EP1698689A1 - Waschmittelzusammensetzungen - Google Patents

Waschmittelzusammensetzungen Download PDF

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Publication number
EP1698689A1
EP1698689A1 EP05251269A EP05251269A EP1698689A1 EP 1698689 A1 EP1698689 A1 EP 1698689A1 EP 05251269 A EP05251269 A EP 05251269A EP 05251269 A EP05251269 A EP 05251269A EP 1698689 A1 EP1698689 A1 EP 1698689A1
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EP
European Patent Office
Prior art keywords
detergent composition
alkyl
preferred
surfactant
peracid
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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EP05251269A
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English (en)
French (fr)
Inventor
Neil Joseph Lant
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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
Priority to EP05251269A priority Critical patent/EP1698689A1/de
Priority to EP06110531.8A priority patent/EP1726636B2/de
Priority to JP2007554364A priority patent/JP2008531758A/ja
Priority to PCT/US2006/007733 priority patent/WO2006094232A1/en
Priority to CNA2006800068987A priority patent/CN101133148A/zh
Priority to CA002597226A priority patent/CA2597226A1/en
Priority to MX2007010725A priority patent/MX2007010725A/es
Priority to KR1020077020160A priority patent/KR20070103764A/ko
Priority to AU2006218400A priority patent/AU2006218400A1/en
Priority to BRPI0607406-5A priority patent/BRPI0607406A2/pt
Publication of EP1698689A1 publication Critical patent/EP1698689A1/de
Priority to EGNA2007000921 priority patent/EG24955A/xx
Withdrawn legal-status Critical Current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
    • C11D17/00Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06Powder; Flakes; Free-flowing mixtures; Sheets
    • 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
    • C11D3/39Organic or inorganic per-compounds
    • C11D3/3902Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905Bleach activators or bleach catalysts
    • C11D3/3907Organic compounds
    • 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
    • C11D3/39Organic or inorganic per-compounds
    • C11D3/3942Inorganic per-compounds
    • 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
    • C11D3/39Organic or inorganic per-compounds
    • C11D3/3945Organic per-compounds
    • 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
    • C11D2111/00Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10Objects to be cleaned
    • C11D2111/12Soft surfaces, e.g. textile

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.
  • the main commercially available lipase enzymes such as Lipolase (trade name, Novozymes) worked particularly effectively at the lower moisture levels of the drying phase of the wash process.
  • Lipolase trade name, Novozymes
  • 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.
  • first wash 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.
  • examples of such enzymes are as described in WO00/60063 and Research Disclsoure IP6553D. Such enzymes are referred to below as first wash lipases.
  • 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 1:1 to 35:1, 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.
  • R is an alkyl group, optionally branched, having from 6 to 14 carbon atoms, more preferably from 8 to 12 carbon atoms; M is a counterion, preferably being sodium, potassium or hydrogen; and L is a leaving group.
  • Preferred leaving groups are benzoic acid and derivatives thereof and especially benzene sulphonate.
  • 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 1:1 to 35:1.
  • Preferred molar ratios are from 2:1 to 10:1, or even 3:1 or even 5:1 to 8:1.
  • the preferred lipase enzymes are described in WO00/160063, 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 N233R.
  • 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 coated enzyme particle.
  • Detergent Composition A A:
  • the percentage of lard removed is determined as;
  • 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.
  • the RA of the detergent compositions of the invention will be greater than 6.5 and preferably greater than 7.5.
  • the RA may be greater than 8 or even greater than 9 or 9.5 or higher.
  • the RA may be up to 20 or higher.
  • 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 af 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 form 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; Cosmacol AESTM 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 dimethyl 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 (AQS).
  • 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 alkalonanudes, 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.
  • lime soap dispersancy functionality such as the aforementioned MES, AES, highly ethoxylated nonionic surfactant or polymers showing excellent lime soap dispersancy such as Acusal 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 900G® ). 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, antitarnish 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 s
  • 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 arc 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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EP05251269A EP1698689A1 (de) 2005-03-03 2005-03-03 Waschmittelzusammensetzungen
EP06110531.8A EP1726636B2 (de) 2005-03-03 2006-02-28 Waschmittelzusammensetzungen
CA002597226A CA2597226A1 (en) 2005-03-03 2006-03-02 Detergent compositions comprising a humicola lanuginosa lipase variant and a bleaching system
PCT/US2006/007733 WO2006094232A1 (en) 2005-03-03 2006-03-02 Detergent compositions
CNA2006800068987A CN101133148A (zh) 2005-03-03 2006-03-02 洗涤剂组合物
JP2007554364A JP2008531758A (ja) 2005-03-03 2006-03-02 洗剤組成物
MX2007010725A MX2007010725A (es) 2005-03-03 2006-03-02 Composiciones detergentes.
KR1020077020160A KR20070103764A (ko) 2005-03-03 2006-03-02 세제 조성물
AU2006218400A AU2006218400A1 (en) 2005-03-03 2006-03-02 Detergent compositions
BRPI0607406-5A BRPI0607406A2 (pt) 2005-03-03 2006-03-02 composições detergentes
EGNA2007000921 EG24955A (en) 2005-03-03 2007-08-29 Detergent compositions.

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DE102006004697A1 (de) * 2006-01-31 2007-08-02 Henkel Kgaa Wasch- oder Reinigungsmittel mit Farbübertragungsinhibitor
WO2011005813A1 (en) * 2009-07-09 2011-01-13 The Procter & Gamble Company Method of laundering fabric using a compacted laundry detergent composition
EP2377914A1 (de) * 2010-04-19 2011-10-19 The Procter & Gamble Company Schwach alkalische, feste Waschmittelzusammensetzung mit Perhydrolase und wenig Builder
WO2014200658A1 (en) 2013-06-13 2014-12-18 Danisco Us Inc. Alpha-amylase from promicromonospora vindobonensis
WO2014200656A1 (en) 2013-06-13 2014-12-18 Danisco Us Inc. Alpha-amylase from streptomyces umbrinus
WO2014200657A1 (en) 2013-06-13 2014-12-18 Danisco Us Inc. Alpha-amylase from streptomyces xiamenensis
WO2014204596A1 (en) 2013-06-17 2014-12-24 Danisco Us Inc. Alpha-amylase from bacillaceae family member
WO2015050723A1 (en) 2013-10-03 2015-04-09 Danisco Us Inc. Alpha-amylases from exiguobacterium, and methods of use, thereof
WO2015050724A1 (en) 2013-10-03 2015-04-09 Danisco Us Inc. Alpha-amylases from a subset of exiguobacterium, and methods of use, thereof
WO2015077126A1 (en) 2013-11-20 2015-05-28 Danisco Us Inc. Variant alpha-amylases having reduced susceptibility to protease cleavage, and methods of use, thereof
WO2017173190A2 (en) 2016-04-01 2017-10-05 Danisco Us Inc. Alpha-amylases, compositions & methods
WO2017173324A2 (en) 2016-04-01 2017-10-05 Danisco Us Inc. Alpha-amylases, compositions & methods

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MX2010004139A (es) * 2007-10-22 2010-04-30 Lion Corp Granulos secados por rocio, metodo de produccion de los mismos y composicion detergente granular que contiene los granulos secados por rocio.
CN102112602A (zh) * 2008-02-29 2011-06-29 宝洁公司 包含脂肪酶的洗涤剂组合物
JP5347156B2 (ja) * 2008-06-12 2013-11-20 ライオン株式会社 高嵩密度粒状洗剤組成物
EP2270124A1 (de) * 2009-06-30 2011-01-05 The Procter & Gamble Company Bleichzusammensetzungen mit Parfümliefersystem
US8846107B2 (en) 2010-12-29 2014-09-30 Ecolab Usa Inc. In situ generation of peroxycarboxylic acids at alkaline pH, and methods of use thereof
EP2687094B1 (de) 2010-12-29 2018-05-02 Ecolab USA Inc. Erzeugung von Peroxycarboxylsäuren mit alkalischem pH-Wert und deren Verwendung als Textilienbleichmittel und antimikrobielle Wirkstoffe
US9321664B2 (en) 2011-12-20 2016-04-26 Ecolab Usa Inc. Stable percarboxylic acid compositions and uses thereof
CA2867565C (en) 2012-03-30 2021-01-19 Victor KEASLER Use of peracetic acid/hydrogen peroxide and peroxide-reducing agents for treatment of drilling fluids, frac fluids, flowback water and disposal water
US20140256811A1 (en) 2013-03-05 2014-09-11 Ecolab Usa Inc. Efficient stabilizer in controlling self accelerated decomposition temperature of peroxycarboxylic acid compositions with mineral acids
US8822719B1 (en) 2013-03-05 2014-09-02 Ecolab Usa Inc. Peroxycarboxylic acid compositions suitable for inline optical or conductivity monitoring
US10165774B2 (en) 2013-03-05 2019-01-01 Ecolab Usa Inc. Defoamer useful in a peracid composition with anionic surfactants
JP2017149936A (ja) * 2016-02-23 2017-08-31 ライオン株式会社 衣料用粉末洗浄剤組成物
ES2877130T3 (es) * 2018-06-29 2021-11-16 Procter & Gamble Composición detergente para lavado de ropa que comprende un copolímero tribloque de óxido de etileno-óxido de propileno-óxido de etileno (OE/OP/OE) y una lipasa

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Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102006004697A1 (de) * 2006-01-31 2007-08-02 Henkel Kgaa Wasch- oder Reinigungsmittel mit Farbübertragungsinhibitor
WO2011005813A1 (en) * 2009-07-09 2011-01-13 The Procter & Gamble Company Method of laundering fabric using a compacted laundry detergent composition
EP2377914A1 (de) * 2010-04-19 2011-10-19 The Procter & Gamble Company Schwach alkalische, feste Waschmittelzusammensetzung mit Perhydrolase und wenig Builder
WO2011133381A1 (en) * 2010-04-19 2011-10-27 The Procter & Gamble Company A mildly alkaline, low-built, solid fabric treatment detergent composition comprising perhydrolase
WO2014200658A1 (en) 2013-06-13 2014-12-18 Danisco Us Inc. Alpha-amylase from promicromonospora vindobonensis
WO2014200656A1 (en) 2013-06-13 2014-12-18 Danisco Us Inc. Alpha-amylase from streptomyces umbrinus
WO2014200657A1 (en) 2013-06-13 2014-12-18 Danisco Us Inc. Alpha-amylase from streptomyces xiamenensis
WO2014204596A1 (en) 2013-06-17 2014-12-24 Danisco Us Inc. Alpha-amylase from bacillaceae family member
WO2015050723A1 (en) 2013-10-03 2015-04-09 Danisco Us Inc. Alpha-amylases from exiguobacterium, and methods of use, thereof
WO2015050724A1 (en) 2013-10-03 2015-04-09 Danisco Us Inc. Alpha-amylases from a subset of exiguobacterium, and methods of use, thereof
WO2015077126A1 (en) 2013-11-20 2015-05-28 Danisco Us Inc. Variant alpha-amylases having reduced susceptibility to protease cleavage, and methods of use, thereof
WO2017173190A2 (en) 2016-04-01 2017-10-05 Danisco Us Inc. Alpha-amylases, compositions & methods
WO2017173324A2 (en) 2016-04-01 2017-10-05 Danisco Us Inc. Alpha-amylases, compositions & methods

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EG24955A (en) 2011-02-21
KR20070103764A (ko) 2007-10-24
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