atoms; water- soluble phosphine oxides containing one alkyl moiety of from about 10 to about 18 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from about 1 to about 3 carbon atoms; and water-soluble sulfoxides containing one alkyl moiety of from about 10 to about 18 carbon atoms and a moiety selected from the group consisting of alkyl and hydroxyalkyl moieties of from about 1 to about 3 carbon atoms.
  • Semi-polar nonionic detergent surfactants include the amine oxide surfactants having the formula
  • R 3 (OR 4 )xN(R 5 )2 wherein R 3 is an alkyl, hydroxyalkyl, or alkyl phenyl group or mixtures therof containing from about 8 to about 22 carbon atoms; R4 is an alkylene or hydroxyalkylene group containing from about 2 to about 3 carbon atoms or mixtures thereof; x is from 0 to about 3; and each R ⁇ is an alkyl or hydroxyalkyl group containing from about 1 to about 3 carbon atoms or a polyethylene oxide group containing from about 1 to about 3 ethylene oxide groups.
  • the R 5 groups can be attached to each other, e.g., through an oxygen or nitrogen atom, to form a ring structure.
  • amine oxide surfactants in particular include CiQ-Cig alkyl dimethyl amine oxides and Cg-Ci2 alkoxy ethyl dihydroxy ethyl amine oxides.
  • the laundry detergent compositions of the present invention typically comprise from 0.2% to about 15%, preferably from about 1% to about 10% by weight of such semi-polar nonionic surfactants.
  • the detergent composition of the present invention may further comprise a cosurfactant selected from the group of primary or tertiary amines.
  • Suitable primary amines for use herein include amines according to the formula R1NH2 wherein Ri is a C5-C12 preferably Cg-Cio alkyl chain or R4X(CH2 )n , X is -O-,- C(0)NH- or -NH- R4 is a Cg-C ⁇ alkyl chain n is between 1 to 5, preferably 3.
  • Ri 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 amido propylamine and amido propylamine.
  • Suitable tertiary amines for use herein include tertiary amines having the formula R1R2R 3 N wherein Rl and R2 are C ⁇ Cg alkylchains or
  • R3 is either a C6-C12, preferably Cg-Cio alkyl chain, or R3 is R4X(CH2 )n , whereby X is -0-, -C(0)NH- or -NH- ⁇ 4 is a c 4 ⁇ c 12, n i s 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
  • Most preferred amines of the present invention include 1-octylamine, 1-hexylamine, 1-decylamine, 1- dodecylamine,C8-10oxypropylamine, 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 detergent compositions can in addition to specific lipolytic enzyme enzymes 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, other amylases, xylanases, other lipases, other esterases, other cutinases, pectinases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases, pentosanases, malanases, ⁇ -glucanases, arabinosidases, chondroitinase, laccase or mixtures thereof.
  • a preferred combination is a cleaning composition having a cocktail of conventional applicable enzymes like protease, amylase, lipase, cutinase and/or cellulase in conjunction with one or more plant cell wall degrading enzymes.
  • 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, Maxapem and Properase by Gist-Brocades, those sold by Genencor International, and those sold under the tradename Opticlean and Optimase by Solvay Enzymes.
  • proteases described in patent applications EP 251 446 WO91/06637 and WO95/10591 and USSN 08/322 676 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.
  • Suitable lipase enzymes for detergent usage include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as disclosed in British Patent 1,372,034.
  • Suitable lipases include those which show a positive immunological cross- reaction with the antibody of the lipase, produced by the microorganism Pseudomonas fl uorescent IAM 1057. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade name Lipase P "Amano, " hereinafter referred to as "Amano-P".
  • Especially suitable lipases are lipases such as Ml Lipase R anc * Lipomax R (Gist-Brocades) and Lipolase R (Novo) which have found to be very effective when used in combination with the compositions of the present invention.
  • cutinases [EC 3.1.1.50] which can be considered as a special kind of lipase, namely lipases which do not require interfacial activation.
  • Suitable cutinases are described in WO 94/14963 and WO 94/14964. Addition of cutinases to detergent compositions have been described in e.g. WO-A-88/09367 (Genencor) .
  • These other 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 can be included for removal of carbohydrate-based stains.
  • WO/94/02597 Novo Nordisk A/S published February 03, 1994, describes cleaning compositions which incorporate mutant amylases. See also WO/94/18314, Genencor, published August 18, 1994 and WO/95/10603, Novo Nordisk A/S, published April 20,1995.
  • Other amylases known for use in cleaning compositions include both ⁇ - and ⁇ -amylases.
  • ⁇ -Amylases are known in the art and include those disclosed in US Pat. no.
  • amylases include stability-enhanced amylases including Purafact Ox Am R described in WO 94/18314, published August 18, 1994 and amylase variants having additional modification in the immediate parent available from Novo Nordisk A/S, disclosed in WO 95/10603, published April 95.
  • Examples of commercial ⁇ -amylases products are Termamyl ® , Ban ® , Fungamyl ® and Duramyl ® all available from Novo Nordisk A/S Denmark.
  • W095/26397 describes other suitable amylases : ⁇ - amylases characterised by having a specific activity at least 25% higher than the specific activity of Termamyl ® at a temperature range of 25°C to 55°C and at a pH value in the range of 8 to 10, measured by the Phadebas ® ⁇ -amylase activity assay.
  • ⁇ - amylases characterised by having a specific activity at least 25% higher than the specific activity of Termamyl ® at a temperature range of 25°C to 55°C and at a pH value in the range of 8 to 10, measured by the Phadebas ® ⁇ -amylase activity assay.
  • Other amylolytic enzymes with improved properties with respect to the activity level and the combination of thermostability and a higher activity level are described in W095/35382.
  • 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.
  • the enzymes can be added as single ingredients (prills, granulates, stabilised liquids, etc..) or as mixture of of two or more enzymes (e.g. cogranulates) .
  • enzyme oxidation scavengers which are described in the copending European patent application 92870018.6 filed on January 31, 1992.
  • enzyme oxidation scavengers are ethoxylated tetraethylene polyamines.
  • Bleach systems that can be included in the detergent compositions of the present invention include bleaching agents such as PBl, PB4 and percarbonate with a particle size of 400-800 microns. These bleaching agent components can include one or more oxygen bleaching agents and, depending upon the bleaching agent chosen, one or more bleach activators. When present oxygen bleaching compounds will typically be present at levels of from about 1% to about 25%.
  • the bleaching agent component for use herein can be any of the bleaching agents useful for detergent compositions including oxygen bleaches as well as others known in the art.
  • the bleaching agent suitable for the present invention can be an activated or non-activated bleaching agent.
  • oxygen bleaching agent that can be used encompasses percarboxylic acid bleaching agents and salts thereof. Suitable examples of this class of agents include magnesium monoperoxyphthalate hexahydrate, the magnesium salt of meta-chloro perbenzoic acid, 4- nonylamino-4-oxoperoxybytyric acid and diperoxydodecanedioic acid.
  • Such bleaching agents are disclosed in U.S. Patent 4,483,781, U.S. Patent Application 740,446, European Patent Application 0,133,354 and U.S. Patent 4,412,934.
  • Highly preferred bleaching agents also include 6-nonylamino-6-oxoperoxycaproic acid as described in U.S. Patent 4,634,551.
  • bleaching agents that can be used encompasses the halogen bleaching agents.
  • hypohalite bleaching agents include trichloro isocyanuric acid and the sodium and potassium dichloroisocyanurates and N-chloro and N-bromo alkane sulphonamides. Such materials are normally added at 0.5-10% by weight of the finished product, preferably 1-5% by weight.
  • the hydrogen peroxide releasing agents can be used in combination with bleach activators such as tetraacetylethylenediamine (TAED), nonanoyloxybenzene- sulfonate (NOBS, described in US 4,412,934), 3,5,- trimethylhexanoloxybenzenesulfonate (ISONOBS, described in EP 120, 591) ,pentaacetylglucose (PAG) or Phenolsulfonate ester of N-nonanoyl-6-aminocaproic acid (NACA-OBS, described in WO94/28106) , which are perhydrolyzed to form a peracid as the active bleaching species, leading to improved bleaching effect.
  • bleach activators such as tetraacetylethylenediamine (TAED), nonanoyloxybenzene- sulfonate (NOBS, described in US 4,412,934), 3,5,- trimethylhexanoloxybenz
  • bleaching agents including peroxyacids and bleaching systems comprising bleach activators and peroxygen bleaching compounds for use in detergent compositions according to the invention are described in our co-pending applications USSN 08/136, 626, PCT/US95/07823, W095/27772, W095/27773, W095/27774 and W095/27775.
  • the hydrogen peroxide may also be present by adding an enzymatic system (i.e. an enzyme and a substrate therefore) which is capable of generating hydrogen peroxide at the beginning or during the washing and/or rinsing process.
  • an enzymatic system i.e. an enzyme and a substrate therefore
  • Such enzymatic systems are disclosed in EP Patent Application 91202655.6 filed October 9, 1991.
  • Bleaching agents other than oxygen bleaching agents are also known in the art and can be utilized herein.
  • One type of non-oxygen bleaching agent of particular interest includes photoactivated bleaching agents such as the sulfonated zinc and/or aluminum phthalocyanines. These materials can be deposited upon the substrate during the washing process. Upon irradiation with light, in the presence of oxygen, such as by hanging clothes out to dry in the daylight, the sulfonated zinc phthalocyanine is activated and, consequently, the substrate is bleached.
  • Preferred zinc phthalocyanine and a photoactivated bleaching process are described in U.S. Patent 4,033,718.
  • detergent compositions will contain about 0.025% to about 1.25%, by weight, of sulfonated zinc phthalocyanine.
  • compositions according to the present invention may further comprise 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, diethylene triamine pentamethyleneacetate, metal ion sequestrants such as aminopolyphosphonates, particularly ethylenediamine tetramethylene phosphonic acid and diethylene triamine pentamethylenephosphonic acid.
  • Phosphate builders as sodium tripolyphosphate can also be used herein.
  • Suitable builders can be an inorganic ion exchange material, commonly an inorganic hydrated aluminosilicate material, more particularly a hydrated synthetic zeolite such as hydrated zeolite A, X, B, HS or MAP.
  • SKS-6 is a crystalline layered silicate consisting of sodium silicate (Na2Si2 ⁇ 5) .
  • Suitable polycarboxylates containing one carboxy group include lactic acid, glycolic acid and ether derivatives thereof as disclosed in Belgian Patent Nos. 831,368, 821,369 and 821,370.
  • Polycarboxylates containing two carboxy groups include the water-soluble salts of succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid, diglycollic acid, tartaric acid, tartronic acid and fumaric acid, as well as the ether carboxylates described in German Offenlegenschrift 2,446,686, and 2,446,687 and U.S. Patent No. 3,935,257 and the sulfinyl carboxylates described in Belgian Patent No. 840,623.
  • Polycarboxylates containing three carboxy groups include, in particular, water-soluble citrates, aconitrates and citraconates as well as succinate derivatives such as the carboxymethyloxysuccinates described in British Patent No. 1,379,241, lactoxysuccinates described in Netherlands Application 7205873, and the oxypolycarboxylate materials such as 2-oxa-l, 1, 3-propane tricarboxylates described in British Patent No. 1,387,447.
  • Polycarboxylates containing four carboxy groups include oxydisuccinates disclosed in British Patent No. 1,261,829, 1, 1,2,2-ethane tetracarboxylates, 1,1,3,3- propane tetracarboxylates and 1, 1, 2, 3-propane tetracarboxylates.
  • Polycarboxylates containing sulfo substituents include the sulfosuccinate derivatives disclosed in British Patent Nos. 1,398,421 and 1,398,422 and in U.S. Patent No. 3,936,448, and the sulfonated pyrolysed citrates described in British Patent No. 1,082,179, while polycarboxylates containing phosphone substituents are disclosed in British Patent No. 1,439,000.
  • Alicyclic and heterocyclic polycarboxylates include cyclopentane-cis,cis, cis-tetracarboxylates, cyclopentadienide pentacarboxylates, 2, 3, 4, 5-tetrahydro- furan - cis, cis, cis-tetracarboxylates, 2, 5-tetrahydro- furan -cis - dicarboxylates, 2,2, 5, 5-tetrahydrofuran tetracarboxylates, 1, 2, 3, 4, 5, 6-hexane -hexacar-boxylates and and carboxymethyl derivatives of polyhydric alcohols such as sorbitol, mannitol and xylitol.
  • Aromatic poly ⁇ carboxylates include mellitic acid, pyromellitic acid and the phthalic acid derivatives disclosed in British Patent No. 1,425,343.
  • the preferred polycarboxylates are hydroxycarboxylates containing up to three carboxy groups per molecule, more particularly citrates.
  • Preferred builder systems for use in the present compositions include a mixture of a water-insoluble aluminosilicate builder such as zeolite A or of a layered silicate (SKS-6) , and a water-soluble carboxylate chelating agent such as citric acid.
  • a water-insoluble aluminosilicate builder such as zeolite A or of a layered silicate (SKS-6)
  • a water-soluble carboxylate chelating agent such as citric acid.
  • a suitable chelant for inclusion in the detergent compositions in accordance with the invention is ethylenediamine-N,N'-disuccinic acid (EDDS) or the alkali metal, alkaline earth metal, ammonium, or substituted ammonium salts thereof, or mixtures thereof.
  • EDDS compounds are the free acid form and the sodium or magnesium salt thereof. Examples of such preferred sodium salts of EDDS include Na2EDDS and Na4EDDS. Examples of such preferred magnesium salts of EDDS include MgEDDS and Mg2EDDS. The magnesium salts are the most preferred for inclusion in compositions in accordance with the invention.
  • Preferred builder systems include a mixture of a water-insoluble aluminosilicate builder such as zeolite A, and a watersoluble carboxylate chelating agent such as citric acid.
  • builder materials that can form part of the builder system for use in granular compositions include inorganic materials such as alkali metal carbonates, bicarbonates, silicates, and organic materials such as the organic phosphonates, amino polyalkylene phosphonates and amino polycarboxylates.
  • inorganic materials such as alkali metal carbonates, bicarbonates, silicates
  • organic materials such as the organic phosphonates, amino polyalkylene phosphonates and amino polycarboxylates.
  • suitable water-soluble organic salts are the homo- or co-polymeric acids or their salts, in which the polycarboxylic acid comprises at least two carboxyl radicals separated from each other by not more than two carbon atoms.
  • Polymers of this type are disclosed in GB-A-1, 596, 756.
  • Examples of such salts are polyacrylates of MW 2000-5000 and their copolymers with maleic anhydride, such copolymers having a molecular weight of from 20,000 to 70,000, especially about 40,000.
  • Detergency builder salts are normally included in amounts of from 10% to 80% by weight of the composition preferably from 20% to 70% and most usually from 30% to 60% by weight.
  • a suds suppressor exemplified by silicones, and silica-silicone mixtures.
  • Silicones can be generally represented by alkylated polysiloxane materials while silica is normally used in finely divided forms exemplified by silica aerogels and xerogels and hydrophobic silicas of various types. These materials can be incorporated as particulates in which the suds suppressor is advantageously releasably incorporated in a water-soluble or water-dispersible, substantially non- surface-active detergent impermeable carrier.
  • the suds suppressor can be dissolved or dispersed in a liquid carrier and applied by spraying on to one or more of the other components.
  • a preferred silicone suds controlling agent is disclosed in Bartollota et al. U.S. Patent 3 933 672.
  • Other particularly useful suds suppressors are the self- emulsifying silicone suds suppressors, described in German Patent Application DTOS 2 646 126 published April 28, 1977.
  • An example of such a compound is DC-544, commercially available from Dow Corning, which is a siloxane-glycol copolymer.
  • Especially preferred suds controlling agent are the suds suppressor system comprising a mixture of silicone oils and 2-alkyl-alcanols. Suitable 2-alkyl-alkanols are 2- bytyl-octanol which are commercially available under the trade name Isofol 12 R.
  • Such suds suppressor system are described in Copending European Patent application N 92870174.7 filed 10 November, 1992.
  • Especially preferred silicone suds controlling agents are described in Copending European Patent application N°92201649.8.
  • Said compositions can comprise a silicone/silica mixture in combination with fumed nonporous silica such as Aerosil R .
  • the suds suppressors described above are normally employed at levels of from 0.001% to 2% by weight of the composition, preferably from 0.01% to 1% by weight.
  • detergent compositions may be employed, such as soil-suspending agents, soil-release agents, optical brighteners, abrasives, bactericides, tarnish inhibitors, coloring agents, and/or encapsulated or non-encapsulated perfumes.
  • encapsulating materials are water soluble capsules which consist of a matrix of polysaccharide and polyhydroxy compounds such as described in GB 1,464, 616.
  • Suitable water soluble encapsulating materials comprise dextrins derived from ungelatinized starch acid- esters of substituted dicarboxylic acids such as described in US 3,455,838. These acid-ester dextrins are,preferably, prepared from such starches as waxy maize, waxy sorghum, sago, tapioca and potato. Suitable examples of said encapsulating materials include N-Lok manufactured by National Starch. The N-Lok encapsulating material consists of a modified maize starch and glucose. The starch is modified by adding monofunctional substituted groups such as octenyl succinic acid anhydride.
  • Antiredeposition and soil suspension agents suitable herein include cellulose derivatives such as methylcellulose, carboxymethylcellulose and hydroxyethylcellulose, and homo- or co-polymeric polycarboxylic acids or their salts.
  • Polymers of this type include the polyacrylates and maleic anhydride-acrylic acid copolymers previously mentioned as builders, as well as copolymers of maleic anhydride with ethylene, methylvinyl ether or methacrylic acid, the maleic anhydride constituting at least 20 mole percent of the copolymer. These materials are normally used at levels of from 0.5% to 10% by weight, more preferably from 0.75% to 8%, most preferably from 1% to 6% by weight of the composition.
  • Preferred optical brighteners are anionic in character, examples of which are disodium 4, 4'-bis- (2- diethanolamino-4-anilino -s- triazin-6-ylamino) stilbene- 2:2' disulphonate, disodium 4, - 4 '-bis- (2-morpholino-4- anilino-s-triazin-6-ylamino-stilbene-2:2' - disulphonate, disodium 4,4' - bis- (2, 4-dianilino-s-triazin-6- ylamino) stilbene-2:2' - disulphonate, monosodium 4 ',4'' - bis- (2, 4-dianilino-s-tri-azin-6 ylamino) stilbene-2- sulphonate, disodium 4,4' -bis- (2-anilino-4- (N-methyl-N-2- hydroxyethylamino) -s-triazin-6-ylamino) stilbene
  • polyethylene glycols particularly those of molecular weight 1000-10000, more particularly 2000 to 8000 and most preferably about 4000. These are used at levels of from 0.20% to 5% more preferably from 0.25% to 2.5% by weight. These polymers and the previously mentioned homo- or co-polymeric polycarboxylate salts are valuable for improving whiteness maintenance, fabric ash deposition, and cleaning performance on clay, proteinaceous and oxidizable soils in the presence of transition metal impurities.
  • Soil release agents useful in compositions of the present invention are conventionally copolymers or terpolymers of terephthalic acid with ethylene glycol and/or propylene glycol units in various arrangements. Examples of such polymers are disclosed in the commonly assigned US Patent Nos. 4116885 and 4711730 and European Published Patent Application No. 0 272 033. A particular preferred polymer in accordance with EP-A-0 272 033 has the formula
  • polyesters as random copolymers of dimethyl terephthalate, dimethyl sulfoisophthalate, 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 terephthalic acid, about 16% by weight of propane -1.2 diol, about 10% by weight ethylene glycol about 13% by weight of dimethyl sulfobenzoic acid and about 15% by weight of sulfoisophthalic 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.
  • chlorine scavenger such as perborate, ammonium sulfate, sodium sulphite or polyethyleneimine at a level above 0.1% by weight of total composition, in the formulas will provide improved through the wash stability of the amylase enzymes.
  • Compositions comprising chlorine scavenger are described in the European patent application 92870018.6 filed January 31, 1992.
  • Fabric softening agents can also be incorporated into laundry detergent compositions in accordance with the present invention. These agents may be inorganic or organic in type. Inorganic softening agents are exemplified by the smectite clays disclosed in GB-A-1 400 898 and in USP 5,019,292. Organic fabric softening agents include the water, insoluble tertiary amines as disclosed in GB-A1 514 276 and EP-B0 011 340 and their combination with mono C12- C14 quaternary ammonium salts are disclosed in EP-B-0 026 527 and EP-B-0 026 528 and di-long-chain amides as disclosed in EP-B-0 242 919. Other useful organic ingredients of fabric softening systems include high molecular weight polyethylene oxide materials as disclosed in EP-A-0 299 575 and 0 313 146.
  • Levels of smectite clay are normally in the range from 2% to 20%, more preferably from 5% to 15% by weight, with the material being added either spray-dried or as a dry mixed component.
  • Organic fabric softening agents such as the water-insoluble tertiary amines or dilong chain amide materials are incorporated at levels of from 0.5% to 5% by weight, normally from 1% to 3% by weight whilst the high molecular weight polyethylene oxide materials and the water soluble cationic materials are added at levels of from 0.1% to 2%, normally from 0.15% to 1.5% by weight.
  • These materials are normally added to the spray dried portion of the composition, although in some instances it may be more convenient to add them as a dry mixed particulate, or spray them as molten liquid on to other solid components of the composition.
  • the detergent composition of the present invention can also include compounds for inhibiting dye transfer from one fabric to another of solubilized and suspended dyes encountered during fabric laundering operations involving colored fabrics.
  • the detergent compositions according to the present invention also comprise from 0.001% to 10 %, preferably from 0.01% to 2%, more preferably from 0.05% to 1% by weight of polymeric dye transfer inhibiting agents.
  • Said polymeric dye transfer inhibiting agents are normally incorporated into detergent compositions in order to inhibit the transfer of dyes from colored fabrics onto fabrics washed therewith. These polymers have the ability to complex or adsorb the fugitive dyes washed out of dyed fabrics before the dyes have the opportunity to become attached to other articles in the wash.
  • polymeric dye transfer inhibiting agents are polyamine N-oxide polymers, copolymers of N- vinylpyrrolidone and N-vinylimidazole, polyvinylpyrrolidone polymers, polyvinyloxazolidones and polyvinylimidazoles or mixtures thereof.
  • polyamine N-oxide polymers suitable for use contain units having the following structure formula :
  • P is a polymerisable unit, whereto the R-N-0 group can be attached to or wherein the R-N-0 group forms part of the polymerisable unit or a combination of both.
  • N-0 group can be represented by the following general structures :
  • Rl, R2, and R3 are aliphatic groups, aromatic, heterocyclic or alicyclic groups or combinations thereof, x or/and y or/and z is 0 or 1 and wherein the nitrogen of the N-0 group can be attached or wherein the nitrogen of the N-0 group forms part of these groups.
  • the N-0 group can be part of the polymerisable unit (P) or can be attached to the polymeric backbone or a combination of both.
  • Suitable polyamine N-oxides wherein the N-0 group forms part of the polymerisable unit comprise polyamine N-oxides wherein R is selected from aliphatic, aromatic, alicyclic or heterocyclic groups.
  • R is selected from aliphatic, aromatic, alicyclic or heterocyclic groups.
  • One class of said polyamine N-oxides comprises the group of polyamine N-oxides wherein the nitrogen of the N-0 group forms part of the R-group.
  • Preferred polyamine N-oxides are those wherein R is a heterocyclic group such as pyrridine, pyrrole, imidazole, pyrrolidine, piperidine, quinoline, acridine and derivatives thereof.
  • Another class of said polyamine N-oxides comprises the group of polyamine N-oxides wherein the nitrogen of the N-0 group is attached to the R-group.
  • polyamine N-oxides are the polyamine oxides whereto the N-0 group is attached to the polymerisable unit.
  • Preferred class of these polyamine N-oxides are the polyamine N-oxides having the general formula (I) wherein R is an aromatic, heterocyclic or alicyclic groups wherein the nitrogen of the N-0 functional group is part of said R group.
  • polyamine oxides wherein R is a heterocyclic compound such as pyrridine, pyrrole, imidazole and derivatives thereof.
  • R is a heterocyclic compound such as pyrridine, pyrrole, imidazole and derivatives thereof.
  • Another preferred class of polyamine N-oxides are the polyamine oxides having the general formula (I) wherein R are aromatic, heterocyclic or alicyclic groups wherein the nitrogen of the N-0 functional group is attached to said R groups.
  • polyamine oxides wherein R groups can be aromatic such as phenyl.
  • Any polymer backbone can be used as long as the amine oxide polymer formed is water-soluble and has dye transfer inhibiting properties.
  • suitable polymeric backbones are polyvinyls, polyalkylenes, polyesters, polyethers, polyamide, polyimides, polyacrylates and mixtures thereof.
  • the amine N-oxide polymers of the present invention typically have a ratio of amine to the amine N-oxide of
  • the amount of amine oxide groups present in the polyamine oxide polymer can be varied by appropriate copolymerization or by appropriate degree of N- oxidation.
  • the ratio of amine to amine N-oxide is from 2:3 to 1:1000000. More preferably from 1:4 to
  • the polymers of the present invention actually encompass random or block copolymers where one monomer type is an amine N- oxide and the other monomer type is either an amine N-oxide or not.
  • the amine oxide unit of the polyamine N-oxides has a PKa ⁇ 10, preferably PKa ⁇ 7, more preferred PKa ⁇ 6.
  • the polyamine oxides can be obtained in almost any degree of polymerisation. The degree of polymerisation is not critical provided the material has the desired water- solubility and dye-suspending power.
  • the average molecular weight is within the range of 500 to 1000,000; preferably from 1,000 to 50,000, more preferably from 2,000 to 30,000, most preferably from 3,000 to 20,000.
  • N-vinylimidazole N-vinylpyrrolidone polymers used in the present invention have an average molecular weight range from 5,000-1,000,000, preferably from 5,000-200,000.
  • Highly preferred polymers for use in detergent compositions according to the present invention comprise a polymer selected from N-vinylimidazole N-vinylpyrrolidone copolymers wherein said polymer has an average molecular weight range from 5,000 to 50,000 more preferably from 8,000 to 30,000, most preferably from 10,000 to 20,000.
  • the average molecular weight range was determined by light scattering as described in Barth H.G. and Mays J.W. Chemical Analysis Vol 113, "Modern Methods of Polymer Characterization" .
  • N-vinylimidazole N-vinylpyrrolidone copolymers have an average molecular weight range from 5,000 to 50,000; more preferably from 8,000 to 30,000; most preferably from 10,000 to 20,000.
  • the N-vinylimidazole N-vinylpyrrolidone copolymers characterized by having said average molecular weight range provide excellent dye transfer inhibiting properties while not adversely affecting the cleaning performance of detergent compositions formulated therewith.
  • the N-vinylimidazole N-vinylpyrrolidone copolymer of the present invention has a molar ratio of N-vinylimidazole to N-vinylpyrrolidone from 1 to 0.2, more preferably from 0.8 to 0.3, most preferably from 0.6 to 0.4 .
  • the detergent compositions of the present invention may also utilize polyvinylpyrrolidone ("PVP") having an average molecular weight of from about 2,500 to about 400,000, preferably from about 5,000 to about 200,000, more preferably from about 5,000 to about 50,000, and most preferably from about 5,000 to about 15,000.
  • PVP polyvinylpyrrolidone
  • Suitable polyvinylpyrrolidones are commercially vailable from ISP Corporation, New York, NY and Montreal, Canada under the product names PVP K-15 (viscosity molecular weight of
  • polyvinylpyrrolidones which are commercially available from BASF Cooperation include Sokalan HP 165 and Sokalan HP 12; polyvinylpyrrolidones known to persons skilled in the detergent field (see for example EP-A-262,897 and EP-A- 256, 696) .
  • the detergent compositions of the present invention may also utilize polyvinyloxazolidone as a polymeric dye transfer inhibiting agent.
  • Said polyvinyloxazolidones have an average molecular weight of from about 2,500 to about 400,000, preferably from about 5,000 to about 200,000, more preferably from about 5,000 to about 50,000, and most preferably from about 5,000 to about 15,000.
  • Polyvinylimidazole The detergent compositions of the present invention may also utilize polyvinylimidazole as polymeric dye transfer inhibiting agent. Said polyvinylimidazoles have an average about 2,500 to about 400,000, preferably from about 5,000 to about 200,000, more preferably from about 5,000 to about 50,000, and most preferably from about 5,000 to about 15,000.
  • Cross-linked polymers are polymers whose backbone are interconnected to a certain degree; these links can be of chemical or physical nature, possibly with active groups n the backbone or on branches; cross-linked polymers have been described in the Journal of Polymer Science, volume 22, pages 1035-1039.
  • the cross-linked polymers are made in such a way that they form a three-dimensional rigid structure, which can entrap dyes in the pores formed by the three-dimensional structure.
  • the cross-linked polymers entrap the dyes by swelling.
  • compositions of the invention may be used in essentially any washing or cleaning methods, including soaking methods, pretreatment methods and methods with rinsing steps for which a separate rinse aid composition may be added.
  • the process described herein comprises contacting fabrics with a laundering solution in the usual manner and exemplified hereunder.
  • the process of the invention is conveniently carried out in the course of the cleaning process.
  • the method of cleaning is preferably carried out at 5 °C to 95 °c, especially between 10°C and 60°C.
  • the pH of the treatment solution is preferably from 7 to 11.
  • the following dosing quantities under european and american washing conditions are respectively : 4-10 g and 1-2 g of the detergent compositon per litre.
  • a preferred machine dishwashing method comprises treating soiled articles with an aqueous solution of the machine diswashing or rinsing composition.
  • a conventional effective amount of the machine dishwashing composition means from 8-60 g of product dissolved or dispersed in a wash volume from 3-10 litres.
  • soiled dishes are contacted with an effective amount of the diswashing composition, typically from 0.5-20g (per 25 dishes being treated) .
  • Preferred manual dishwashing methods include the application of a concentrated solution to the surfaces of the dishes or the soaking in large volume of dilute solution of the detergent composition.
  • compositions of the invention may also be formulated as hard surface cleaner compositions.
  • the level of the enzymes other than the specific lypolytic enzyme of the present invention are expressed in % pure enzyme by weight of total composition and the abbreviated component identifications have the following meanings: LAS Sodium linear C12 alkyl benzene sulphonate
  • SAS Ci2 ⁇ Ci4 secondary (2,3) alkyl sulfate in the form of the sodium salt SAS Ci2 ⁇ Ci4 secondary (2,3) alkyl sulfate in the form of the sodium salt.
  • APG Alkyl poly glucoside surfactant according to the present invention
  • PA30 Polyacrylic acid of average molecular weight of approximately 8,000.
  • NACA-OBS Phenolsulfonate ester of N-nonanoyl- 6-aminocaproic acid.
  • Paraffin Paraffin oil sold under the tradename Winog 70 by Wintershall.
  • Pectinase Pectolytic enzyme sold under the tradename Pectinex AR by Novo Nordisk A/S. 1
  • Xylanase Xylanolytic enzyme sold under the tradenames Pulpzyme HB or SP431 by Novo Nordisk A/S or Lyxasan by Gist- Brocades or Optipulp or Xylanase by Solvay.
  • Protease Proteolytic enzyme sold under the tradename Savinase, Alcalase, Durazym by Novo Nordisk A/S, Maxacal, Maxapem sold by Gist-Brocades and proteases described in patents WO91/06637 and/or WO95/10591 and/or EP 251 446.
  • Amylase Amylolytic enzyme sold under the tradename Purafact Ox Am R described in WO 94/18314, sold by Genencor; Termamyl ® , Fungamyl ® and Duramyl ® all available from Novo Nordisk A/S and those described in Wo95/26397.
  • Lipolytic Lipolytic enzyme sold under the Enzyme tradename Lipolase Ultra by Novo Nordisk A/S.
  • HEDP 1, 1-hydroxyethane diphosphonic acid DETPMP Diethylene triamine penta (methylene phosphonic acid) marketed by Monsanto under the Trade name Dequest 2060.
  • PVP Polyvinyl pyrrolidone polymer
  • PVNO Poly(4-vinylpyridine) -N-Oxide
  • LSD C ⁇ g-C ⁇ g dimethyl amine oxide, Ci2 ⁇ C ⁇ g alkyl ethoxysulfates etoxylation degree 1-5, and the c l3 ⁇ c i5 ethoxylated alcohols 12 or 30, sold under the trade names Lutensol A012 and Lutensol A030 respectively, by BASF GmbH.
  • SRP Sulfonated poly-ethoxy/propoxy end capped ester oligomer and/or short block polymer synthetised from Dimethyl-terephtalate, 1,2 propylene Glycol, methyl capped PEG or sulfoethoxylate.
  • PEG(-6) Polyethylene glycol (having a molecular weight of 600) .
  • Granular fabric cleaning compositions in accord with the invention were prepared as follows:
  • Granular fabric cleaning compositions in accord with the invention were prepared as follows:
  • Example 3 Granular fabric cleaning compositions in accord with the invention which are especially useful in the laundering of coloured fabrics were prepared as follows :
  • Example 4 Granular fabric cleaning compositions in accord with the invention were prepared as follows:
  • Zeolite A 26.0 22.0 24.0 28.0
  • a compact granular fabric cleaning composition in accord with the invention was prepared as follows: I II
  • Granular suds suppressor 3.5 3.0 water/minors/sulfate Up to 100%
  • a granular fabric cleaning compositions in accord with the invention which provide "softening through the wash” capability were prepared as follows: I II
  • Heavy duty liquid fabric cleaning compositions suitable for use in the pretreatment of stained fabrics, and for use in a machine laundering method, in accord with the invention were prepared as follows: I II III IV V
  • Heavy duty liquid fabric cleaning compositions in accord with the invention were prepared as follows:
  • Oleic acid 1.8 - 1.0 -
  • Heavy duty liquid fabric cleaning compositions in accord with the invention were prepared as follows:
  • Bleach-containing non-aqueous fabric cleaning composition in accord with the invention was prepared as follows:
  • Syndet bar fabric cleaning compositions in accord with the invention were prepared as follows:
  • Filler* balance to 100% *Can be selected from convenient materials such as CaC03, talc, clay (Kaolinite, Smectite), silicates, and the like.
  • Example 15 The following detergent composition tablets of 25g weight were prepared in accord with the present invention by compression of a granular dishwashing detergent composition at a pressure of 13KN/cm 2 using a standard 12 head rotary press:
  • liquid dishwashing detergent compositions in accord with the present invention I to II, of density 1.40Kg/L were prepared:
  • liquid hard surface cleaning compositions were prepared in accord with the present invention :

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Abstract

La présente invention concerne des compositions de détergence comprenant une enzyme lipolytique spécifique ainsi qu'un tensioactif à base de polyglucoside d'alkyle. De telles compositions démontrent des performances globales améliorées de détergence, consistant à limiter tout redépôt de substances graisseuses/huileuses sur des tissus, sur des surfaces dures et sur la vaisselle, à améliorer l'entretien des textiles blancs, à nettoyer et à enlever les tâches sans laisser de traces ni de film.
PCT/US1996/007088 1996-05-15 1996-05-15 Compositions de detergence comprenant une enzyme lipolytique specifique ainsi qu'un tensioactif a base de polyglucoside d'alkyle WO1997043377A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
PCT/US1996/007088 WO1997043377A1 (fr) 1996-05-15 1996-05-15 Compositions de detergence comprenant une enzyme lipolytique specifique ainsi qu'un tensioactif a base de polyglucoside d'alkyle
BR9612608A BR9612608A (pt) 1996-05-15 1996-05-15 Composições detergentes compreendendo enzima lipolítica específica e tensoativo de alquil poli glicosídeo
AU58618/96A AU5861896A (en) 1996-05-15 1996-05-15 Detergent compositions comprising specific lipolytic enzyme and alkyl poly glucoside surfactant
EP96920251A EP0912683A1 (fr) 1996-05-15 1996-05-15 Compositions de detergence comprenant une enzyme lipolytique specifique ainsi qu'un tensioactif a base de polyglucoside d'alkyle

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PCT/US1996/007088 WO1997043377A1 (fr) 1996-05-15 1996-05-15 Compositions de detergence comprenant une enzyme lipolytique specifique ainsi qu'un tensioactif a base de polyglucoside d'alkyle

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Cited By (11)

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WO2003055974A2 (fr) 2001-12-22 2003-07-10 Henkel Kommanditgesellschaft Auf Aktien Nouvelle protease alcaline obtenue a partir de bacillus sp. (dsm 14392) et agents de lavage et de nettoyage contenant cette protease alcaline
DE10354213A1 (de) * 2003-11-20 2005-06-23 Henkel Kgaa Mehrphasiges kosmetisches Mittel zur Haar- und Hautreinigung
US7153818B2 (en) 2000-07-28 2006-12-26 Henkel Kgaa Amylolytic enzyme extracted from bacillus sp. A 7-7 (DSM 12368) and washing and cleaning agents containing this novel amylolytic enzyme
US7262042B2 (en) 2001-12-20 2007-08-28 Henkel Kommanditgesellschaft Auf Aktien (Henkel Kgaa) Alkaline protease from Bacillus gibsonii (DSM 14393) and washing and cleaning products comprising said alkaline protease
US7320887B2 (en) 2001-10-31 2008-01-22 Henkel Kommanditgesellschaft Auf Aktien Alkaline protease variants
US7449187B2 (en) 2001-12-20 2008-11-11 Henkel Kommanditgesellschaft Auf Aktien (Henkel Kgaa) Alkaline protease from Bacillus gibsonii (DSM 14391) and washing and cleaning products comprising said alkaline protease
WO2010107489A1 (fr) * 2009-03-17 2010-09-23 S. C. Johnson & Son, Inc. Compositions de prétraitement de lessive respectueuses pour l'environnement
US7888104B2 (en) 2000-11-28 2011-02-15 Henkel Ag & Co. Kgaa Cyclodextrin glucanotransferase (CGTase), obtained from<I>Bacillus agaradherens<λ>(DSM 9948) and detergents and cleaning agents containing said novel cyclodextrin glucanotransferase
WO2011078949A1 (fr) * 2009-12-21 2011-06-30 Danisco Us Inc. Agents tensio-actifs qui améliorent le nettoyage de taches à base de lipides traitées par des lipases
WO2019121057A1 (fr) * 2017-12-20 2019-06-27 Basf Se Formulation de lessive pour l'élimination de composés gras ayant une température de fusion &gt; 30 °c déposés sur des textiles
CN113583764A (zh) * 2021-09-03 2021-11-02 广州立白企业集团有限公司 一种温和洗涤剂组合物

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Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7803604B2 (en) 2000-07-28 2010-09-28 Henkel Ag & Co. Kgaa Amylolytic enzyme extracted from Bacillus sp. A 7-7 (DSM 12368) and washing and cleaning agents containing this novel amylolytic enzyme
US7153818B2 (en) 2000-07-28 2006-12-26 Henkel Kgaa Amylolytic enzyme extracted from bacillus sp. A 7-7 (DSM 12368) and washing and cleaning agents containing this novel amylolytic enzyme
US7888104B2 (en) 2000-11-28 2011-02-15 Henkel Ag & Co. Kgaa Cyclodextrin glucanotransferase (CGTase), obtained from<I>Bacillus agaradherens<λ>(DSM 9948) and detergents and cleaning agents containing said novel cyclodextrin glucanotransferase
US7320887B2 (en) 2001-10-31 2008-01-22 Henkel Kommanditgesellschaft Auf Aktien Alkaline protease variants
US7449187B2 (en) 2001-12-20 2008-11-11 Henkel Kommanditgesellschaft Auf Aktien (Henkel Kgaa) Alkaline protease from Bacillus gibsonii (DSM 14391) and washing and cleaning products comprising said alkaline protease
US7262042B2 (en) 2001-12-20 2007-08-28 Henkel Kommanditgesellschaft Auf Aktien (Henkel Kgaa) Alkaline protease from Bacillus gibsonii (DSM 14393) and washing and cleaning products comprising said alkaline protease
US7569226B2 (en) 2001-12-22 2009-08-04 Henkel Kommanditgesellschaft Auf Aktien (Henkel Kgaa) Alkaline protease from Bacillus sp. (DSM 14392) and washing and cleaning products comprising said alkaline protease
WO2003055974A2 (fr) 2001-12-22 2003-07-10 Henkel Kommanditgesellschaft Auf Aktien Nouvelle protease alcaline obtenue a partir de bacillus sp. (dsm 14392) et agents de lavage et de nettoyage contenant cette protease alcaline
DE10354213A1 (de) * 2003-11-20 2005-06-23 Henkel Kgaa Mehrphasiges kosmetisches Mittel zur Haar- und Hautreinigung
US8470756B2 (en) 2009-03-17 2013-06-25 S.C. Johnson & Son, Inc. Eco-friendly laundry pretreatment compositions
WO2010107489A1 (fr) * 2009-03-17 2010-09-23 S. C. Johnson & Son, Inc. Compositions de prétraitement de lessive respectueuses pour l'environnement
WO2011078949A1 (fr) * 2009-12-21 2011-06-30 Danisco Us Inc. Agents tensio-actifs qui améliorent le nettoyage de taches à base de lipides traitées par des lipases
CN102666824A (zh) * 2009-12-21 2012-09-12 丹尼斯科美国公司 能够改进经脂肪酶处理的脂质基污渍的清洁的表面活性剂
WO2019121057A1 (fr) * 2017-12-20 2019-06-27 Basf Se Formulation de lessive pour l'élimination de composés gras ayant une température de fusion &gt; 30 °c déposés sur des textiles
CN111566195A (zh) * 2017-12-20 2020-08-21 巴斯夫欧洲公司 用于除去沉积在纺织品上的熔融温度>30°c的脂肪族化合物的洗衣配制剂
US20210139817A1 (en) * 2017-12-20 2021-05-13 Basf Se Laundry formulation for removing fatty compounds having a melting temperature > 30°c deposited on textiles
CN113583764A (zh) * 2021-09-03 2021-11-02 广州立白企业集团有限公司 一种温和洗涤剂组合物
CN113583764B (zh) * 2021-09-03 2023-11-24 广州立白企业集团有限公司 一种温和洗涤剂组合物

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