EP1726636B2 - Compositions de lavage - Google Patents

Compositions de lavage Download PDF

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Publication number
EP1726636B2
EP1726636B2 EP06110531.8A EP06110531A EP1726636B2 EP 1726636 B2 EP1726636 B2 EP 1726636B2 EP 06110531 A EP06110531 A EP 06110531A EP 1726636 B2 EP1726636 B2 EP 1726636B2
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Prior art keywords
detergent composition
alkyl
preferred
amino acid
lipase
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German (de)
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EP1726636B1 (fr
EP1726636A1 (fr
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Neil Joseph Lant
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Procter and Gamble Co
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Procter and Gamble Co
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Priority claimed from EP05251269A external-priority patent/EP1698689A1/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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3945—Organic per-compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • 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
    • 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
    • C11D3/38636—Preparations containing enzymes, e.g. protease or amylase containing enzymes other than protease, amylase, lipase, cellulase, oxidase or reductase
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3942—Inorganic per-compounds

Definitions

  • the present invention relates to detergent compositions, particularly laundry detergents and in particular to detergents comprising lipolytic or lipase enzymes.
  • bleaching systems for assisting in stain removal of articles being washed.
  • These bleaching systems commonly comprise a source of hydrogen peroxide such as perborate or percarbonate.
  • the performance of hydrogen peroxide bleaches is often enhanced by use of a peracid which may be pre-formed or a peracid precursor (often called a bleach activator) in addition to the hydrogen peroxide (or oxygen source).
  • a peracid precursor often called a bleach activator
  • oxygen source oxygen source
  • the bleach activator reacts with an excess of hydrogen peroxide to form a peracid bleaching species.
  • Typical laundry formulations use an excess of hydrogen peroxide source.
  • the most common bleach activator is TAED (tetra acetyl ethylene diamine), the active bleach species that is formed on reaction with hydrogen peroxide being peracetic acid.
  • Other activators result in bleaching species that have a longer carbon chain and that are hydrophobic. These are desirable for producing effective bleaching, especially on oily stains.
  • nonanoyl oxybenzene sulphonate This bleach activator reacts to form a reactive bleaching species pemonanoic acid.
  • this bleaching species will react with the bleach activator itself to form a di-C 9 acyl peroxide; other hydrophobic bleach activators react to form their corresponding diacyl peroxides in the same way.
  • These species are strong bleaching species and are useful in the washing process, but they are insoluble. In some types of washing machines, there may be a tendency for these compounds to settle out in the sump of washing machines as the wash water drains out of the washing machine.
  • the problem addressed by this invention is how to alleviate this problem such that the benefits of hydrophobic bleaches may be achieved whilst at the same time minimizing or preventing damage to washing equipment.
  • Lipase enzymes have been used in detergents since the late 1980s for removal of fatty soils by breakdown of fatty soils into tri-glycerides.
  • lipase enzymes such as Lipolase (trade name, Novozymes) worked particularly effectively at the lower moisture levels of the drying phase of the wash process. These enzymes tended to produce significant cleaning only in the second wash step because the active site of the enzyme was occupied by water during the washing process, so that fat breakdown was significant only on soils remaining on laundered clothes during the drying stage, the broken down fats then being removed in the next washing step.
  • lipases have been developed that also work effectively during the wash phase of the cleaning process, so that as well as cleaning in the second washing step, a significant improvement in cleaning effect due to lipase enzyme can be found in the first wash-cycle.
  • first wash lipases examples include certain variants of lipolase (wild-type Humicola lanuginosa) which should comprise one or more substitutions with positive amino acids near the N-terminal in the three-dimensional structure.
  • the variants should further comprise a peptide addition at the C-terminal and/or should meet certain limitations on electrically charged amino acids at positions 90-101 and 210.
  • the present inventors have found that using a combination of these first wash enzymes with a specific type of detergent formulation enables use of these hydrophobic bleach activators to achieve good stain removal, whilst reducing any of the disadvantages set out above.
  • the present inventors have found that when a first wash lipase is used in a detergent composition in conjunction with high reserve alkalinity and with a molar ratio of available oxygen (from the peroxide source): peracid of from 2:1 to 8:1, diacyl peroxide formation is controlled such that the disadvantages of this type of hydrophobic peracid or peracid precursor are alleviated.
  • the detergent compositions of the invention comprise less than 15 wt% builders selected from aluminosilicate (zeolite) builder and/or phosphate builder. In a further preferred aspect of the invention, the compositions comprise less than 10 wt% zeolite and/or phosphate builder, or even less than 5 wt% or 4 wt % zeolite and/or phosphate builder.
  • zeolite aluminosilicate
  • Inorganic perhydrate salts are a preferred source of peroxide. Preferably these salts are present at a level from 0.05 to 40 wt%, more preferably from 1 to 30 wt% based on the detergent composition, or from 2 to 20 wt%.
  • Examples of inorganic perhydrate salts include perborate, percarbonate, persulphate, perphosphate and persilicate salts.
  • Perborate usually monohydrate or tetrahydrate, or more especially percarbonate salts are most preferred. These are usually alkali metal salts, preferably sodium salts.
  • the inorganic perhydrate salts are typically incorporated into the detergent compositions of the invention as a crystalline solid, which may be optionally coated for example to achieve improved storage stability. Suitable coatings comprise inorganic salts such as alkali metal silicate, carbonate or borate salts or mixture thereof, or organic materials such as waxes, oils or fatty soaps.
  • Suitable examples include decanoyl oxybenzoic acid or salt thereof, sodium or potassium salts of dodecanonyl oxybenzene sulphonate, decanoyl oxybenzenesulponate, 3,5,5-trimethyl hexanoyloxybenzene sulphonate, or even more preferred nonanoyloxybenzene sulphonate (NOBS).
  • NOBS nonanoyloxybenzene sulphonate
  • the peracid or peracid precursor is generally present in the composition in an amount of from 0.5 to 10 wt%, preferably from 0.5 to 5 wt%, preferably 0.5 to 4 wt% based on the detergent composition.
  • a hydrophilic peracid or peracid precursor may also be incorporated into the detergent compositions of the invention.
  • these include materials of the formulae given above for the hydrophobic peracids/precursors, but with the R group comprising less than 6 carbon atoms, preferably less than 4.
  • a preferred example is TAED. If present it will generally be present in amounts no greater than 7 wt%, generally in amounts from 0.1 to 5 wt%.
  • the amounts of hydrogen peroxide source and peracid or peracid precursor are selected such that the molar ratio of Available oxygen (from the peroxide source) to peracid is from 2:1 to 8:1.
  • Preferred molar ratios are from 3:1 or even 5:1 to 8:1.
  • the reference lipase used in this invention is the wild type lipase derived from Humicola lanuginosa strain DSM 4109. It is described in EP258068 and EP305216 and has the amino acid sequence shown in positions 1-269 of SEQ ID NO: 2 of US5869438 (attached hereto). In this specification, the reference lipase is also referred to as Lipolase.
  • the lipase of the invention comprises one or more (e.g. 2-4, particularly two) substitutions of an electrically neutral or negatively charged amino acid near E1 or Q249 with a positively charged amino acid, preferably R.
  • substitution is at the surface of the three-dimensional structure within 15 A of E1 or Q249, e.g. at any of positions 1-11, 90, 95, 169, 171-175, 192-211, 213-226, 228-258, 260-262.
  • substitution may be within 10 ⁇ of E 1 or Q249, e.g. at any of positions 1-7, 10, 175, 195, 197-202, 204-206, 209, 215, 219-224, 230-239, 242-254.
  • substitution may be within 15 ⁇ of E1, e.g. at any of positions 1-11, 169, 171, 192-199, 217-225, 228-240, 243-247, 249, 261-262.
  • substitution is most preferably within 10 ⁇ of E1, e.g. at any of positions 1-7, 10, 219-224 and 230-239.
  • substitutions are S3R, S224R, P229R, T231R, N23 3R, D234R and T244R.
  • the lipase may comprise a peptide addition attached to C-terminal L269.
  • the peptide addition improves the first-wash performance in a variety of detergents.
  • the peptide addition preferably consists of 1-5 amino acids, e.g. 2, 3 or 4 amino acids.
  • the amino acids of the peptide addition will be numbered 270, 271, etc.
  • the peptide addition may consist of electrically neutral (e.g. hydrophobic) amino acids, e.g. PGL or PG.
  • the lipase peptide addition consists of neutral (e.g. hydrophobic) amino acids and the amino acid C, and the lipase comprises substitution of an amino acid with C at a suitable location so as to form a disulfide bridge with the C of the peptide addition. Examples are:
  • the lipase used in the invention preferably meets certain limitations on electrically charged amino acids at positions 90-101 and 210.
  • amino acid 210 may be negative.
  • E210 may be unchanged or it may have the substitution E210D/C/Y, particularly E210D.
  • the lipase may comprise a negatively charged amino acid at any of positions 90-101 (particularly 94-101), e.g. at position D96 and/or E99.
  • the lipase may comprise a neutral or negative amino acid at position N94, i.e. N94 (neutral or negative), e.g. N94N/D/E.
  • the lipase may have a negative or neutral net electric charge in the region 90-101 (particularly 94-101), i.e. the number of negative amino acids is equal to or greater than the number of positive amino acids.
  • the region may be unchanged from Lipolase, having two negative amino acids (D96 and E99) and one positive (K98), and having a neutral amino acid at position 94 (N94), or the region may be modified by one or more substitutions.
  • N94, N96 and E99 may have a negative or unchanged electric charge.
  • all three amino acids may be unchanged or may be changed by a conservative or negative substitution, i.e. N94 (neutral or negative), D(negative) and E99(negative).
  • N94D/E and D96E are examples of the three amino acids.
  • one of the three may be substituted so as to increase the electric charge, i.e. N94 (positive), D96 (neutral or positive) or E99 (neutral or positive).
  • Examples are N94K/R, D96I/L/N/S/W or E99N/Q/K/R/H.
  • the substitution of a neutral with a negative amino acid may improve the performance in an anionic detergent.
  • the substitution of a neutral amino acid with a positive amino acid may provide a variant lipase with good performance both in an anionic detergent and in an anionic/non-ionic detergent (a detergent with e.g. 40-70 % anionic out of total surfactant).
  • a substitution Q249R/K/H and/or a substitution of R209 with a neutral or negative amino acid e.g. R209P/S
  • the lipase may optionally comprise the substitution G91A.
  • the lipase may optionally comprise substitutions of one or more additional amino acids.
  • substitutions may, e.g. be made according to principles known in the art, e.g. substitutions described in WO92/05249 , WO94/25577 , WO95/22615 , WO97/04079 and WO97/07202 .
  • Specific examples of suitable combinations of substitutions are given in the table bridging pages 4 and 5 of WO00/60063 . Nomenclature for amino acid modifications is as described in WO00/60063 .
  • the preferred lipase enzymes are described in WO00/60063 , the most preferred being Lipex (registered tradename of Novozymes), a variant of the Humicola lanuginosa (Thermomyces lanuginosus) lipase (Lipolase registered tradename of Novozymes) with the mutations T231R and N23 3R.
  • the lipase enzyme incorporated into the detergent compositions of the present invention is generally present in an amount of 10 to 20000 LU/g of the detergent composition, or even 100 to 10000 LU/g.
  • the LU unit for lipase activity is defined in WO99/42566 .
  • the lipase dosage in the wash solution is typically from 0.01 to 5 mg/l active lipase protein, more typically from 0.1 to 2mg/l as enzyme protein.
  • the lipase enzyme may be incorporated into the detergent composition in any convenient form, generally in the form of a non-dusting granulate, a stabilised liquid or a protected, for example, coated enzyme particle.
  • the reflectance (which may also be termed remission) is measured on an Elrepho 2000 apparatus from Datacolor which illuminates the sample with 2 xenon blitz lamps and measures the amount of reflected light so that entirely white corresponds to a 100% reflectance and entirely black a 0% reflectance. Comparing the results for lard removal due to the presence of enzyme, lipase enzymes giving better performance than WT LipolaseTM are suitable for use in the compositions of the present invention.
  • Adequate reserve alkalinity may be provided, for example, by one or more of alkali metal silicates (excluding crystalline layered silicate), typically amorphous silicate salts, generally 1.2 to 2.2 ratio sodium salts, alkali metal typically sodium carbonate, bicarbonate and/or sesquicarbonates.
  • alkali metal silicates excluding crystalline layered silicate
  • typically amorphous silicate salts generally 1.2 to 2.2 ratio sodium salts
  • alkali metal typically sodium carbonate, bicarbonate and/or sesquicarbonates.
  • STPP and persalts such as perborates and percarbonates also contribute to alkalinity. Buffering is necessary to maintain an alkaline pH during the wash process counteracting the acidity of soils, especially fatty acids liberated by the lipase enzyme.
  • the detergent composition preferably comprises from 0 wt% to 50 wt% silicate salt, more usually 5 to 30 wt% silicate salt, or 7 to 20 wt% silicate salt, usually sodium silicate.
  • the detergent compositions of the invention may comprise a carbonate salt, typically from 1 wt% to 70 wt%, or from 5 wt% to 50 wt% or from 10 wt% to 30 wt% carbonate salt.
  • Preferred carbonate salts are sodium carbonate and/or sodium bicarbonate and/or sodium sesquicarbonate.
  • the carbonate salt may be incorporated into the detergent composition wholly or partially via a mixed salt such as Burkeite.
  • a highly preferred carbonate salt is sodium carbonate.
  • the composition may comprise from 5 wt% to 50 wt% sodium carbonate, or from 10 to 40 wt% or even 15 to 35 wt% sodium carbonate. It may also be desired for the composition to comprise from 1wt% to 20 wt% sodium bicarbonate, or even 2 to 10 or 8 wt%.
  • the weight ratio of sodium carbonate and/or sodium silicate to zeolite builder may be at least 5:1, preferably at least 10:1, or at least 15:1, or at least 20:1 or even at least 25:1
  • the carbonate salt, or at least part thereof is typically in particulate form, typically having a weight average particle size in the range of from 200 to 500 micrometers. However, it may be preferred for the carbonate salt, or at least part thereof, to be in micronised particulate form, typically having a weight average particle size in the range of from 4 to 40 micrometers; this is especially preferred when the carbonate salt, or at least part thereof, is in the form of a co-particulate admixture with a detersive surfactant, such as an alkoxylated anionic detersive surfactant.
  • a detersive surfactant such as an alkoxylated anionic detersive surfactant.
  • the levels of carbonate and/or silicate salts typically sodium carbonate and sodium silicate will be from 10 to 70 wt%, or from 10 or even 15 to 50 wt% based on the total weight of the composition.
  • the amount of strong builder selected from phosphate and/or zeolite builder is less than 15 wt% based on the total weight of the detergent composition, preferably below 10 wt%, or even below 8 or 5 or 4 or 3 or 2 wt%.
  • the total level of weak builders selected from layered silicate (SKS-6), citric acid, citrate salts and nitrilo triacetic acid or salt thereof is below 15 wt%, more preferably below 8 wt%, more preferably below 4 wt% or even below 3 or 2 wt% based on the total weight of the detergent composition.
  • the level of each of layered silicate, citric acid, citrate salts and nitrilo triacetic acid or salt thereof will be below 10 wt% or even below 5 wt% or wt% based on the total weight of the composition.
  • a highly preferred adjunct component of the compositions of the invention is a surfactant.
  • the detergent composition comprises one or more surfactants.
  • the detergent composition comprises (by weight of the composition) from 0% to 50%, preferably from 5% and more preferably from 10 or even 15 wt% to 40%, or to 30%, or to 20% one or more surfactants.
  • Preferred surfactants are anionic surfactants, non-ionic surfactants, cationic surfactants, zwitterionic surfactants, amphoteric surfactants, cationic surfactants and mixtures thereof.
  • Suitable anionic surfactants typically comprise one or more moieties selected from the group consisting of carbonate, phosphate, phosphonate, sulphate, sulphonate, carboxylate and mixtures thereof.
  • the anionic surfactant may be one or mixtures of more than one of C 8-18 alkyl sulphates and C 8-18 alkyl sulphonates.
  • Suitable anionic surfactants incorporated alone or in mixtures in the compositions of the invention are also the C 8-18 alkyl sulphates and/or C 8-18 alkyl sulphonates optionally condensed with from 1 to 9 moles of C 1-4 alkylene oxide per mole of C 8-18 alkyl sulphate and/or C 8-18 alkyl sulphonate.
  • the alkyl chain of the C 8-18 alkyl sulphates and/or C 8-18 alkyl sulphonates may be linear or branched, preferred branched alkyl chains comprise one or more branched moieties that are C 1-6 alkyl groups.
  • suitable anionic surfactants include the C 10 -C 20 primary, branched-chain, linear-chain and random-chain alkyl sulphates (AS), typically having the following formula: CH 3 (CH 2 ) x CH 2 -OSO 3 - M + wherein, M is hydrogen or a cation which provides charge neutrality, preferred cations are sodium and ammonium cations, wherein x is an integer of at least 7, preferably at least 9; C 10 -C 18 secondary (2,3) alkyl sulphates, typically having the following formulae: wherein, M is hydrogen or a cation which provides charge neutrality, preferred cations include sodium and ammonium cations, wherein x is an integer of at least 7, preferably at least 9, y is an integer of at least 8, preferably at least 9; C 10 -C 18 alkyl alkoxy carboxylates; mid-chain branched alkyl sulphates as described in more detail in US 6,020,303 and US 6,060,443
  • Preferred anionic surfactants are C 8-18 alkyl benzene sulphates and/or C 8-18 alkyl benzene sulphonates.
  • the alkyl chain of the C 8-18 alkyl benzene sulphates and/or C 8-18 alkyl benzene sulphonates may be linear or branched, preferred branched alkyl chains comprise one or more branched moieties that are C 1-6 alkyl groups.
  • Suitable anionic surfactants are selected from the group consisting of: C 8-18 alkenyl sulphates, C 8-18 alkenyl sulphonates, C 8-18 alkenyl benzene sulphates, C 8-18 alkenyl benzene sulphonates, C 8-18 alkyl di-methyl benzene sulphate, C 8-18 alkyl di-methyl benzene sulphonate, fatty acid ester sulphonates, di-alkyl sulphosuccinates, and combinations thereof.
  • esters of alpha-sulfonated fatty acids typically containing from 6 to 20 carbon atoms in the fatty acid group and from 1 to 10 carbon atoms in the ester group; 2-acyloxy-alkane-1-sulfonic acid and salts thereof, typically containing from about 2 to 9 carbon atoms in the acyl group and from about 9 to 23 carbon atoms in the alkane moiety; alpha-olefin sulfonates (AOS), typically containing from about 12 to 24 carbon atoms; and beta-alkoxy alkane sulfonates, typically containing from about 1 to 3 carbon atoms in the alkyl group and from about 8 to 20 carbon atoms in the alkane moiety.
  • AOS alpha-olefin sulfonates
  • beta-alkoxy alkane sulfonates typically containing from about 1 to 3 carbon atoms in the alkyl group and from about 8 to 20 carbon atoms in the alkane moiety.
  • fatty acid esters containing an alkyl group typically with from 10 to 20 carbon atoms.
  • C 1-4 most preferably methyl ester sulphonates.
  • Preferred are C 16-18 methyl ester sulphonates (MES).
  • the anionic surfactants may be present in the salt form.
  • the anionic surfactant(s) may be an alkali metal salt of any of the above.
  • Preferred alkali metals are sodium, potassium and mixtures thereof.
  • Preferred anionic detersive surfactants are selected from the group consisting of: linear or branched, substituted or unsubstituted, C 12-18 alkyl sulphates; linear or branched, substituted or unsubstituted, C 10-13 alkylbenzene sulphonates, preferably linear C 10-13 alkylbenzene sulphonates; and mixtures thereof. Highly preferred are linear C 10-13 alkylbenzene sulphonates.
  • linear C 10-13 alkylbenzene sulphonates that are obtainable, preferably obtained, by sulphonating commercially available linear alkyl benzenes (LAB);
  • suitable LAB include low 2-phenyl LAB, such as those supplied by Sasol under the tradename Isochem® or those supplied by Petresa under the tradename Petrelab®, other suitable LAB include high 2-phenyl LAB, such as those supplied by Sasol under the tradename Hyblene®.
  • the anionic detersive surfactant may be structurally modified in such a manner as to cause the anionic detersive surfactant to be more calcium tolerant and less likely to precipitate out of the wash liquor in the presence of free calcium ions.
  • This structural modification could be the introduction of a methyl or ethyl moiety in the vicinity of the head group of the anionic detersive surfactant, as this can lead to a more calcium tolerant anionic detersive surfactant due to steric hindrance of the head group, which may reduce the affinity of the anionic detersive surfactant for complexing with free calcium cations in such a manner as to cause precipitation out of solution.
  • the composition may comprise an alkoxylated anionic surfactant. Where present such a surfactant will generally be present in amounts from 0.1 wt% to 40 wt%, generally 0.1 to 10 wt%based on the detergent composition as a whole. It may be preferred for the composition to comprise from 3wt% to 5wt% alkoxylated anionic detersive surfactant, or it may be preferred for the composition to comprise from 1wt% to 3wt% alkoxylated anionic detersive surfactant.
  • the alkoxylated anionic detersive surfactant is a linear or branched, substituted or unsubstituted C 12-18 alkyl alkoxylated sulphate having an average degree of alkoxylation of from 1 to 30, preferably from 1 to 10.
  • the alkoxylated anionic detersive surfactant is a linear or branched, substituted or unsubstituted C 12-18 alkyl ethoxylated sulphate having an average degree of ethoxylation of from 1 to 10.
  • the alkoxylated anionic detersive surfactant is a linear unsubstituted C 12-18 alkyl ethoxylated sulphate having an average degree of ethoxylation of from 3 to 7.
  • the alkoxylated anionic detersive surfactant may also increase the non-alkoxylated anionic detersive surfactant activity by making the non-alkoxylated anionic detersive surfactant less likely to precipitate out of solution in the presence of free calcium cations.
  • the weight ratio of non-alkoxylated anionic detersive surfactant to alkoxylated anionic detersive surfactant is less than 5:1, or less than 3:1, or less than 1.7:1, or even less than 1.5:1. This ratio gives optimal whiteness maintenance performance combined with a good hardness tolerency profile and a good sudsing profile.
  • the weight ratio of non-alkoxylated anionic detersive surfactant to alkoxylated anionic detersive surfactant is greater than 5:1, or greater than 6:1, or greater than 7:1, or even greater than 10:1. This ratio gives optimal greasy soil cleaning performance combined with a good hardness tolerency profile, and a good sudsing profile.
  • Suitable alkoxylated anionic detersive surfactants are: Texapan LESTTM by Cognis; CosmacolAESTM by Sasol; BES151TM by Stephan; Empicol ESC70/UTM; and mixtures thereof.
  • compositions of the invention may comprise non-ionic surfactant. Where present it is generally present in amounts of from 0.5wt% to 20, more typically 0.5 to 10 wt% based on the total weight of the composition.
  • the composition may comprise from 1wt% to 7wt% or from 2wt% to 4wt% non-ionic detersive surfactant.
  • non-ionic detersive surfactant helps to provide a good overall cleaning profile, especially when laundering at high temperatures such as 60°C or higher.
  • the non-ionic detersive surfactant could be an alkyl polyglucoside and/or an alkyl alkoxylated alcohol.
  • the non-ionic detersive surfactant is a linear or branched, substituted or unsubstituted C 8-18 alkyl ethoxylated alcohol having an average degree of ethoxylation of from 1 to 50, more preferably from 3 to 40.
  • Non-ionic surfactants having a degree of ethoxylation from 3 to 9 may be especially useful either.
  • Nonionic surfactants having an HLB value of from 13 to 25, such as C 8-18 alkyl ethoxylated alcohols having an average degree of ethoxylation from 15 to 50, or even from 20 to 50 may also be preferred non-ionic surfactants in the compositions of the invention.
  • these latter non-ionic surfactants are Lutensol AO30 and similar materials disclosed in WO04/041982 These may be beneficial as they have good lime soap dispersant properties.
  • the non-ionic detersive surfactant not only provides additional soil cleaning performance but may also increase the anionic detersive surfactant activity by making the anionic detersive surfactant less likely to precipitate out of solution in the presence of free calcium cations.
  • the weight ratio of non-alkoxylated anionic detersive surfactant to non-ionic detersive surfactant is in the range of less than 8:1, or less than 7:1, or less than 6:1 or less than 5:1, preferably from 1:1 to 5:1, or from 2:1 to 5:1, or even from 3:1 to 4:1.
  • the detergent compositions are free of cationic surfactant.
  • the composition optionally may comprise from 0.1wt% to 10 or 5wt% cationic detersive surfactant.
  • the composition comprises from 0.5wt% to 3wt%, or from 1% to 3wt%, or even from 1wt% to 2wt% cationic detersive surfactant. This is the optimal level of cationic detersive surfactant to provide good cleaning.
  • Suitable cationic detersive surfactants are alkyl pyridinium compounds, alkyl quaternary ammonium compounds, alkyl quaternary phosphonium compounds, and alkyl ternary sulphonium compounds.
  • the cationic detersive surfactant can be selected from the group consisting of: alkoxylate quaternary ammonium (AQA) surfactants as described in more detail in US 6,136,769 ; dimethyl hydroxyethyl quaternary ammonium as described in more detail in US 6,004,922 ; polyamine cationic surfactants as described in more detail in WO 98/35002 , WO 98/35003 , WO 98/35004 , WO 98/35005 , and WO 98/35006 ; cationic ester surfactants as described in more detail in US 4,228,042 , US 4,239,660 , US 4,260,529 and US 6,022,844 ; amino surfactants as described in more detail in US 6,221,825 and WO 00/47708 , specifically amido propyldimethyl amine; and mixtures thereof.
  • AQA alkoxylate quaternary ammonium
  • Preferred cationic detersive surfactants are quaternary ammonium compounds having the general formula: (R)(R 1 )(R 2 )(R 3 )N + X - wherein, R is a linear or branched, substituted or unsubstituted C 6-18 alkyl or alkenyl moiety, R 1 and R 2 are independently selected from methyl or ethyl moieties, R 3 is a hydroxyl, hydroxymethyl or a hydroxyethyl moiety, X is an anion which provides charge neutrality, preferred anions include halides (such as chloride), sulphate and sulphonate.
  • Preferred cationic detersive surfactants are mono-C 6-18 alkyl mono-hydroxyethyl di-methyl quaternary ammonium chlorides. Highly preferred cationic detersive surfactants are mono-C 8-10 alkyl mono-hydroxyethyl di-methyl quaternary ammonium chloride, mono-C 10-12 alkyl mono-hydroxyethyl di-methyl quaternary ammonium chloride and mono-C 10 alkyl mono-hydroxyethyl di-methyl quaternary ammonium chloride. Cationic surfactants such as Praepagen HY (tradename Clariant) may be useful and may also be useful as a suds booster.
  • Praepagen HY tradename Clariant
  • the cationic detersive surfactant provides additional greasy soil cleaning performance.
  • the cationic detersive surfactant may increase the tendency of any non-alkoxylated anionic detersive surfactant to precipitate out of solution.
  • the cationic detersive surfactant and any non-alkoxylated anionic detersive surfactant are separated in the detergent composition of the invention, for example if cationic surfactant is present, preferably the cationic a dn any anionic surfactant, particularly non-alkoxylated anionic surfactant will be present in the composition in separate particles.
  • the weight ratio of non-alkoxylated anionic detersive surfactant to cationic detersive surfactant is in the range of from 5:1 to 25:1, more preferably from 5:1 to 20:1 or from 6:1 to 15:1, or from 7:1 to 10:1, or even from 8:1 to 9:1.
  • the detergent composition comprises from 1 to 50 wt% anionic surfactant, more typically from 2 to 40 wt%.
  • Alkyl benzene sulphonates are preferred anionic surfactants.
  • compositions of the present invention comprise at least two different surfactants in combination comprising at least one selected from a first group, the first group comprising alkyl benzene sulphonate and MES surfactant; and at least one selected from a second group, the second group comprising alkoxylated anionic surfactant, MES and alkoxylated non-ionic surfactant and alpha olefin sulfonates (AOS).
  • a particularly preferred combination comprises alkyl benzene sulphonate, preferably LAS in combination with MES.
  • a further particularly preferred combination comprises alkyl benzene sulphonate, preferably LAS with an alkoxylated anionic surfactant, preferably C 8-18 alkyl alkoxylated sulphate having an average degree of alkoxylation of from 1 to 10.
  • a third particularly preferred combination comprises alkyl benzene sulphonate, preferably LAS in combination with an alkoxylated non-ionic surfactant, preferably C 8-18 alkyl ethoxylated alcohol having a degree of alkoxylation of from 15 to 50, preferably from 20 to 40.
  • the weight ratio of the surfactant from the first group to the weight ratio of the surfactant from the second group is typically 1:5 to 100:1, preferably 1:2 to 100:1 or 1:1 to 50:1 or even to 20:1 or 10:1.
  • the levels of the surfactants are as described above under the specific classes of surfactants. Presence of AE3S and/or MES in the system is preferred on account of their exceptional hardness-tolerance and ability to disperse lime soaps which are formed during the wash by lipase.
  • the surfactant in the detergent compositions of the invention comprises at least three surfactants, at least one from each of the first and second groups defined above and in addition a third surfactant, preferably also from the first or second groups defined above.
  • the detergent compositions of the invention may surprisingly contain relatively low levels of surfactant and yet still perform good cleaning, on account of the soil removal functionality delivered by the lipase, so that the overall level of surfactant may be below 12 wt%, or 10 wt% or 8 wt% based on total weight of the composition
  • the detergent composition also comprises a suds booster, typically in amounts from 0.01 to 10 wt%, preferably in amounts from 0.02 to 5 wt% based on the total weight of the composition.
  • Suitable suds boosters include fatty acid amides, fatty acid alkalonamides, betaines, sulfobetaines and amine oxides. Particularly preferred materials are cocamidopropyl betaine, cocomonoethanolamide and amine oxide.
  • a suitable amine oxide is Admox 12, supplied by Albemarle.
  • the detergent compositions of the invention may additionally comprise anti-redeposition polymers such as the polymeric polycarboxylates described below.
  • anti-redeposition polymers such as the polymeric polycarboxylates described below.
  • cellulose ethers such as carboxymethyl cellulose (CMC) will be useful.
  • a suitable CMC is Tylose CR1500 G2, sold by Clariant.
  • Suitable polymers are also sold by Andercol, Colombia under the Textilan brand name.
  • additives with lime soap dispersancy functionality such as the aforementioned MES, AES, highly ethoxylated nonionic surfactant or polymers showing excellent lime soap dispersancy such as Acusol 460N (Rohm & Haas). Lists of suitable lime soap dispersants are given in the following references and documents cited therein.
  • a soil release polymer has been found to be especially beneficial in further strengthening the stain removal and cleaning benefits of the development, especially on synthetic fibres.
  • Modified cellulose ethers such as methyl hydroxyethyl cellulose (MHEC), for example as sold by Clariant as Tylose MH50 G4 and Tylose MH300 G4, are preferred.
  • Polyester-based Soil Release Polymers are especially preferred as they can also be effective as lime soap dispersants. Examples of suitable materials are Repel-o-Tex PF (supplied by Rhodia), Texcare SRA100 (supplied by Clariant) and Sokalan SR100 (BASF)
  • the formulations may contain one or more other enzymes in addition to the first wash lipase, for example protease, amylase, cellulase (especially endoglucanase), pectate lyase and/or mannanase.
  • enzymes for example protease, amylase, cellulase (especially endoglucanase), pectate lyase and/or mannanase.
  • the detergent compositions of the invention may be in any convenient form such as solids such as powdered or granular or tablet solids, bars, or liquids which may be aqueous or on-aqueous, gels or liquigels. Any of these forms may be partially or completely encapsulated.
  • the present invention particularly relates to solid detergent compositions, especially granular compositions.
  • surfactants are incorporated into agglomerates, extrudates or spray dried particles along with solid materials, usually builders, and these may be admixed to produce a fully formulated detergent composition according to the invention.
  • the detergent compositions of the present invention are preferably those having an overall bulk density of from 350 to 1200 g/l, more preferably 450 to 1000g/l or even 500 to 900g/l.
  • the detergent particles of the detergent composition in a granular form have a size average particle size of from 200 ⁇ m to 2000 ⁇ m, preferably from 350 ⁇ m to 600 ⁇ m.
  • the detergent compositions of the invention will comprise a mixture of detergent particles including combinations of agglomerates, spray-dried powders and/or dry added materials such as bleaching agents, enzymes etc.
  • the detergent compositions of the invention comprise an anionic surfactant from the list above which is a non-alkoxylated anionic detersive surfactant and this is preferably incorporated into the detergent composition in particulate form, such as via an agglomerate, a spray-dried powder, an extrudate, a bead, a noodle, a needle or a flake. Spray-dried particles are preferred.
  • the agglomerate preferably comprises at least 20%, by weight of the agglomerate, of a non-alkoxylated anionic detersive surfactant, more preferably from 25wt% to 65wt%, by weight of the agglomerate, of a non-alkoxylated anionic detersive surfactant. It may be preferred for part of the non-alkoxylated anionic detersive surfactant to be in the form of a spray-dried powder (e.g. a blown powder), and for part of the non-alkoxylated anionic detersive surfactant to be in the form of a non-spray-dried powder (e.g.
  • agglomerate, or an extrudate, or a flake such as a linear alkyl benzene sulphonate flake; suitable linear alkyl benzene sulphonate flakes are supplied by Pilot Chemical under the tradename F90®, or by Stepan under the tradename Nacconol 90G®). This is especially preferred when it is desirable to incorporate high levels of non-alkoxylated anionic detersive surfactant in the composition.
  • Any alkoxylated anionic detersive surfactant may be incorporated into the detergent compositons of the invention via a spray-dried particle of a non-spray-dried powder such as an extrudate, agglomerate, preferably an agglomerate.
  • a spray-dried particle of a non-spray-dried powder such as an extrudate, agglomerate, preferably an agglomerate.
  • Non- spray dried particles are preferred when it is desirable to incorporate high levels of alkoxylated anionic detersive surfactant in the composition
  • any non-ionic detersive surfactant, or at least part thereof can be incorporated into the composition in the form of a liquid spray-on, wherein the non-ionic detersive surfactant, or at least part thereof, in liquid form (e.g. in the form of a hot-melt) is sprayed onto the remainder of the composition.
  • the non-ionic detersive surfactant, or at least part thereof may be in included into a particulate for incorporation into the detergent composition of the invention and the non-ionic detersive surfactant, or at least part thereof, may be dry-added to the remainder of the composition.
  • the non-ionic surfactant, or at least part thereof may be in the form of a co-particulate admixture with a solid carrier material such as carbonate salt, sulphate salt, burkeite, silica or any mixture thereof.
  • Any non-ionic detersive surfactant, or at least part thereof, may be in a co-particulate admixture with either an alkoxylated anionic detersive surfactant, a non-alkoxylated anionic detersive surfactant or a cationic detersive surfactant.
  • the non-ionic detersive surfactant, or at least part thereof, may be agglomerated or extruded with either an alkoxylated anionic detersive surfactant, a non-alkoxylated anionic detersive surfactant or a cationic detersive surfactant.
  • the cationic detersive surfactant if present may be incorporated into the composition by incorporation in a particulate, such as a spray-dried powder, an agglomerate, an extrudate, a flake, a noodle, a needle, or any combination thereof.
  • a particulate such as a spray-dried powder, an agglomerate, an extrudate, a flake, a noodle, a needle, or any combination thereof.
  • the cationic detersive surfactant, or at least part thereof is in the form of a spray-dried powder or an agglomerate.
  • the detergent ingredients can include one or more other detersive adjuncts or other materials for assisting or enhancing cleaning performance, treatment of the substrate to be cleaned, or to modify the aesthetics of the detergent composition.
  • Usual detersive adjuncts of detergent compositions include the ingredients set forth in U.S. Pat. No. 3,936,537, Baskerville et al. and in Great Britain Patent Application No. 9705617.0, Trinh et al., published September 24, 1997 .
  • adjuncts are included in detergent compositions at their conventional art-established levels of use, generally from 0 wt% to about 80 wt% of the detergent ingredients, preferably from about 0.5 wt% to about 20wt % and can include color speckles, suds boosters, suds suppressors, anti-tarnish and/or anticorrosion agents, soil-suspending agents, soil release agents, dyes, fillers, optical brighteners, germicides, alkalinity sources, hydrotropes, antioxidants, enzymes, enzyme stabilizing agents, solvents, solubilizing agents, chelating agents, clay soil removal/anti-redeposition agents, polymeric dispersing agents, processing aids, fabric softening components, static control agents, bleaching agents, bleaching activators, bleach stabilizers, dye-transfer inhibitors, flocculants, fabric softeners, suds supressors, fabric integrity agents, perfumes, whitening agents, photobleach, alkali metal sulphate salts, sulphamic acid, sodium
  • Preferred zwitterionic surfactants comprise one or more quaternized nitrogen atoms and one or more moieties selected from the group consisting of: carbonate, phosphate, sulphate, sulphonate, and combinations thereof.
  • Preferred zwitterionic surfactants are alkyl betaines.
  • Other preferred zwitterionic surfactants are alkyl amine oxides.
  • Catanionic surfactants which are complexes comprising a cationic surfactant and an anionic surfactant may also be included. Typically, the molar ratio of the cationic surfactant to anionic surfactant in the complex is greater than 1:1, so that the complex has a net positive charge.
  • compositions of the invention may comprise bleach boosters.
  • Preferred bleach boosters are selected from the group consisting of: zwitterionic imines, anionic imine polyions, quaternary oxaziridinium salts, and combinations thereof.
  • Highly preferred bleach boosters are selected from the group consisting of aryliminium zwitterions, aryliminium polyions, and combinations thereof.
  • Suitable bleach boosters are described in US360568 , US5360569 and US5370826 .
  • a preferred adjunct component is an anti-redeposition agent.
  • the detergent composition comprises one or more anti-redeposition agents.
  • Preferred anti-redeposition agents are cellulosic polymeric components, most preferably carboxymethyl celluloses.
  • a preferred adjunct component is a chelant.
  • the detergent composition comprises one or more chelants.
  • the detergent composition comprises (by weight of the composition) from 0.01 % to 10% chelant, or 0.01 to 5 wt% or 4 wt% or 2 wt%.
  • Preferred chelants are selected from the group consisting of: hydroxyethane-dimethylene-phosphonic acid, ethylene diamine tetra(methylene phosphonic) acid, diethylene triamine pentacetate, ethylene diamine tetraacetate, diethylene triamine penta(methyl phosphonic) acid, ethylene diamine disuccinic acid, and combinations thereof.
  • a preferred adjunct component is a dye transfer inhibitor.
  • the detergent composition comprises one or more dye transfer inhibitors.
  • dye transfer inhibitors are polymeric components that trap dye molecules and retain the dye molecules by suspending them in the wash liquor.
  • Preferred dye transfer inhibitors are selected from the group consisting of: polyvinylpyrrolidones, polyvinylpyridine N-oxides, polyvinylpyrrolidone-polyvinylimidazole copolymers, and combinations thereof.
  • Preferred adjunct components include other enzymes.
  • the detergent composition comprises one or more additional enzymes.
  • Preferred enzymes are selected from then group consisting of: amylases, arabinosidases, carbohydrases, cellulases, chondroitinases, cutinases, dextranases, esterases, ⁇ -glucanases, gluco-amylases, hyaluronidases, keratanases, laccases, ligninases, lipoxygenases, malanases, mannanases, oxidases, pectinases, pentosanases, peroxidases, phenoloxidases, phospholipases, proteases, pullulanases, reductases, tannases, transferases, xylanases, xyloglucanases, and combinations thereof.
  • Preferred additional enzymes are selected from the group consisting of: amylases, carbohydrases, cellul
  • a preferred adjunct component is a fabric integrity agent.
  • the detergent composition comprises one or more fabric integrity agents.
  • fabric integrity agents are polymeric components that deposit on the fabric surface and prevent fabric damage during the laundering process.
  • Preferred fabric integrity agents are hydrophobically modified celluloses. These hydrophobically modified celluloses reduce fabric abrasion, enhance fibre-fibre interactions and reduce dye loss from the fabric.
  • a preferred hydrophobically modified cellulose is described in WO99/14245 .
  • Other preferred fabric integrity agents are polymeric components and/or oligomeric components that are obtainable, preferably obtained, by a process comprising the step of condensing imidazole and epichlorhydrin.
  • a preferred adjunct component is a salt.
  • the detergent composition comprises one or more salts.
  • the salts can act as alkalinity agents, buffers, builders, co-builders, encrustation inhibitors, fillers, pH regulators, stability agents, and combinations thereof.
  • the detergent composition comprises (by weight of the composition) from 5% to 60% salt.
  • Preferred salts are alkali metal salts of aluminate, carbonate, chloride, bicarbonate, nitrate, phosphate, silicate, sulphate, and combinations thereof.
  • Other preferred salts are alkaline earth metal salts of aluminate, carbonate, chloride, bicarbonate, nitrate, phosphate, silicate, sulphate, and combinations thereof.
  • Especially preferred salts are sodium sulphate, sodium carbonate, sodium bicarbonate, sodium silicate, sodium sulphate, and combinations thereof.
  • the alkali metal salts and/or alkaline earth metal salts may be anhydrous.
  • a preferred adjunct component is a soil release agent.
  • the detergent composition comprises one or more soil release agents.
  • soil release agents are polymeric compounds that modify the fabric surface and prevent the redeposition of soil on the fabric.
  • Preferred soil release agents are copolymers, preferably block copolymers, comprising one or more terephthalate unit.
  • Preferred soil release agents are copolymers that are synthesised from dimethylterephthalate, 1,2-propyl glycol and methyl capped polyethyleneglycol.
  • Other preferred soil release agents are anionically end capped polyesters.
  • compositions of the invention may comprise at least 0.1wt%, or at least 0.5 wt%, or at least 2 or 3 wt%, or even at least 5 wt% polymeric polycarboxylates up to levels of 30 wt% or 20 wt% or 10 wt%.
  • Preferred polymeric polycarboxylates include polyacrylates and co-polymers of maleic acid and acrylic acid.
  • Suitable polycarboxylates are the Sokalan CP, PA and HP ranges (BASF) such as Sokalan CP5, PA40 and HP22, and the Alcosperse range of polymers (Alco) such as Alcosperse 725, 747, 408, 412 and 420.
  • the composition comprises at least 1wt%, or at least 2wt%, or at least 3wt% soil dispersants.
  • the detergent compositions of the invention may comprise softening agents for softening through the wash such as clay optionally also with flocculant and enzymes.
  • the invention also includes methods of washing textiles comprising contacting textiles with an aqueous solution comprising the detergent composition of the invention.
  • the invention may be particularly beneficial at low water temperatures such as below 30°C or below 25 or 20°C.
  • the aqueous wash liquor will comprise at least 100 ppm, or at least 500ppm of the detergent composition

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Claims (9)

  1. Composition détergente comprenant une source de péroxyde d'hydrogène, un peracide hydrophobe et/ou un précurseur de celui-ci ayant pour formule R-(C=O)-L où R est un groupe alkyl ayant de 6 à 14, préférablement de 8 à 12 atomes de carbone, et L est un groupe partant de benzènesulfonate, et une enzyme lipase qui est un polypeptide ayant une séquence d'acide aminés qui : (a) a au moins 90 % d'identité avec la lipase de type sauvage dérivée de la souche d'Humicola lanuginosa DSM 4109 ; (b) par comparaison avec ladite lipase de type sauvage, comprend une substitution d'un acide aminé électriquement neutre ou chargé négativement à la surface de la structure tridimensionnelle dans les 15 Å de E1 ou Q249 avec un acide aminé chargé positivement dans laquelle la substitution est à n'importe laquelle des positions 1 à 11, 90, 95, 169, 171 à 175, 192 à 211, 213 à 226, 228 à 258, 260 à 262 ; et (c) comprend une addition de peptide à la terminaison C ; et/ou (d) comprend une addition de peptide à la terminaison N et/ou (e) rencontre les limitations suivantes : i) comporte un acide aminé négatif en position E210 de ladite lipase de type sauvage ; ii) comprend un acide aminé chargé négativement dans la région correspondant aux positions 90 à 101 de ladite lipase de type sauvage ; et iii) comprend un acide aminé neutre ou négatif à une position correspondant à N94 de ladite lipase de type sauvage et/ou a une charge électrique nette négative ou neutre dans la région correspondant aux positions 90 à 101 de ladite lipase de type sauvage ; la composition détergente ayant une alcalinité de réserve de plus de 6,5, la quantité d'oxygène disponible (provenant de la source de péroxyde) et de peracide et/ou de précurseur de celui-ci étant de sorte à fournir à la composition détergente un rapport molaire d'oxygène disponible (provenant de la source de peroxyde) : peracide allant de 2:1 à 8:1.
  2. Composition détergente selon la revendication 1 ayant une alcalinité de réserve supérieure à 8, ou supérieure à 9.
  3. Composition détergente selon l'une quelconque des revendications précédentes, dans laquelle l'activateur de blanchiment hydrophobe comprend du sulfonate nonanoyloxybenzène.
  4. Composition détergente selon l'une quelconque des revendications précédentes comprenant de 0,1 à 40 % en poids d'agent tensioactif alkylsulfate alcoxylé et/ou de 0,1 à 40 % en poids de sulfonate d'ester d'alkyle en C1 à 4, de préférence du sulfonate d'ester de méthyle (MES), de préférence en combinaison avec un agent tensioactif de sulfonate de benzène d'alkyle en une quantité allant de 5 à 40 % en poids.
  5. Composition détergente selon l'une quelconque des revendications précédentes, comprenant un renforçateur de mousse en une quantité allant de 0,05 à 2 % en poids, de préférence choisi parmi les amides d'acide gras, alcanolamides d'acide gras, bétaïnes, sulfobétaïnes et oxydes d'amine ou des mélanges de ceux-ci.
  6. Composition détergente selon l'une quelconque des revendications précédentes, comprenant de 0,05 à 5, préférablement de 0,1 à 1 % en poids de tétraacétyléthylènediamine (TAED).
  7. Composition détergente selon l'une quelconque des revendications précédentes, qui est une composition détergente solide, de préférence granulaire.
  8. Procédé de lavage comprenant le lavage d'articles textiles dans une solution aqueuse comprenant la composition détergente selon l'une quelconque des revendications précédentes.
  9. Procédé de lavage selon la revendication 8, dans lequel la solution aqueuse est à une température inférieure à 30 °C.
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CN101484565B (zh) 2006-01-23 2011-12-14 宝洁公司 包含脂肪酶和漂白催化剂的组合物
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WO2014200658A1 (fr) 2013-06-13 2014-12-18 Danisco Us Inc. Alpha-amylase issue de promicromonospora vindobonensis
WO2014200657A1 (fr) 2013-06-13 2014-12-18 Danisco Us Inc. Alpha-amylase provenant destreptomyces xiamenensis
US20160130571A1 (en) 2013-06-17 2016-05-12 Danisco Us Inc. Alpha-Amylase from Bacillaceae Family Member
EP3052622B1 (fr) 2013-10-03 2018-09-19 Danisco US Inc. Alpha-amylases faisant partie d'un sous-ensemble d'exiguobacterium, et procédés d'utilisation correspondants
US20160160199A1 (en) 2013-10-03 2016-06-09 Danisco Us Inc. Alpha-amylases from exiguobacterium, and methods of use, thereof
CN105960456A (zh) 2013-11-20 2016-09-21 丹尼斯科美国公司 对蛋白酶裂解敏感性降低的变体α-淀粉酶及其使用方法
US9783766B2 (en) 2015-04-03 2017-10-10 Ecolab Usa Inc. Enhanced peroxygen stability using anionic surfactant in TAED-containing peroxygen solid
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