EP0912687A1 - DETERGENT COMPOSITIONS COMPRISING A COMBINATION OF $g(a)-AMYLASES FOR MALODOR STRIPPING - Google Patents

DETERGENT COMPOSITIONS COMPRISING A COMBINATION OF $g(a)-AMYLASES FOR MALODOR STRIPPING

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Publication number
EP0912687A1
EP0912687A1 EP97925549A EP97925549A EP0912687A1 EP 0912687 A1 EP0912687 A1 EP 0912687A1 EP 97925549 A EP97925549 A EP 97925549A EP 97925549 A EP97925549 A EP 97925549A EP 0912687 A1 EP0912687 A1 EP 0912687A1
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EP
European Patent Office
Prior art keywords
amylase
alkyl
amylases
detergent composition
composition according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP97925549A
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German (de)
English (en)
French (fr)
Inventor
Thomas Wilhelm Horner
Kristien Greta Govers
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Procter and Gamble Co
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Procter and Gamble Co
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Filing date
Publication date
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Publication of EP0912687A1 publication Critical patent/EP0912687A1/en
Withdrawn legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/38Products with no well-defined composition, e.g. natural products
    • C11D3/386Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38627Preparations containing enzymes, e.g. protease or amylase containing lipase
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/38Products with no well-defined composition, e.g. natural products
    • C11D3/386Preparations containing enzymes, e.g. protease or amylase

Definitions

  • the present invention relates to detergent compositions comprising a combination of different ⁇ -amylases delivering improved malodor stripping from soiled items in hard surface cleaning, dishwashing and laundry applications.
  • amylase enzymes have been used for a variety of different purposes, the most important of which are starch liquefaction, textile desizing, starch modification in the paper and pulp industry, and for brewing and baking, A further use of amylases which is becoming increasingly important, is the removal of starch containing soils and stains during the washing of fabrics, hard surfaces and dishes.
  • amylase enzymes have long been recognised in dishwashing, hard surface cleaning and laundry compositions to provide the removal of starchy food residues or starchy films from dishware, flatware, glasses and hard surfaces or to provide cleaning performance on starchy soils as well as other soils typically encountered in laundry applications.
  • WO94/02597 Novo Nordisk A/S published February 03, 1 994, describes cleaning compositions which incorporate mutant amylases. See also WO94/18314, Genencor, published August 18, 1 994 and WO95/1 0603, Novo Nordisk A/S, published April 20, 1 995.
  • 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. 5,003,257; EP 252,666; WO91 /00353; FR 2,676,456; EP 285, 1 23; EP 525,610; EP 368,341 ; and British Patent specification no. 1 ,296,839 (Novo).
  • ⁇ -amylases products examples include Termamyl ® , Ban® and Fungamyl ® , all available from Novo Nordisk A/S Denmark.
  • the present invention relates to detergent compositions comprising a combination of different ⁇ -amylases delivering improved malodor stripping from soiled items in hard surface cleaning, dishwashing and laundry applications.
  • Essential components of the detergent compositions of the present invention are ⁇ -amylase enzymes.
  • ⁇ -amylases provides a more effective activity in solution and/or a broader hydrolytic cleavage pattern than a single amylase type as different amylases show different hydrolytic activity on various substrates. Odorous materials are entrapped into these substrates and a rapid and effective hydrolysis achieved on several different cleavage points allows a more effective suspension and dissolution of the odorous materials therein entrapped.
  • Suitable ⁇ -amylases include those disclosed in US Pat. no. 5,003,257; EP 252,666; WO91 /00353; FR 2,676,456; EP 285, 1 23; EP 525,610; EP 368,341 ; and British Patent specification no. 1 ,296,839 (Novo).
  • Examples of commercial ⁇ -amylases products are Termamyl ® , Ban ® and Fungamyl ® , all available from Novo Nordisk A/S Denmark.
  • Other suitable ⁇ -amylases are derived from B. Subtilis or B. stearothermophil ⁇ s .
  • Other ⁇ -amylases herein have the commonality of being derived using site-directed mutagenesis from one or more of the Bacillus ⁇ -amylases, regardless of whether one, two or multiple amylases strains are the immediate precursors.
  • ⁇ -Amylases of this invention include those amylases having improved stability in detergents, especially improved oxidative stability.
  • the stability-enhanced amylases can be obtained from Novo Nordisk A/S or from Genencor International :
  • corresponding ⁇ -amylases will therefore include : (i) a variant ⁇ -amylase that is the expression product of a mutated
  • DNA sequence encoding an ⁇ -amylase the mutated DNA sequence being derived from a precursor ⁇ -amylase by the deletion or substitution of one or more oxidisable acids selected from the group consiting of Met, Trp, Cys and Tyr amino acid residues, in the precursor ⁇ -amylase,
  • amylase variants having additional modification in the immediate parent available from Novo Nordisk A/S. These amylases are disclosed in WO95/10603, published April 1 995 :
  • WO95/26397 Novo Nordisk, published October 05, 1995 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.
  • Phadebas ® ⁇ -amylase activity assay is described at pages 9-10, WO95/26397.
  • Variants of these new amylases demonstrating at least one of the following properties relative to the parent enzymes : 1 ) improved thermal stability, 2) oxidation stability and 3) reduced calcium ion dependency properties.
  • Examples of other desirable improvements or modifications of properties (relative to the parent- ⁇ -amylase) which may be achieved with a variant according to the present invention are : increased stability and/or ⁇ - amylolytic activity at neutral to relatively high pH values, increased ⁇ - amylolytic activity at relatively high temperature and increase or decrease of the isoelectric point (pi) so as to better match the pi value for ⁇ -amylase variant to the pH of the medium, have been described in the co-pending application by Novo Nordisk WO96/23873.
  • Amylolytic enzymes with improved properties with respect to the activity level and the combination of thermostability and a higher activity level are described in WO95/35382. These improved properties render the ⁇ -amylases more suitable for more acidic or alkaline conditions and allow the reduction of the calcium concentration without a loss of performance of the enzyme :
  • Said ⁇ -amylase is derived from an ⁇ -amylase of Bacillus licheniformis or an enzyme having at least 70% amino acid identity therewith which comprises one or more amino acid changes at positions selected from the group consisting of positions 104, 1 28, 1 87 and 1 88 of the amino acid sequence of the ⁇ -amylase of Bacillus licheniformis,
  • the parent hybrid ⁇ -amylase comprising at least 430 amino acid residues of the C-terminal part of the B. licheniformis ⁇ - amylase and an amino acid segment corresponding to the 37 N-terminal amino acid residues of the B. amyloliquefaciens ⁇ -amylase having the amino acid sequence shown in SEQ. ID No. 4 and the amino acid segment corresponding to the 445 C-terminal amino acid residues of the B. Licheniformis ⁇ -amylase having the amino acid sequence shown in SEQ ID No. 2.
  • Preferred combinations of ⁇ -amylases are combinations of a non- modified ⁇ -amylase derived from B. licheniformis, B. amyloliquefaciens, B. Subtilis or B. stearothermophilus with a ⁇ -amylase as described herein above under (a)-(c) and/or WO95/26397 and/or WO95/35382. More preferred combination are the combination of an ⁇ -amylase as described in WO95/10603, known as Duramyl® and the ⁇ -amylase derived from B.
  • the detergent compositions of the present invention can comprise a combination of more than two ⁇ - amylases.
  • a cellulase can be added to such combinations.
  • These enzymes are incorporated into detergent compositions at a level from 0.0001 % to 0.1 % total pure ⁇ -enzymes by weight of the total composition, preferably from 0.0002% to 0.06%, more preferably from 0.0003% to 0.05% total pure ⁇ -amylase enzymes by weight of total composition.
  • the ⁇ -amylases are preferably incorporated into the detergent compositions of the present invention in the range of from 1 :3 to 3: 1 , more preferred ratios are 1 : 1 , 3:7 or 7:3.
  • the cellulases usable in the present invention include both bacterial or fungal cellulases. Preferably, they will have a pH optimum of between 5 and 1 2 and an activity above 50 CEVU (Cellulose Viscosity Unit).
  • CEVU Cellulose Viscosity Unit
  • Suitable cellulases are disclosed in U.S. Patent 4,435,307, Barbesgoard et al, J61078384 and WO96/02653 which discloses fungal cellulase produced respectively from Humicola insolens, Trichoderma, Thielavia and Sporotrichum.
  • EP 739 982 describes cellulases isolated from novel Bacillus species. Suitable cellulases are also disclosed in GB-A-2.075.028; GB-A- 2.095.275; DE-OS-2.247.832 and WO95/26398.
  • cellulase components which may be usable in the present invention are :
  • WO91 /1 7244 or an endoglucanase component which is immunoreactive with an antibody raised against a highly purified " 50kD (apparent molecular weight, the amino acid composition corresponds to 45kD with 2n glycosylation sites) endoglucanase derived from Fusarium oxysporum, DSM 2672, or which is a homologue or derivative of the ⁇ 50kD endoglucanase exhibiting cellulase activity; a preferred endoglucanase component has the amino acid sequence disclosed in PCT Patent Application No. WO91 /1 7244, or any of the cellulases disclosed in the published European Patent Application No.
  • the cellulases having a non-degrading index (NDI) of not less than 500 and being alkalophilic cellulases having an optimum pH not less than 7 or whose relative activity at a pH of not less than 8 is 50% or over of the activity under optimum conditions when carboxy methyl cellulose (CMC) is used as a substrate, or an endoglucanase component which is immunoreactive with an antibody raised against a highly purified ⁇ 43kD endoglucanase derived from Humicola insolens, DSM 1 800, or which is a homologue or derivative of the " 43kD endoglucanase exhibiting cellulase activity; a preferred endoglucanase component has the amino acid sequence disclosed in PCT Patent Application No.
  • WO 91 /1 7243 or an endoglucanase component which is immunoreactive with an antibody raised against a highly purified " 60kD endoglucanase derived from Bacillus lautus, NCIMB 40250, or which is a homologue or derivative of the " 60kD endoglucanase exhibiting cellulase activity; a preferred endoglucanase component has the amino acid sequence disclosed in PCT Patent Application No. WO 91 /10732.
  • cellulases having color care benefits.
  • Examples of such cellulases are cellulases described in European patent application No. 91 202879.2, filed November 6, 1 991 (Novo).
  • preferred cellulases are those as described in Danish Patent Application 1 1 59/90 or PCT patent application WO91 /1 7243 which is also known as Carezyme ⁇ M) available from Novo Nordisk A/S in Bagsvaerd, in Denmark.
  • the cellulase preparation described in these publications and the Carezyme(TM) consistent with this description can consist essentially of a homogeneous endoglucanase component, which is immunoreactive with an anti-body raised against a highly purified 43 kD cellulase derived from Humicola Insulens, DSM 1 800, or which is homologous to said 43 kD endoglucanase.
  • An alternative screening for appropriate cellulases for use in the laundry detergent composition according to the present invention is the method specified in EP-A-495 258 or more specifically in EP-A-350 098.
  • recombinant DNA techniques or other techniques involving adjustments of fermentations or mutation of the microorganisms involved to ensure overproduction of the desired enzymatic activities.
  • Such methods and techniques are known in the art and may readily be carried out by persons skilled in the art.
  • Preferred cellulases to be used in the present invention are 50 kD endoglucanase and 43kD endoglucanase.
  • the detergent compositions of the invention may also contain additional detergent components.
  • additional detergent 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 "compact” form, the 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 of the invention When formulated as compositions suitable for use in a laundry machine washing method, the compositions of the invention 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 suspension and anti-redeposition agents and corrosion inhibitors. Laundry compositions can also contain softening agents, as additional detergent components.
  • the compositions of the invention can also be used as detergent additive products. Such additive products are intended to supplement or boost the performance of conventional detergent compositions.
  • the density of the granular laundry detergent compositions herein ranges from 400 to 1 200 g/litre, preferably 600 to 950 g/litre of composition measured at 20°C.
  • 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 1 7-35% by weight of the total composition.
  • the filler salt is present in amounts not exceeding 1 5% 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 comprise a surfactant system wherein the surfactant can be selected from 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 20% by weight of detergent compositions in accord with the invention.
  • the surfactant is preferably formulated to be compatible with enzyme components present in the composition.
  • the surfactant is most preferably formulated such that it promotes, or at least does not degrade, the stability of any enzyme in these compositions.
  • 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 1 5 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-1 1 4, X- 100 and X-102, all marketed by the Rohm & Haas Company. These surfactants are commonly referred to as alkylphenol alkoxylates (e.g., alkyl phenol ethoxylates).
  • the condensation products of primary and secondary aliphatic alcohols with from 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.
  • NeodolTM 45-9 the condensation product of C 14-C1 5 linear alcohol with 9 moles of ethylene oxide
  • NeodolTM 23-3 the condensation product of C1 2-C 1 3 linear alcohol with 3.0 moles of ethylene oxide
  • NeodolTM 45.7 the condensation product of C1 4-C 1 5 linear alcohol with 7 moles of ethylene oxide
  • Neodol ⁇ M 45-5 the condensation product of C14-C1 5 linear alcohol with 5
  • alkylpolysaccharides disclosed in U.S. Patent 4,565,647, Llenado, issued January 21 , 1 986, having a hydrophobic group containing from about 6 to about 30 carbon atoms, preferably from about 10 to about 1 6 carbon atoms and a polysaccharide, e.g. a polyglycoside, hydrophilic group containing from about 1 .3 to about 1 0, preferably from about 1 .3 to about 3, most preferably from about 1 .3 to about 2.7 saccharide units.
  • Any reducing saccharide containing 5 or 6 carbon atoms can be used, e.g., glucose, galactose and galactosyl moieties can be substituted for the glucosyl moieties (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 1 8, preferably from about 1 2 to about 1 4, 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.
  • the alcohol or alkylpolyethoxy alcohol is formed first and then reacted with glucose, or a source of glucose, to form the glucoside (attachment at the 1 - position).
  • the additional glycosyl units can then be attached between their 1 -position and the preceding glycosyl units 2-, 3-, 4- and/or 6-position, preferably predominately the 2-position.
  • 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 1 500 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 Pluronic ⁇ M 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 1 1 ,000.
  • Examples of this type of nonionic surfactant include certain of the commercially available TetronicTM compounds, marketed by BASF.
  • Preferred for use as the nonionic surfactant of the surfactant systems of the present invention are polyethylene oxide condensates of alkyl phenols, condensation products of primary and secondary aliphatic alcohols with from about 1 to about 25 moles of ethylene oxide, alkylpolysaccharides, and mixtures thereof. Most preferred are C8-C14 alkyl phenol ethoxylates having from 3 to 1 5 ethoxy groups and Cg-C-j g alcohol ethoxylates (preferably C-
  • Highly preferred nonionic surfactants are polyhydroxy fatty acid amide surfactants of the formula.
  • R ⁇ is H, or R ⁇ is C1.4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl or a mixture thereof
  • R 2 is C ⁇ . ⁇ i 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 Ci -j _ -
  • Z is derived from a reducing sugar such as glucose, fructose, maltose, lactose, in a reductive amination reaction.
  • 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 SO3 according to "The Journal of the American Oil Chemists Society", 52 (1 975), 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 ⁇ is a C8-C20 hydrocarbyl, preferably an alkyl, or combination thereof
  • R 4- is a C -
  • 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 T Q- C 1 6 alkyl
  • R 4 is methyl, ethyl or isopropyl.
  • the methyl ester sulfonates wherein R 3 is C 1 0 -C 1 6 alkyl.
  • Suitable anionic surfactants include the linear alkyl benzene sulfonate, alkyl sulfate surfactants which are water soluble salts or acids of the formula ROSO3M wherein R preferably is a C ⁇ o _ C24 hydrocarbyl, preferably an alkyl or hydroxyalkyl having a C 10-C20 alkyl component, more preferably a C-
  • R preferably is a C ⁇ o _ C24 hydrocarbyl, preferably an alkyl or hydroxyalkyl having a C 10-C20 alkyl component, more preferably a C-
  • M is H or a cation, e.g.
  • alkylamines such as ethylamine, diethylamine, triethylamine, and mixtures thereof, and the like.
  • alkyl chains of C1 2-C16 are preferred for lower wash temperatures (e.g. below about 50°C) and C-j ⁇ -
  • 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. These can include salts (including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts) of soap, C8-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 1 0 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-j 2 _ Ci 8 monoesters) and diesters of sulfosuccinates (especially saturated and unsaturated C ⁇ -Ci 2 diesters), acyl sarcosinates, sulfates of alkylpolysaccharide
  • 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, 1 975 to Laughlin, et al. at Column 23, line 58 through Column 29, line 23 (herein incorporated by reference). When included therein, the laundry 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.
  • alkyl alkoxylated sulfate surfactants hereof are water soluble salts or acids of the formula
  • R is an unsubstituted C -10-C24 alkyl or hydroxyalkyl group having a C-
  • 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
  • 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.
  • 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 C1 2-C1 8 alkyl polyethoxylate (1 .0) sulfate (C1 2- C-
  • 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.
  • 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 1 8 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 C-
  • 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
  • Quaternary ammonium surfactant suitable for the present invention has the formula (I):
  • R1 is a short chainiength alkyl (C6-C10) or alkylamidoalkyl of the 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 C1 -C4 and z is 1 or 2.
  • Preferred quat ammonium surfactants are those as defined in formula I whereby
  • Highly preferred cationic surfactants are the water-soluble quaternary ammonium compounds useful in the present composition having the formula :
  • R-j is CQ-C - ⁇ Q alkyl
  • each of R2, 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-j is C1 2-C 1 5 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.
  • 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-1 2-1 5 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 -
  • 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 1 8 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, 1 975 at column 1 9, lines 1 8-35, for examples of ampholytic surfactants.
  • the detergent compositions of the present invention typically comprise from 0.2% to about 1 5%, 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, 1 975 at column 1 9, 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 1 5%, preferably from about 1 % to about 10% by weight of such zwitterionic surfactants.
  • Semi-polar nonionic surfactants are a special category of nonionic surfactants which include water-soluble amine oxides containing one alkyl moiety of from about 10 to about 1 8 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 1 8 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 1 8 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 0
  • 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; R 4 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 ⁇ groups can be attached to each other, e.g., through an oxygen or nitrogen atom, to form a ring structure.
  • amine oxide surfactants in particular include C ⁇ o ⁇ Cl 8 a " ⁇ yl dimethyl amine oxides and Cg-C -
  • the detergent compositions of the present invention typically comprise from 0.2% to about 1 5%, 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 R1 NH2 wherein R-
  • Ri alkyl chains may be straight or branched and may be interrupted with up to 1 2, 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 R1 R2R3N wherein R 1 and R2 are C-
  • R3 is either a C6-C12, preferably C ⁇ -Ci o a'kyl chain, or R3 is R4X(CH2)rv whereby X is -O-, -C(O)NH- or -NH- R4 is a C4-C 1 2, n is between 1 to 5, preferably 2-3.
  • R5 is H or C1 -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 1 2, preferably less than 5, ethylene oxide moieties.
  • Preferred tertiary amines are R1 R2R3N where R1 is a C6-C1 2 alkyl chain, R2 and R3 are C1 -C3 alkyl or
  • Ri is CQ-C - ⁇ 2 alkyl; n is 2-4, preferably n is 3; R2 and R3 is C 1 -C4
  • Most preferred amines of the present invention include 1 -octylamine, 1 -hexylamine, 1 -decylamine, 1 -dodecylamine,C8- 10oxypropylamine, N coco 1 -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 C10 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 the combination of ⁇ - amylase enzymes and eventually cellulases further comprise one or more enzymes which provide cleaning performance and/or fabric care benefits.
  • Said enzymes include enzymes selected from hemicellulases, peroxidases, proteases, gluco-amylases, other amylases, xylanases, lipases, esterases, cutinases, pectinases, reductases, oxidases, phenoioxidases, 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.
  • 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. 91 202882.6, filed on November 6, 1 991 .
  • Said 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, WO94/10591 and US serial number 08/322676 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 1 9.1 54, as disclosed in British Patent 1 ,372,034.
  • Suitable lipases include those which show a positive immunological cross-reaction with the antibody of the lipase, produced by the microorganism Pseudomonas fluorescent IAM 1057. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade name Lipase P "Amano, " hereinafter referred to as "Amano-P".
  • lipases such as M 1 Lipase ⁇ anc ' Lipoma ⁇ R (Gist-Brocades) and Lipolase ⁇ and Lipolase Ultra ⁇ (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
  • 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.
  • 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. They can be added as separate ingredients ( prills, granulates, ...) or as cogranulate of two or more enzymes.
  • enzyme oxidation scavengers which are described in the copending European patent application 92870018.6 filed on January 31 , 1 992.
  • enzyme oxidation scavengers are ethoxylated tetraethylene polyamines.
  • Bleaching agent Bleach systems that can be included in the detergent compositions of the present invention include bleaching agents such as PB1 , 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, 1 33,354 and U.S. Patent 4,41 2,934.
  • Highly preferred bleaching agents also include 6- nonylamino-6-oxoperoxycaproic acid as described in U.S. Patent 4,634,551 .
  • hypohalite bleaching agents include trichloro isocyanuric acid and the sodium and potassium dichloroisocyanurates and N-chloro and N-bromo alkane suiphonamides. 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 4,41 2,934), 3,5,- trimethylhexanoloxybenzenesulfonate (ISONOBS, described in EP 1 20,591 ), Phenolsulfonate ester of N-nonanoyl-6-aminocaproic acid (NACA-OBS, described in WO94/28106) or pentaacetylglucose (PAG), which are perhydrolyzed to form a peracid as the active bleaching species, leading to improved bleaching effect.
  • bleach activators such as tetraacetylethylenediamine (TAED), nonanoyloxybenzene-sulfonate (NOBS, described in US 4,41 2,934), 3,5,- trimethylhexanoloxybenzenesulf
  • 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 08/1 36,626, PCT/US95/07823, WO95/27772, WO95/27773, WO95/27774 and WO95/27775.
  • 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
  • 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 4,033,71 8.
  • 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, (ethyienedioxy) diacetic acid, maleic acid, diglycollic acid, tartaric acid, tartronic acid and fumaric acid, as well as the ether carboxylates described in German Offenlegenschrift 2,446,686, and 2,446,687 and U.S. Patent No. 3,935,257 and the sulfinyl carboxylates described in Belgian Patent No. 840,623.
  • Polycarboxylates containing three carboxy groups include, in particular, water-soluble citrates, aconitrates and citraconates as well as succinate derivatives such as the carboxymethyloxysuccinates described in British Patent No. 1 ,379,241 , lactoxysuccinates described in Netherlands Application 7205873, and the oxypolycarboxylate materials such as 2-oxa- 1 , 1 ,3-propane tricarboxylates described in British Patent No. 1 ,387,447.
  • Polycarboxylates containing four carboxy groups include oxydisuccinates disclosed in British Patent No. 1 ,261 ,829, 1 , 1 ,2,2-ethane tetracarboxylates, 1 , 1 ,3,3-propane tetracarboxylates and 1 , 1 ,2,3-propane tetracarboxylates.
  • Polycarboxylates containing sulfo substituents include the sulfosuccinate derivatives disclosed in British Patent Nos. 1 ,398,421 and 1 ,398,422 and in U.S. Patent No. 3,936,448, and the sulfonated pyrolysed citrates described in British Patent No.
  • 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,
  • 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, zeolite MAP 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, zeolite MAP 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 MAP, zeolite A, and a watersoluble carboxylate chelating agent such as citric acid.
  • a water-insoluble aluminosilicate builder such as zeolite MAP, zeolite A
  • 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.
  • 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 no ⁇ -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 1 26 published April 28, 1 977.
  • 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 1 2 R.
  • Such suds suppressor system are described in Copending European Patent application N 928701 74.7 filed 10 November, 1 992.
  • Especially preferred silicone suds controlling agents are described in Copending European Patent application N°92201 649.8.
  • Said compositions can comprise a silicone/silica mixture in combination with fumed nonporous silica such as Aerosil ⁇ .
  • 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 ,464,61 6.
  • 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 1 0% 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-2,2
  • polyethylene glycols particularly those of molecular weight 1000-1 0000, 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. 41 16885 and 471 1730 and European Published Patent Application No. 0 272 033.
  • a particular preferred polymer in accordance with EP-A-0 272 033 has the formula (CH 3 (PEG)43)o.75(POH)o.25[T-PO) 2 .8(T-PEG)o.4]T(PO- H) ⁇ .25UPEG) 4 3CH 3 )o.75
  • 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 1 6% by weight of propane - 1 .2 diol, about 10% by weight ethylene glycol about 1 3% by weight of dimethyl sulfobenzoic acid and about 1 5% 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 31 1 342.
  • 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 9287001 8.6 filed January 31 , 1 992.
  • 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 5,01 9,292. Organic fabric softening agents include the water insoluble tertiary amines as disclosed in GB-A1 514 276 and EP-BO 01 1 340 and their combination with mono C1 2-C1 4 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 91 9. 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 31 3 146.
  • Levels of smectite clay are normally in the range from 2% to 20%, more preferably from 5% to 1 5% by weight, with the material being added as a dry mixed component to the remainder of the formulation.
  • 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 0.1 5% 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-O group can be attached to or wherein the R-N-O group forms part of the polymerisable unit or a combination of both.
  • the N-O group can be represented by the following general structures
  • R1 , 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-O group can be attached or wherein the nitrogen of the N-O group forms part of these groups.
  • the N-O 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-O group forms part of the polymerisable unit comprise polyamine N-oxides wherein R is selected from aliphatic, aromatic, alicyclic or heterocyclic groups.
  • polyamine N-oxides comprises the group of polyamine N- oxides wherein the nitrogen of the N-O 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-O group is attached to the R-group.
  • polyamine N-oxides are the polyamine oxides whereto the N-O 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-O functional group is part of said R group.
  • Examples o,f these classes are polyamine oxides wherein 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-O functional group is attached to said R groups.
  • Examples of these classes are 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.
  • polymeric backbones examples include 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 10: 1 to 1 : 1000000.
  • 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 1 : 1000000, most preferably from 1 :7 to 1 : 1 000000.
  • 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 1 000,000; preferably from 1 ,000 to 50,000, more preferably from 2,000 to 30,000, most preferably from 3,000 to 20,000.
  • 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 1 0,000 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 1 1 3, "Modem 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 1 0,000 to 20,000.
  • 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-vinyiimidazole 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 1 5,000.
  • PVP polyvinylpyrrolidone
  • Suitable polyvinylpyrrolidones are commercially vailable from ISP Corporation, New York, NY and Montreal, Canada under the product names PVP K-1 5 (viscosity molecular weight of 1 0,000), PVP K-30 (average molecular weight of 40,000), PVP K-60 (average molecular weight of 1 60,000), and PVP K-90 (average molecular weight of 360,000).
  • polyvinylpyrrolidones which are commercially available from BASF Cooperation include Sokalan HP 165 and Sokalan HP 1 2; 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 1 5,000.
  • 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
  • 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.
  • specific amylase enzymes within the specified enzymatic concentration have demonstrated superior starch cleaning even for wash cycles occuring at very low temperatures (between 1 0°C and 25°C).
  • the pH of the treatment solution is preferably from 7 to 1 1 .
  • 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 enzymes levels are expressed in pure enzyme by weight of the total composition and the abbreviated component identifications have the following meanings:
  • LAS Sodium linear Ci 2 alkyl benzene sulphonate.
  • TAS Sodium tallow alkyl sulphate.
  • XYAS Sodium C x - C-
  • 5 predominantly linear primary alcohol condensed with an average of Y moles of ethylene oxide.
  • Ci2 ⁇ Ci5 mixed ethoxylated and/or propoxylated fatty alcohol with an average degree of ethoxylation of 3 to 7 and an average degree of propoxylation of 4.5.
  • PA30 Polyacrylic acid of average molecular weight of approximately 8,000.
  • Terpolymer Terpolymer of average molecular weight approx. 7,000, comprising acrylic:maleic:ethylacrylic acid monomer units at a weight ratio of 60:20:20
  • Citric Citric Acid Perborate Anhydrous sodium perborate monohydrate bleach, empirical formula NaB ⁇ 2-H2 ⁇ 2
  • 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.
  • Xylanase Xylanolytic enzyme sold under the tradenames Pulpzyme HB or SP431 by Novo Nordisk A/S or Lyxasan (Gist-Brocades) or Optipulp or Xylanase (Solvay).
  • Protease Proteolytic enzyme sold under the tradename Savinase, Alcalase, Durazym by Novo Nordisk A/S, Maxapem and Maxacal sold by Gist- Brocades and proteases described in patent applications WO91 /06637 and/or WO95/1 0591 and/or EP 251 446.
  • Lipase Lipolytic enzyme sold under the tradename Lipolase and Lipolase Ultra by Novo Nordisk A/S.
  • DETPMP Diethylene triamine penta (methylene phosphonic acid), marketed by Monsanto under the Trade name Dequest 2060.
  • PAAC pentaamine acetate cobalt (III) salt PAAC pentaamine acetate cobalt (III) salt.
  • PVP Polyvinyl pyrrolidone polymer
  • Granular Suds 1 2% Silicone/silica, 1 8% stearyl alcohol, 70% Suppressor starch in granular form
  • HMWPEO High molecular weight polyethylene oxide.
  • TAE 25 Tallow alcohol ethoxylate (25). BTA Benzotriazole.
  • Granular fabric cleaning compositions in accord with the invention were prepared as follows:
  • Amylase I 0.0035 0.01 0.005 0.003 0.014
  • Amylase II 0.0025 0.01 0.005 0.007 0.006
  • Granular fabric cleaning compositions in accord with the invention were prepared as follows:
  • Zeolite A 26.0 26.0 26.0 26.0 26.0 26.0 26.0
  • Amylase I 0.01 0.0045 0.05 0.014 0.005
  • Amylase II 0.01 0.0105 0.05 0.006 0.005 Water & minors Up to 100%
  • Granular fabric cleaning compositions in accord with the invention which are especially useful in the laundering of coloured fabrics were prepared as follows :
  • Amylase 1 0.01 5 0.02 0.0025
  • Granular fabric cleaning compositions in accord with the invention were prepared as follows:
  • a compact granular fabric cleaning composition in accord with the invention was prepared as follows:
  • Granular suds suppressor 3.5 water/minors Up to 1 00%
  • a granular fabric cleaning composition in accord with the invention which provide "softening through the wash” capability were prepared as follows:
  • Coco-alkyl-dimethyl hydroxy ⁇ 1 .4 1 .0 ethyl ammonium chloride Citrate 5.0 3.0 Na-SKS-6 - 1 1 .0 Zeolite A 1 5.0 15.0 MA/AA 4.0 4.0 DETPMP 0.4 0.4 Perborate 15.0 - Percarbonate - 1 5.0 TAED 5.0 5.0 Smectite clay 10.0 10.0 HMWPEO 0.1
  • Liquid fabric cleaning compositions in accord with the invention were prepared as follows:
  • Citric acid 2.0 1 .0 1 .0 2.0 3.0 1 .0
  • Amylase I 0.006 0.007 0.008 0.009 0.006 0.006
  • Amylase II 0.006 0.003 0.005 0.004 0.009 0.007
  • Borax-Ca Format 2.0 3.0 2.0 1 .5 2.0 2.0
  • Brightener 36 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1
  • Liquid fabric cleaning compositions in accord with the invention were prepared as follows:
  • Amylase I 0.006 0.007 0.008 0.009 0.006
  • Amylase II 0.006 0.003 0.005 0.004 0.009
  • Borax-Ca Format 2.0 3.0 2.0 1 .5 2.0
  • Brightener 36 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1
  • Liquid fabric cleaning compositions in accord with the invention were prepared as follows:
  • Amylase I 0.01 5 0.006 0.007 0.008 0.009
  • Amylase II 0.014 0.006 0.003 0.005 0.004
  • Borax-Ca Format 2.0 3.0 2.0 1 .5 2.0
  • Brightener 36 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1
  • 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:
  • Amylase I 0.005 0.005 0.001 0.01 0.002
  • Amylase II 0.0025 0.002 0.001 0.007 0.002
  • Heavy duty liquid fabric cleaning compositions in accord with the invention were prepared as follows:
  • Amylase I 0.002 0.007 0.003 0.005
  • Amylase II 0.002 0.003 0.002 0.005
  • the following rinse added fabric softener composition in accord with the invention, was prepared (parts by weight).
  • Syndet bar fabric cleaning compositions in accord with the invention were prepared as follows:
  • Amylase II 0.005 0.014 0.003 0.005
  • Amylase 1 0.005 0.003 0.005 0.01 0.005 0.0007
  • Amylase II 0.005 0.002 0.01 0.005 0.005 0.0018
  • Amylase I 0.002 0.001 0.005 0.006 0.007 0.01
  • Amylase II 0.001 0.001 0.005 0.014 0.003 0.005
  • Cellulase 1 0.001 0.005 - - - 0.001
  • 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 1 3KN/cm2 using a standard 1 2 head rotary press:
  • Amylase I 0.005 0.002 0.001
  • Amylase II 0.005 0.003 0.001 cellulase I - 0.01 0.01
  • liquid dishwashing detergent compositions in accord with the present invention I to II, of density 1 .40Kg/L were prepared:
  • Amylase II 0.00025 0.0007
  • liquid hard surface cleaning compositions were prepared in accord with the present invention :
  • Amylase I 0.01 0.002 0.005 0.006 0.0007 0.003
  • Amylase II 0.01 0.003 0.005 0.01 4 0.0003 0.002

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  • Chemical & Material Sciences (AREA)
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  • Engineering & Computer Science (AREA)
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  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
EP97925549A 1996-05-15 1997-05-13 DETERGENT COMPOSITIONS COMPRISING A COMBINATION OF $g(a)-AMYLASES FOR MALODOR STRIPPING Withdrawn EP0912687A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
PCT/US1996/007090 WO1997043378A1 (en) 1996-05-15 1996-05-15 DETERGENT COMPOSITIONS COMPRISING A COMBINATION OF α-AMYLASES FOR MALODOR STRIPPING
WOPCT/US96/07090 1996-05-15
PCT/US1997/008103 WO1997043385A1 (en) 1996-05-15 1997-05-13 DETERGENT COMPOSITIONS COMPRISING A COMBINATION OF α-AMYLASES FOR MALODOR STRIPPING

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CA2243011C (en) * 1998-07-13 2007-02-13 Life Science Technology Group, Inc. Odor control agent for carpet and the like and method of use thereof
US6794350B2 (en) 2001-02-17 2004-09-21 Novozymes A/S Reduction of malodor from laundry
AU2002231607B2 (en) * 2001-02-17 2008-02-28 Novozymes A/S Reduction of malodour from laundry
CN101501183B (zh) * 2006-08-11 2012-12-05 诺维信生物股份有限公司 细菌培养物和包含细菌培养物的组合物
JP5890193B2 (ja) * 2012-02-15 2016-03-22 花王株式会社 自動洗浄機用粉末洗浄剤組成物
EP2856896A1 (en) 2013-09-23 2015-04-08 Life Science TGO, SRL Impregnated odour control products and methods of making the same
EP3464536A1 (en) * 2016-05-26 2019-04-10 Novozymes A/S Use of enzymes, cleaning composition and method for washing
CN114616312A (zh) * 2019-09-19 2022-06-10 诺维信公司 洗涤剂组合物

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DE2036477A1 (de) * 1970-07-23 1972-01-27 Rohm Gmbh, 6100 Darmstadt Enzymhaltiges flussiges Geschirrspul mittel
ES2052565T3 (es) * 1986-07-09 1994-07-16 Novo Nordisk As Un procedimiento para licuar una suspension de almidon o granos amilaceos.
US5030377A (en) * 1988-11-11 1991-07-09 Kao Corporation Detergent compositions containing starch debranching enzymes
DK0576424T3 (da) * 1990-06-14 1996-08-05 Novo Nordisk As Aktivering af polysaccharidhtdrolase
JP2516551B2 (ja) * 1993-04-09 1996-07-24 ティーポール株式会社 粉末漂白洗浄剤組成物
BR9407767A (pt) * 1993-10-08 1997-03-18 Novo Nordisk As Variante de enzima &-amilase uso da mesma construção de DNA vetor de express o recombinante célula processos para produzir uma &-amilase hibrida e para preparar uma variante de uma &-amilase aditivo detergente e composições detergentes

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JPH11511784A (ja) 1999-10-12
WO1997043378A1 (en) 1997-11-20
CZ364998A3 (cs) 1999-04-14
CA2254069A1 (en) 1997-11-20
JP3095786B2 (ja) 2000-10-10
CN1225674A (zh) 1999-08-11
BR9709004A (pt) 1999-08-03

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