EP2707472B1 - Konzentrierte wässrige waschmittelzusammensetzungen - Google Patents

Konzentrierte wässrige waschmittelzusammensetzungen Download PDF

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Publication number
EP2707472B1
EP2707472B1 EP12719395.1A EP12719395A EP2707472B1 EP 2707472 B1 EP2707472 B1 EP 2707472B1 EP 12719395 A EP12719395 A EP 12719395A EP 2707472 B1 EP2707472 B1 EP 2707472B1
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EP
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Prior art keywords
surfactant
alkyl
composition according
hydroxamate
epei
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French (fr)
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EP2707472A1 (de
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Julie Bennett
Anthony Mckee
Alyn James Parry
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Unilever PLC
Unilever NV
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Unilever PLC
Unilever NV
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/86—Mixtures of anionic, cationic, and non-ionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29—Sulfates of polyoxyalkylene ethers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with anionic 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
    • C11D10/00—Compositions of detergents, not provided for by one single preceding group
    • C11D10/04—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/32—Amides; Substituted amides
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3723—Polyamines or polyalkyleneimines
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/52—Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides

Definitions

  • This invention relates to aqueous concentrated laundry detergent compositions and their use at low dosage, and hence low in wash surfactant concentrations, for cleaning of red clay from polyester fabrics under hard water washing conditions.
  • EP 388 389 A2 discloses bleach free under-built liquid detergent compositions containing hydroxamic acids and their derivatives which assist in the removal of bleachable wine stains from fabrics during laundering.
  • Hydroxamates as in Formula I are disclosed, wherein R 1 represents an optionally substituted straight- or branched chain C 5 -C 21 alkyl or C 5 -C 21 alkenyl group or an optionally-substituted phenyl group.
  • R 1 represents an optionally substituted straight- or branched chain C 5 -C 21 alkyl or C 5 -C 21 alkenyl group or an optionally-substituted phenyl group.
  • One of the examples shows an improved bleaching performance when a hydroxamate is used in a detergent composition in hard water (20° German hardness (DH), which is about 143 milligram calcium per litre).
  • the examples use C 12 linear, C 12 branched, C 13 branched and C 18 hydroxamates in detergent formulations comprising mixtures of anionic surfactant and nonionic surfactant.
  • examples I, II and IV there is an excess of nonionic surfactant of at least 1.25 to 1 and in example III there is 100% anionic sur
  • WO2010/069957 discloses the use of hydroxamate in conjunction with a specific anionic and nonionic surfactant system to improve the cleaning performance of both powder and liquid compositions on certain stains, notably red clay.
  • Various formulation possibilities are discussed. The examples all use high in-wash surfactant levels. Washing is done under both soft (6°FH) and hard (26°FH) water conditions. A builder (1 wt% sodium citrate) is added for washing in hard water.
  • the ratio of surfactant to hydroxamate claimed is from 5:1 to 15:1.
  • WO2011/151170 discloses that the beneficial effect described in WO2010/069957 can also be obtained when using similar laundry detergent formulations that containing less than 0.5 wt% hydroxamic acid, or its corresponding hydroxamate.
  • the weight ratio of the defined surfactant system to the hydroxamate is correspondingly extended up to 16 000:1, the preferred ratio being from 10:1 to 400:1.
  • EPEI ethoxylated polyethylene imine polymer
  • EPEI is known from many publications as a polymer that can be added to detergent compositions along with the usual surfactants to improve stain removal: both oily stains and particulate stains.
  • EPEI is available in the original nonionic form based on PEI of various molecular weights (typically 200 to 2000) and degrees of branching and various further modifications have been proposed.
  • the EPEI may be cationic (quaternised) and possibly sulphated. It may have nitrogen oxide groups added to make amine oxides and the alkoxyl groups may comprise a mixture of ethylene oxide and other alkylene oxides, for example propylene oxide or butylene oxide. These may be arranged in blocks.
  • US 5 834 412 is primarily concerned with soil release polymers.
  • EP 2135934 A1 discloses a synergistic clay soil removal benefit when nonionic EPEI is used in combination with a specific type of first wash lipase (Lipex).
  • the clay is not necessarily red clay (i.e. clay with high iron content).
  • Paragraph 12 of this publication contains an obvious error. In defining what is meant by primary detergency it makes use of a definition transferred from a different application and refers in error to a composition in which "the hydroxamate is used as cosurfactant according to the invention". Firstly, hydroxamate is a properly categorised as a sequestrant, not as a cosurfactant, secondly hydroxamate is totally absent from the invention described and claimed in EP 2135934 .
  • WO2009/153184 (Unilever) describes a method of laundering fabrics that uses very low levels of in wash surfactant (that may be an anionic surfactant). Wash performance is boosted by inclusion of high levels of specific polymers and enzymes.
  • a preferred enzyme is lipase, most preferably Lipex.
  • Preferred polymers are a combination of EPEI and a polyester soil release polymer.
  • the surfactant system preferably includes SLES and most preferably also carbobetaine.
  • a sequestrant is included in the exemplified compositions: Dequest 2066. This is Diethylenetriamine penta(methylene phosphonic acid). No mention is made of hydroxamate.
  • compositions comprising surfactants and hydroxamate and having excellent performance when used at low in-wash surfactant levels as discussed in WO2009/153184 , particularly when the composition does not also comprise a lipase enzyme and most particularly when used under hard water conditions for the removal of red clay stains from polyester.
  • wt% refers to the total weight percentage in the liquid as dry weight.
  • an aqueous concentrated liquid laundry detergent comprising:
  • Polyethylene imines comprise amino moieties where one two or three hydrogens on a nitrogen have been replaced.
  • a substitution site means a residual hydrogen on the nitrogen.
  • the nitrogen is a terminal one having two hydrogens then it has two substitution sites and replacing each hydrogen with a 20EO group means that there are 20 ethoxy units on each substitution site on the nitrogen and the average substitution is also 20.
  • the amount of (a) is greater than or equal to the amount of (b), more preferably the amount of (b) is at least 3 wt%.
  • the preferred anionic surfactants (a) comprise a mixture of LAS and AES.
  • compositions according to the invention have a weight ratio of non-soap surfactant [(a)+(b)+(c) - soap] to EPEI of from 3:1 to 6:1, even about 5:1.
  • Preferred detersive surfactant (c) is soap, amphoteric surfactants, for example betaine and mixtures thereof.
  • Component (c) also includes any amine oxide surfactant present in the composition. Soap levels in the composition are preferably less than 3 wt%.
  • compositions of the invention are concentrated compositions designed for dilution by a factor of at least 500 when forming a wash liquor, the amount of alkyl hydroxamate in the compositions is large as a weight percentage of the composition.
  • the preferred weight ratio of alkyl hydroxamate (d) to total detersive surfactant system (a), (b) and (c) for optimum particulate red clay soil removal lies In the range 1:4 to 1: 8000. More preferred Is 1:7 to 1:40. An even more preferred range of ratios being 1:10 to 1:30 parts by weight.
  • the amount of alkyl hydroxamate (d) is preferably at least 0.5, more preferably at least 1.0 wt%
  • compositions may comprise polyester based soil release polymers that are particularly effective with the EPEI and hydroxamate combination at low surfactant levels.
  • Lipase is generally incompatible with such ester containing materials. It is therefore preferred that lipase is absent from the compositions.
  • the composition further comprises at least 0.4 wt% perfume, preferably at least 0.5 wt%.
  • the perfume is selected from free oil perfume encapsulated perfume and mixtures thereof. Preferably it comprises mixtures of these types of perfume.
  • a method of washing polyester fabrics comprising the steps of combining 15 to 25 ml of the composition according to the invention with water having a hardness of at least 20°FH to form a wash liquor having a non-soap surfactant concentration of less than 0.5 g/L and washing the polyester with the wash liquor.
  • the invention further comprises the use of a composition according to the invention in a washing process carried out in water of hardness of at least 20°FH to remove red clay from polyester.
  • a concentrated laundry liquid with lower surfactant than is normal for such a concentrated composition is used, as described in WO2009/153184 .
  • a low volume of less than 25 ml and preferably around 20 ml, of the concentrated liquid composition of the invention is dosed to a wash load and diluted with water to form the wash liquor for use in the washing method according to the second aspect of the invention.
  • suitable compositions for use in the process according to the invention may comprise the ingredients described below at the levels detailed below.
  • compositions comprise surfactant.
  • the non-soap detersive surfactant makes up at least 10 wt% of the liquid composition, preferably it makes up from 12 to 60 wt%.
  • the compositions for use according to the invention most preferably have total active detersive surfactant levels of at least 15 wt%.
  • compositions are used in small doses that require them to be diluted in at least 500 times their own volume of water to form a main-wash liquor comprising at most 0.5 g/l surfactant.
  • They may be concentrated compositions designed for front-loading automatic washing machines, hand-washing or top-loading automatic washing machines. In hand-washing less water may be used and in top-loading automatic washing machines a higher amount of water would normally be used than for a front-loading automatic machine.
  • the dose of detergent liquid is adjusted accordingly to give similar wash liquor concentrations.
  • compositions are aqueous.
  • the amount of water is a least 5 wt%, preferably at least 25 wt%.
  • Hydroxamic acids are a class of chemical compounds in which a hydroxylamine is inserted into a carboxylic acid.
  • the general structure of a hydroxamic acid is the following: in which R 1 is an organic residue, for example alkyl or alkylene groups.
  • the hydroxamic acid may be present as its corresponding alkali metal salt, or hydroxamate.
  • the preferred salt is the potassium salt.
  • the hydroxamates may conveniently be formed from the corresponding hydroxamic acid by substitution of the acid hydrogen atom by a cation as shown in Formula II.
  • L + is a monovalent cation for example the alkali metals (e.g. potassium, sodium), or ammonium or a substituted ammonium.
  • alkyl hydroxamic acid or its corresponding alkyl hydroxamate has the structure shown in Formula I: wherein R 1 is:
  • references to a number of carbon atoms include mixed chain length materials provided that some of the hydroxamate material falls within the ranges specified and the ratios and amounts are determined by excluding any material falling outside of the specified range.
  • the preferred alkyl hydroxamates are those where R 1 is C 8 to C 14 alkyl, preferably normal alkyl, most preferably saturated.
  • the alkyl hydroxamate containing compositions according to the invention are particularly suitable for use on red clay and especially suited to the removal of red clay stains from polyester under hard water washing conditions and with low levels of detersive surfactant in the wash water.
  • R 1 is chosen from the group consisting of C 4 , C 5 , C 6 , C 7 , C 8 , C 9 , C 10 , C 11 , C 12 and C 14 normal alkyl group, most preferably R 1 is at least a C 8-14 normal alkyl group.
  • R 1 is at least a C 8-14 normal alkyl group.
  • the potassium salt is particularly useful.
  • hydroxamic acids whilst less preferred, are suitable for use in the present invention.
  • suitable compounds include, but are not limited to, the following compounds:
  • Such hydroxamic acids are commercially available.
  • the alkyl hydroxamate is thought to act by binding to metal ions that are present in the soil on the fabric. This binding action, which is, in effect, the known sequestrant property of the hydroxamate is not, in itself, of any use to remove the soil from the fabric.
  • the key is the "tail" of the hydroxamate i.e. the group R 1 .
  • the tail is selected to have an affinity for the surfactant system.
  • the soil removal ability of an already optimised surfactant system is further enhanced by the use of the hydroxamate as it, in effect, labels the difficult to remove particulate material (clay) as "soil” for removal by the surfactant system acting on the hydroxamate molecules now fixed to the particulates via their binding to the metal ions embedded in the clay type particulates.
  • the non-soap detersive surfactants will adhere to the hydroxamate, leading overall to more surfactants interacting with the fabric, leading to better soil release.
  • the alkyl hydroxamate acts as a linker molecule facilitating the removal and suspension of the particulate soil from the fabric into a wash liquor and thus boosting the primary detergency.
  • Alkyl hydroxamates have a higher affinity for transition metals, like iron, than for alkaline earth metals, for example calcium and magnesium, therefore the hydroxamate primarily acts to improve the removal of soil on fabric, especially particulate soils, and not additionally as a builder for calcium and magnesium.
  • a preferred alkyl hydroxamate is the 80% solids coco hydroxamic acid available under the trade name RK853 from Axis House.
  • the corresponding alkyl hydroxamate Potassium salt is available from Axis House under the trade name RK852.
  • Axis house also supply the coco hydroxamic acid as a 50% solids material under the trade name RK858.
  • the 50% coco hydroxamate potassium salt is available as RK857.
  • Another preferred material is RK842, an Alkyl hydroxamic acid made from Palm Kernel Oil, from Axis House. Alkyl hydroxamates do not generate any residues.
  • Surfactants assist in removing soil from the textile materials and also assist in maintaining removed soil in solution or suspension in the wash liquor.
  • Anionic or blends of anionic and nonionic surfactants are a preferred feature of the present invention.
  • the amount of anionic non-soap surfactant is at least 8 wt%.
  • Preferred anionic surfactants are alkylbenzene sulphonates, particularly linear alkylbenzene sulphonates (LAS) having an alkyl chain length of C 8 -C 15 .
  • the counter ion for the anionic surfactants is generally an alkali metal, typically sodium, although other counter-ions for example MEA, TEA or ammonium can be used.
  • Preferred linear alkyl benzene sulphonate surfactants are Detal LAS with an alkyl chain length of from 8 to 15, more preferably 12 to 14. LAS can be at least partially replaced by methyl ester sulphonate (MES), or, less preferably, partially replaced by up to 20 wt % Primary alcohol sulphate (PAS).
  • MES methyl ester sulphonate
  • PAS Primary alcohol sulphate
  • component (a) of the composition further comprises an alkyl polyethoxylate sulphate (AES) anionic surfactant of Formula 3: RO(C 2 H 4 O) x SO 3 - M + (Formula III) where R is an alkyl chain having from 10 to 22 carbon atoms, saturated or unsaturated, M is a cation which makes the compound water-soluble, especially an alkali metal, ammonium or substituted ammonium cation, and x averages from 1 to 15.
  • AES alkyl polyethoxylate sulphate
  • R is an alkyl chain having from 12 to 16 carbon atoms
  • M is Sodium and x averages from 1 to 3, preferably x is 3.
  • This is the anionic surfactant sodium lauryl ether sulphate (SLES).
  • SLES sodium lauryl ether sulphate
  • the predominantly C 12 lauryl alkyl group has been ethoxylated, in the case of SLES(3EO), with an average of 3 moles of ethylene oxide per mole: i.e. x is 3.
  • the anionic surfactant system comprises SLES, together with optional soap and mixtures thereof. Soap is not included in the calculation of amount of non-soap surfactant.
  • a LAS/AES surfactant blend has a superior foam profile to a LAS / Nonionic surfactant blend and is therefore preferred for hand-wash formulations requiring high levels of foam.
  • AES may be used at levels of up to 30%.
  • the composition comprises at least 2 wt% SLES.
  • alkyl sulphate surfactant may be used, especially the non-ethoxylated C 12-15 primary and secondary alkyl sulphates.
  • PAS is preferably used in admixture with LAS and most preferably in admixture with LAS and SLES.
  • a preferred SLES/AO/LAS/PAS liquid has a detersive surfactant system comprising 60 parts SLES, 20 parts amine oxide, 10 parts LAS and 10 parts PAS.
  • Nonionic surfactants include primary and secondary alcohol ethoxylates, especially C 8 -C 20 aliphatic alcohol ethoxylated with an average of from 1 to 20 moles of ethylene oxide per mole of alcohol, and more especially the C 10 -C 15 primary and secondary aliphatic alcohols ethoxylated with an average of from 1 to 10 moles of ethylene oxide per mole of alcohol.
  • Non-ethoxylated nonionic surfactants include alkyl polyglycosides, glycerol monoethers and polyhydroxy amides (glucamide). Mixtures of nonionic surfactant may be used.
  • the composition contains from 0.2 wt% to 30 wt%, preferably 1 wt% to 20 wt%, more preferably 5 to 15 wt% of a non-ionic surfactant, for example alcohol ethoxylate, nonylphenol ethoxylate, alkylpolyglycoside, alkyldimethylamineoxide, ethoxylated fatty acid monoethanolamide, fatty acid monoethanolamide, polyhydroxy alkyl fatty acid amide, or N-acyl N-alkyl derivatives of glucosamine (“glucamides").
  • a non-ionic surfactant for example alcohol ethoxylate, nonylphenol ethoxylate, alkylpolyglycoside, alkyldimethylamineoxide, ethoxylated fatty acid monoethanolamide, fatty acid monoethanolamide, polyhydroxy alkyl fatty acid amide, or N-acyl N-alkyl derivatives of glucosamine (“glucamides”).
  • Nonionic surfactants that may be used include the primary and secondary alcohol ethoxylates, especially the C 8 -C 20 aliphatic alcohols ethoxylated with an average of from 1 to 35 moles of ethylene oxide per mole of alcohol, and more especially the C 10 -C 15 primary and secondary aliphatic alcohols ethoxylated with an average of from 1 to 10 moles of ethylene oxide per mole of alcohol.
  • composition may comprise up to 10 wt% of amine oxide (AO) of the formula (IV): R 1 N(O)(CH 2 R 2 ) 2 (Formula IV)
  • R 1 is a long chain moiety and each CH 2 R 2 is a short chain moiety.
  • R 2 is preferably selected from hydrogen, methyl and -CH 2 OH.
  • R 1 is a primary or branched hydrocarbyl moiety which can be saturated or unsaturated, preferably, R 1 is a primary alkyl moiety.
  • R 1 is a hydrocarbyl moiety having chain length of from about 8 to about 18.
  • R 1 is C 8 -C 18 alkyl
  • R 2 is H.
  • These amine oxides are illustrated by C 12 - 14 alkyldimethyl amine oxide, hexadecyl dimethylamine oxide, octadecylamine oxide.
  • a preferred amine oxide material is Lauryl dimethylamine oxide, also known as dodecyldimethylamine oxide or DDAO. Such an amine oxide material is commercially available from Huntsman under the trade name Empigen® OB.
  • Amine oxides suitable for use herein are also available from Akzo Chemie and Ethyl Corp. See McCutcheon's compilation and Kirk-Othmer review article for alternate amine oxide manufacturers.
  • R 2 is H
  • R 2 may be CH 2 OH, for example: hexadecylbis(2-hydroxyethyl)amine oxide, tallowbis(2-hydroxyethyl)amine oxide, stearylbis(2-hydroxyethyl)amine oxide and oleylbis(2- hydroxyethyl)amine oxide.
  • Preferred amine oxides have the Formula (V): O - - N + (Me) 2 R 1 (Formula V) where R 1 is C 12-16 alkyl, preferably C 12-14 alkyl and Me is a methyl group.
  • a preferred surfactant system for use in high suds (foam) applications comprises SLES and AO.
  • Nonionic-free systems with up to 95 wt% of the surfactant system LAS can be made provided that some zwitterionic surfactant, for example carbobetaine, is present.
  • a preferred zwitterionic material is a betaine available from Huntsman under the name Empigen® BB. Betaines further improve particulate soil detergency in the compositions of the invention.
  • Cationic surfactants are preferably substantially absent.
  • compositions may comprise soap which can act as a builder and/or as an antifoam.
  • the amount of non-soap anionic surfactant must exceed the amount of soap.
  • the amount of soap must be less than or equal to 15 wt% of the total liquid composition, preferably it is less than 3 wt%.
  • the fatty acid used preferably contains from about 16 to about 22 carbon atoms, preferably in a straight chain configuration.
  • the anionic contribution from soap may be from 0 to 30 wt% of the total anionic. Use of more than 10 wt% soap is not preferred. Saturated fatty acids are preferred.
  • the composition comprises an ethoxylated polyethyleneimine polymer (EPEI) for cleaning.
  • EPEI ethoxylated polyethyleneimine polymer
  • the EPEI is nonionic. That means it does not have any quaternary nitrogens, or nitrogen oxides or any ionic species other than possible pH effected protonation of nitrogens.
  • Polyethylene imines are materials composed of ethylene imine units -CH2CH2NH- and, where branched, the hydrogen on the nitrogen is replaced by another chain of ethylene imine units.
  • These polyethyleneimines can be prepared, for example, by polymerizing ethyleneimine in the presence of a catalyst for example carbon dioxide, sodium bisulphite, sulphuric acid, hydrogen peroxide, hydrochloric acid, acetic acid, and the like.
  • a catalyst for example carbon dioxide, sodium bisulphite, sulphuric acid, hydrogen peroxide, hydrochloric acid, acetic acid, and the like. Specific methods for preparing these polyamine backbones are disclosed in U.S. Pat. No. 2,182,306, Ulrich et al., issued Dec. 5, 1939 ; U.S. Pat. No.
  • the EPEI comprises a polyethyleneimine backbone wherein the modification of the polyethyleneimine backbone is intended to leave the polymer without quaternisation.
  • Such nonionic EPEI may be represented as PEI(X)YEO where X represents the molecular weight of the unmodified PEI and Y represents the average moles of ethoxylation per nitrogen atom in the polyethyleneimine backbone. This is the same as the average per substitution site if the number of nitrogens with no hydrogen is balanced by the number with two hydrogens in the unethoxylated PEI.
  • the ethoxylation number Y may range from 7 to 40 ethoxy moieties per modification, preferably it is in the range of 16 to 26, most preferably 18 to 22.
  • X is selected to be from about 300 to about 10000 weight average molecular weight and is preferably about 600.
  • the ethoxylated polyethyleneimine polymer (EPEI) is preferably present in the composition at a level of between 2 and 20 wt%, more preferably at a level of less than 9.5 wt%, most preferably from 3 to 9 wt% and with a ratio of non-soap surfactant to EPEI of from 2:1 to 7:1, preferably from 3:1 to 6:1, even about 5:1.
  • composition may optionally further comprise at least 0.5 wt% of a polymeric soil release agent for oily soil removal from polyester.
  • Soil release polymers improve the main wash performance of the compositions when used in the low in wash surfactant process of the second aspect of the present invention.
  • One preferred class of soil release polymer is the fabric-substantive polymers comprising at least one of (i) saccharide or (ii) dicarboxylic acid and polyol monomer units.
  • these polymers have soil release properties and, while they can have a primary detergency effect, they generally assist in subsequent cleaning.
  • these polymers are present at a level of at least 2% wt, more preferably at least 3 wt% of the composition.
  • the soil release polymer will preferably comprise up to 10 wt%, of the detergent composition, more preferably up to 9 wt%, preferably they are used at greater than 2 wt% and more preferably greater than 3 wt% in the composition.
  • the soil release polymers for polyester will comprise polymers of aromatic dicarboxylic acids and alkylene glycols (including polymers containing polyalkylene glycols).
  • the polymeric soil release agents useful herein include those soil release agents having:
  • the polyoxyethylene segments of (a)(i) will have a degree of polymerization of from about 200, although higher levels can be used, preferably from 3 to about 150, more preferably from 6 to about 100.
  • Soil release agents characterized by poly(vinyl ester) hydrophobic segments include graft copolymers of poly(vinyl ester), e.g., C 1 -C 6 vinyl esters, preferably poly(vinyl acetate) grafted onto polyalkylene oxide backbones, for example polyethylene oxide backbones.
  • poly(vinyl ester) e.g., C 1 -C 6 vinyl esters
  • poly(vinyl acetate) grafted onto polyalkylene oxide backbones for example polyethylene oxide backbones.
  • Commercially available soil release agents of this kind include the SOKALAN type of material, e.g., SOKALAN HP22, available from BASF (West Germany).
  • One type of preferred soil release agent is a copolymer having random blocks of ethylene terephthalate and polyethylene oxide (PEO) terephthalate.
  • the molecular weight of this polymeric soil release agent is in the range of from about 25,000 to about 55,000. See U.S. Pat. No. 3,959,230 to Hays, issued May 25, 1976 and U.S. Pat. No. 3,893,929 to Basadur issued Jul. 8, 1975 .
  • Another preferred polymeric soil release agent is a polyester with repeat units of ethylene terephthalate units contains 10 to 15 wt% of ethylene terephthalate units together with 90 to 80 wt% weight of polyoxyethylene terephthalate units, derived from a polyoxyethylene glycol of average molecular weight 300 to 5000.
  • this polymer include ZELCON 5126 (from DuPont) and MILEASE T (from ICI). See also U.S. Pat. No. 4,702,857, issued Oct. 27, 1987 to Gosselink .
  • the most preferred soil release polymers are the water soluble/miscible or dispersible polyesters for example those supplied under the Texcare brand by Clariant, especially Texcare® SRN170, and heavily branched polyesters for example those available from Sasol and described in US 7119056 . Combinations of soil release polymers may be used.
  • compositions may further comprise one or more further polymers selected from the group comprising dye transfer inhibition polymers, anti redeposition polymers and cotton soil release polymers based on modified cellulosic materials.
  • EPEI that is not of the essential nonionic type may provide one or more of these polymer functions.
  • At least one or more enzymes may be present in the compositions for cleaning boost.
  • proteases include those of animal, vegetable or microbial origin. Microbial origin is preferred. Chemically modified or protein engineered mutants are included.
  • the protease may be a serine protease or a metallo protease, preferably an alkaline microbial protease or a trypsin-like protease.
  • Preferred commercially available protease enzymes include AlcalaseTM, SavinaseTM, PrimaseTM, DuralaseTM, DyrazymTM, EsperaseTM, EverlaseTM, PolarzymeTM, and KannaseTM, (Novozymes A/S), MaxataseTM, MaxacalTM, MaxapemTM, ProperaseTM, PurafectTM, Purafect OxPTM , FN2TM, and FN3TM (Genencor International Inc.).
  • Suitable amylases include those of bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Amylases include, for example, alpha-amylases obtained from Bacillus, e.g. a special strain of B. licheniformis, described in more detail in GB 1,296,839 , or the Bacillus sp. strains disclosed in WO 95/026397 or WO 00/060060 .
  • amylases are DuramylTM, TermamylTM, Termamyl UltraTM, NatalaseTM, StainzymeTM, FungamylTM and BANTM (Novozymes A/S), RapidaseTM and PurastarTM (from Genencor International Inc.).
  • Pectate lyases also called polygalacturonate lyases
  • pectate lyases include pectate lyases that have been cloned from different bacterial genera for example Erwinia, Pseudomonas, Klebsiella and Xanthomonas, as well as from Bacillus subtilis ( Nasser et al. (1993) FEBS Letts. 335:319-326 ) and Bacillus sp. YA-14 ( Kim et al. (1994) Biosci. Biotech. Biochem. 58:947-949 ).
  • the pectate lyase comprises the pectate lyase disclosed in Heffron et al., (1995) Mol. Plant-Microbe Interact. 8: 331-334 and Henrissat et al., (1995) Plant Physiol. 107: 963-976 .
  • pectate lyases are disclosed in WO 99/27083 and WO 99/27084 .
  • pectate lyases derived from Bacillus licheniformis
  • US patent no. 6,284,524 Specifically contemplated pectate lyase variants are disclosed in WO 02/006442 , especially the variants disclosed in the Examples in WO 02/006442 .
  • alkaline pectate lyases examples include BIOPREPTM and SCOURZYMETM L from Novozymes A/S, Denmark.
  • Suitable examples of mannanases include mannanases of bacterial and fungal origin.
  • the mannanase is derived from a strain of the filamentous fungus genus Aspergillus, preferably Aspergillus niger or Aspergillus aculeatus ( WO 94/25576 ).
  • WO 93/24622 discloses a mannanase isolated from Trichoderma reseei. Mannanases have also been isolated from several bacteria, including Bacillus organisms. For example, Talbot et al., Appl. Environ. Microbiol., Vol.56, No. 11, pp.
  • JP-A-03047076 discloses a beta-mannanase derived from Bacillus sp.
  • JP-A-63056289 describes the production of an alkaline, thermostable beta-mannanase.
  • JP-A-63036775 relates to the Bacillus microorganism FERM P-8856 which produces beta-mannanase and beta-mannosidase.
  • JP-A-08051975 discloses alkaline beta-mannanases from alkalophilic Bacillus sp. AM-001.
  • a purified mannanase from Bacillus amyloliquefaciens is disclosed in WO 97/11164 .
  • WO 91/18974 describes a hemicellulase for example a glucanase, xylanase or mannanase active.
  • mannanases derived from Bacillus agaradhaerens, Bacillus licheniformis, Bacillus halodurans, Bacillus clausii, Bacillus sp., and Humicola insolens disclosed in WO 99/64619 .
  • Bacillus sp. mannanases concerned in the Examples in WO 99/64619 .
  • mannanases examples include MannawayTM available from Novozymes A/S Denmark.
  • Suitable cellulases include those of bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Suitable cellulases include cellulases from the genera Bacillus, Pseudomonas, Humicola, Fusarium, Thielavia, Acremonium, e.g. the fungal cellulases produced from Humicola insolens, Thielavia terrestris, Myceliophthora thermophila, and Fusarium oxysporum disclosed in US 4,435,307 , US 5,648,263 , US 5,691,178 , US 5,776,757 , WO 89/09259 , WO 96/029397 , and WO 98/012307 .
  • cellulases include CelluzymeTM, CarezymeTM, EndolaseTM, RenozymeTM (Novozymes A/S), ClazinaseTM and Puradax HATM (Genencor International Inc.), and KAC-500(B)TM (Kao Corporation).
  • Suitable peroxidases/oxidases include those of plant, bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Examples of useful peroxidases include peroxidases from Coprinus, e.g. from C. cinereus, and variants thereof as those described in WO 93/24618 , WO 95/10602 , and WO 98/15257 . Commercially available peroxidases include GuardzymeTM and NovozymTM 51004 (Novozymes A/S).
  • the method of the invention may be carried out in the presence of cutinase. classified in EC 3.1.1.74.
  • the cutinase used according to the invention may be of any origin.
  • Preferably cutinases are of microbial origin, in particular of bacterial, of fungal or of yeast origin.
  • Enzymes and any perfume/fragrance or pro-fragrance present may show some interaction and should be chosen such that this interaction is not negative. Some negative interactions may be avoided by encapsulation of one or other of enzyme and pro-fragrance and/or other segregation within the product.
  • Any enzyme present in the composition may be stabilized using conventional stabilizing agents, e.g., a polyol for example propylene glycol or glycerol, a sugar or sugar alcohol, lactic acid, boric acid, or a boric acid derivative, e.g., an aromatic borate ester, or a phenyl boronic acid derivative for example 4-formylphenyl boronic acid, and the composition may be formulated as described in e.g. WO 92/19709 and WO 92/19708 .
  • stabilizing agents e.g., a polyol for example propylene glycol or glycerol, a sugar or sugar alcohol, lactic acid, boric acid, or a boric acid derivative, e.g., an aromatic borate ester, or a phenyl boronic acid derivative for example 4-formylphenyl boronic acid
  • compositions of the invention may contain one or more other ingredients.
  • Such ingredients include viscosity modifiers, foam boosting agents, preservatives (e.g. bactericides), pH buffering agents, polyelectrolytes, anti-shrinking agents, anti-wrinkle agents, anti-oxidants, sunscreens, anti-corrosion agents, drape imparting agents, anti-static agents and ironing aids.
  • the compositions may further comprise, colorants, pearlisers and/or opacifiers, and shading dye.
  • fluorescer in the compositions.
  • these fluorescent agents are supplied and used in the form of their alkali metal salts, for example, the sodium salts.
  • the total amount of the fluorescent agent or agents used in the composition is generally from 0.005 to 2 wt %, more preferably 0.01 to 0.5 wt %.
  • Preferred classes of fluorescer are: Di-styryl biphenyl compounds, e.g. Tinopal (Trade Mark) CBS-X, Di-amine stilbene di-sulphonic acid compounds, e.g. Tinopal DMS pure Xtra and Blankophor (Trade Mark) HRH, and Pyrazoline compounds, e.g. Blankophor SN.
  • Di-styryl biphenyl compounds e.g. Tinopal (Trade Mark) CBS-X
  • Di-amine stilbene di-sulphonic acid compounds e.g. Tinopal DMS pure Xtra and Blankophor (Trade Mark) HRH
  • Pyrazoline compounds e.g. Blankophor SN.
  • Preferred fluorescers are: sodium 2 (4-styryl-3-sulfophenyl)-2H-napthol[1,2-d]triazole, disodium 4,4'-bis ⁇ [(4-anilino-6-(N methyl-N-2 hydroxyethyl) amino 1,3,5-triazin-2-yl)]amino ⁇ stilbene-2-2' disulfonate, disodium 4,4'-bis ⁇ [(4-anilino-6-morpholino-1,3,5-triazin-2-yl)]amino ⁇ stilbene-2-2' disulfonate, and disodium 4,4'-bis(2-sulfostyryl)biphenyl.
  • Detergent compositions according to the invention may comprise a weight efficient bleach system.
  • Such bleach systems typically do not utilise the conventional peracid or bleach activator with perborate/percarbonate "oxygen" bleach systems, but rely instead on a bleach catalyst used at a low level as the main bleach component.
  • the present invention may be used in a formulation that is used to bleach via air, or an air bleach catalyst system.
  • Suitable complexes and organic molecule (ligand) precursors for forming complexes are available to the skilled worker, for example, from: WO 98/39098 ; WO 98/39406 , WO 97/48787 , WO 00/29537 ; WO 00/52124 , and WO00/60045 .
  • An example of a preferred catalyst is a transition metal complex of MeN 4 Py ligand (N,N-bis(pyridin-2-yl-methyl)-1-,1-bis(pyridin-2-yl)-1-aminoethane).
  • Suitable bispidon catalyst materials and their action are described in WO02/48301 .
  • the bleach catalyst is typically incorporated at a level of about 0.0001 to about 10 wt%, preferably about 0.001 to about 5 wt%.
  • Photobleaches may also be employed.
  • a "photobleach” is any chemical species that forms a reactive bleaching species on exposure to sunlight, and preferably is not permanently consumed in the reaction.
  • Preferred photo-bleaches include singlet oxygen photo-bleaches and radical photo-bleaches.
  • Suitable singlet oxygen photo-bleaches may be selected from, water soluble phthalocyanine compounds, particularly metallated phthalocyanine compounds where the metal is Zn or Al-Z1 where Z1 is a halide, sulphate, nitrate, carboxylate, alkanolate or hydroxyl ion.
  • the phthalocyanin has 1-4 SO 3 X groups covalently bonded to it where X is an alkali metal or ammonium ion. Such compounds are described in WO2005/014769 (Ciba ).
  • compositions preferably comprise from 0.001 to 5 wt % perfume. Given that the composition of the present invention is designed to be used at very low levels of product dosage, it is advantageous to ensure that perfume is employed efficiently.
  • a particularly preferred way of ensuring that perfume is employed efficiently is to use an encapsulated perfume.
  • Use of a perfume that is encapsulated reduces the amount of perfume vapour that is produced by the composition before it is diluted. This is important when the perfume concentration is increased to allow the amount of perfume per wash to be kept at a reasonably high level.
  • the perfume is not only encapsulated but also that the perfume encapsulate is provided with a deposition aid to increase the efficiency of perfume deposition and retention on fabrics.
  • the deposition aid is preferably attached to the encapsulate by means of a covalent bond, entanglement or strong adsorption, preferably by a covalent bond or entanglement.
  • Shading dye can be used to improve the performance of the compositions used in the method of the present invention.
  • the deposition of shading dye onto fabric is improved when they are used in compositions of the invention and according to the process of the invention.
  • Preferred dyes are violet or blue. It is believed that the deposition on fabrics of a low level of a dye of these shades, masks yellowing of fabrics.
  • a further advantage of shading dyes is that they can be used to mask any yellow tint in the composition itself.
  • Suitable and preferred classes of dyes are disclosed in WO2009/153184 and elsewhere.
  • Sequestrants other than the alkyl hydroxamate may be present at low levels in the compositions. Because the hydroxamate technology is affected by competing sequestrants, for maximum performance of the hydroxamate any phosphonate or similar sequestrants that may complex with iron are preferably absent or used at a low level of up to 1 wt%, preferably less than 0.5 wt%. Most preferably they are absent. Citric acid and citrate builders are also preferably absent. When used a preferred sequestrant is HEDP (1-Hydroxyethylidene -1,1,-diphosphonic acid), for example sold as Dequest® 2010. Also suitable, but less preferred as it gives inferior cleaning results, is Dequest® 2066 (Diethylenetriamine penta(methylene phosphonic acid or Heptasodium DTPMP).
  • compositions preferably comprise one or more hydrotropes; although the minimum amount consistent with the need for concentration should be used.
  • Suitable hydrotropes include MPG (monopropylene glycol). This and/or other conventionally employed hydrotropes may be used in the composition at levels of from 2 to 25 wt%.
  • a hydrotrope is a solvent that is neither water nor conventional surfactant that aids the solubilisation of the surfactants and other components in the aqueous liquid to render it isotropic.
  • MPG monopropylene glycol
  • suitable hydrotropes there may be mentioned as preferred: glycerol, sodium cumene sulphonate, ethanol, other glycols, e.g. di propylene glycol, diethers and urea.
  • buffers are monoethanolamine (MEA), and triethanolamine (TEA). If present, they are preferably used in the composition at levels of from 5 to 15 wt%.
  • compositions may have their rheology modified by use of a material or materials that form a structuring network within the composition.
  • Suitable structurants include hydrogenated castor oil, microfibrous cellulose and natural based structurants, for example citrus pulp fibre. Citrus pulp fibre is preferred especially if cellulase or pectate lyase enzyme is included in the composition.
  • compositions may comprise visual cues of solid material that is not dissolved in the composition.
  • visual cues are lamellar cues formed from polymer film and possibly comprising functional ingredients that may not be as stable if exposed to the alkaline liquid.
  • Enzymes and bleach catalysts are examples of such ingredients.
  • perfume, particularly microencapsulated perfume are examples of such ingredients.
  • the liquids may be packaged as unit doses. To allow greater flexibility in dosing the liquids may alternatively be supplied in multiuse plastics packs with a top or bottom closure. A dosing system may be supplied with the pack either as a part of the cap or as an integrated system.
  • liquids according to the invention may be formulated to allow them to be dosed to a typical front loading automatic washing machine at a dosage level of 20 ml.
  • the low in wash surfactant level being compensated by the presence of enzymes, soil release polymer and EPEI together with further optional high efficacy cleaning ingredients, for example enzymes.
  • the invention is also suitable for the more conventional dosage levels of about 35 ml. To obtain suitable concentrated liquids of this greater dose volume it is necessary is to add further water and preferably additional perfume to the 20 ml composition before it is packaged.
  • LAS acid is C 12-14 linear alkylbenzene sulphonic acid.
  • Fatty acid is saturated lauric fatty acid Prifac® 5908 ex Croda.
  • SLES 3EO is sodium lauryl ether sulphate with 3 moles EO.
  • SLES 1 EO is sodium lauryl ether sulphate with 1 mole EO.
  • Empigen® BB is an alkyl betaine ex Huntsman (Coco dimethyl carbobetaine).
  • NI 7EO is C12-15 alcohol ethoxylate 7EO nonionic Neodol® 25-7 (ex Shell Chemicals).
  • MPG is mono propylene glycol.
  • TEA is triethanolamine. NaOH is sodium hydroxide (from 47% solution).
  • EPEI Sokalan HP20 - ethoxylated polyethylene imine cleaning polymer: PEI(600) 20E0 ex BASF.
  • SRP soil release polymer (Texcare® SRN170 ex Clariant).
  • Dequest® 2066 is Diethylenetriamine penta(methylene phosphonic acid (or Heptasodium DTPMP) ex Thermphos.
  • Perfume is free oil perfume.
  • HXA is Coco hydroxamic Acid: Axis House RK 853.
  • HXA K + is Coco hydroxamate K + salt: Axis House RK 852.
  • SRI 100 - ⁇ E * aw
  • a SRI of 100 means complete stain removal.
  • Composition A similar to hydroxamate containing compositions taught in WO2010/069957 was prepared as shown in table 1. variants on this composition without any hydroxamate but with EPEI included instead (Composition B) and using a combination of hydroxamate and EPEI (Composition C) were also prepared.
  • Table 1- formulations made Ingredient A B C Glycerol 5.00 5.00 5.00 PPG 9.00 9.00 NaOH 4.73 4.73 4.73 TEA 3.24 3.24 3.24 Citric Acid 0.98 0.98 0.98 LAS 27.60 27.60 27.60 NI 12.50 12.50 12.50 Soap 4.78 4.78 4.78 Potassium Octyl Hydroxamate 5.00 - 2.50 EPEI - 5.00 2.50 Water Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance
  • the three compositions A, B and C were used to wash polyester fabrics stained with red clay using a Linitest equipment.
  • the Linitest pots were filled with 26°FH water (2:1 Ca 2+ :Mg 2+ ) and then 2.6 g/L formulations coactive such that the final wash liquor volume was 100 ml. This equates to a non-soap in-wash surfactant level of just over 1 g/L.
  • To each Linitest pot were added two knitted polyester cloths stained with Georgia clay, a red clay, together with six ballast cloths (four cotton and two knitted polyester) to obtain liquor to cloth ratios of 8:1.
  • Table 2 gives the Soil release index for each composition (a comparative composition with neither hydroxamate nor EPEI gives an SRI of 79.4 under these conditions.
  • Table 2 Composition SRI aw A 89.1 B 79.6 C 84.17
  • composition B having only EPEI is not much better than a composition without any EPEI.
  • Composition C based on the teaching in WO2010/069957 and WO2011/151170 , shows a significant improvement in red clay removal.
  • the ratio of non-soap surfactant to EPEI in these examples is at least 8:1 and is thus in line with the ratio found in a non-concentrated laundry liquid.
  • compositions in Table 3 were used to wash red mud on knitted polyester in a Tergotometer using the wash protocol described below. In all cases the formulation dose was 0.78 g/L giving an in-wash non-soap surfactant level of 0.26 g/L.
  • Wash liquor compositions are given in Table 4.
  • Table 4 Wash Liquors D
  • E F 1 In wash concentration (g/L) LAS Acid 0.10 0.10 0.10 0.10 NI 7EO 0.03 0.03 0.03 0.03 SLES 1 EO 0.13 0.13 0.13 0.13 EPEI 0.00 0.00 0.07 0.07 HXA 0.00 0.018 0.00 0.018
  • composition is designed to dose to European front loading washing machines at a standard dose of 20 ml which is approximately 20% of the normal dose of a dilute liquid and less than the current "concentrated" 3X formulations that are dosed from 30-40 ml per wash.
  • Base 5X Composition G was used at 1.41 g/L. Thus the non-soap surfactant level in wash was about 0.4 g/L. When additional ingredients were added to the composition the water balance was reduced to keep the dose of surfactant to the wash constant.
  • the undiluted compositions had a pH of about 6.5.
  • Knitted polyester stained with Indian red clay was washed using the previously described Tergotometer wash protocol, using 26°FH water as before but at the lower wash temperature of 25°C for 20 minutes, followed by a 1 minute rinse.
  • the liquor to cloth ratio was 25:1.
  • Table 7 gives the results. It is clearly seen that under hard water, low surfactant, wash conditions the combination of EPEI and hydroxamate in Examples 2 and 3 is statistically superior to the other compositions and that under these conditions the composition with hydroxamate only gives inferior results to the composition with EPEI only.
  • the ratio of non-soap surfactant to EPEI in these compositions is the shorter ratio found in the concentrated liquids according to WO2009/153184 and is about 5 to 1.

Claims (11)

  1. Wässriges konzentriertes Flüssigwaschmittel, das Folgendes aufweist:
    (a) mindestens 8 Gew.-%, vorzugsweise höchstens 40 Gew.-% anionisches seifenfreies Tensid;
    (b) höchstens 30 Gew.-% nichtionisches Tensid;
    (c) höchstens 10 Gew.-% eines von (a) und (b) verschiedenen Tensids;
    (d) mindestens 0,1 Gew.-%, vorzugsweise höchstens 10 Gew.-% Alkylhydroxamat mit der Struktur, die mit der Formel I angegeben wird:
    Figure imgb0015
     wobei R1 wie folgt ist:
    eine geradkettige oder verzweigte C4-C20-Alkylgruppe oder
    eine geradkettige oder verzweigte substituierte C4-C20-Alkylgruppe oder
    eine geradkettige oder verzweigte C4-C20-Alkenylgruppe oder
    eine geradkettige oder verzweigte substituierte C4-C20-Alkenylgruppe und
    wobei die Arten der Substitution eine oder mehrere aus NH2, OH, S, -O-,
    COOH und
    Figure imgb0016
    einschließen; und
    (e) mindestens 2 Gew.-%, vorzugsweise höchstens 20 Gew.-% nichtionisches ethoxyliertes Polyethylenimin (EPEI) mit durchschnittlich 7 bis 40 Ethoxy-Einheiten pro Substitutionsstelle an jedem Stickstoffatom;
    wobei das Gewichtsverhältnis zwischen seifenfreiem Tensid und EPEI 2:1 bis 7:1, vorzugsweise 3:1 bis 6:1 beträgt.
  2. Zusammensetzung nach Anspruch 1,
    wobei die Menge von (a) größer als die oder gleich der Menge von (b) ist.
  3. Zusammensetzung nach Anspruch 2,
    wobei die Menge von (b) mindestens 3 Gew.-% beträgt.
  4. Zusammensetzung nach Anspruch 2,
    die weniger als 3 Gew.-% nichtionisches (b) aufweist, und wobei das anionische seifenfreie Tensid (a) ein Gemisch von linearem Alkylbenzolsulfonat (LAS) und Alkylethoxysulfat (AES) aufweist.
  5. Zusammensetzung nach einem der vorstehenden Ansprüche,
    die mindestens 0,4 Gew.-% Duftstoff aufweist.
  6. Zusammensetzung nach einem der vorstehenden Ansprüche,
    die mindestens 1 Gew.-% Alkylhydroxamat (d) aufweist.
  7. Zusammensetzung nach Anspruch 5,
    wobei das weitere Reinigungstensid (c) Seife aufweist.
  8. Zusammensetzung nach Anspruch 7,
    wobei die Seifenmenge in der Zusammensetzung weniger als 3 Gew.-% beträgt.
  9. Zusammensetzung nach einem der vorstehenden Ansprüche,
    wobei das Verhältnis zwischen Hydroxamat und gesamtem Reinigungstensidsystem (Tensid) im Bereich von 1:4 bis 1:8000, vorzugsweise von 1:7 bis 1:40, stärker bevorzugt von 1:10 bis 1:30 Gewichtsteile liegt.
  10. Verfahren zum Waschen von Polyestertextilien,
    das die Schritte des Kombinierens von 15 bis 25 ml einer Zusammensetzung nach einem der Ansprüche 1 bis 9 mit Wasser mit einer Härte von mehr als 20° FH, um eine Waschlauge mit einer Konzentration an seifenfreiem Tensid von weniger als 0,5 g/l zu erzeugen, und des Waschens des Polyesters mit der Waschlauge aufweist.
  11. Verwendung einer Zusammensetzung nach einem der Ansprüche 1 bis 9
    bei einem Waschprozess, der in Wasser mit einer Härte von mindestens 20° FH durchgeführt wird, um roten Ton von Polyester zu entfernen.
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Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104854226B (zh) * 2012-11-27 2017-12-05 荷兰联合利华有限公司 液体硬表面清洁组合物
US20160312152A1 (en) * 2013-12-16 2016-10-27 Conopco, Inc. D/B/A Unilever Free flowing aqueous lamellar gel laundry detergent liquid comprising epei
DE102014212622A1 (de) * 2014-06-30 2015-12-31 Henkel Ag & Co. Kgaa Reinigungsmittel umfassend Hydroxamsäure und/oder deren Salze
WO2016139133A1 (en) * 2015-03-02 2016-09-09 Unilever Plc Perfumed fluid cleaning fluids
WO2016139127A1 (en) 2015-03-02 2016-09-09 Unilever Plc A method of separating rhamnolipids from a fermentation broth
WO2016139032A1 (en) 2015-03-02 2016-09-09 Unilever Plc Compositions with reduced dye-transfer properties
CN107920978A (zh) 2015-08-20 2018-04-17 荷兰联合利华有限公司 改善的内酰胺溶解度
CN116983220A (zh) * 2015-08-20 2023-11-03 联合利华知识产权控股有限公司 改善的内酰胺溶解度
EP3337454B1 (de) 2015-08-20 2018-12-26 Unilever Plc. Verbesserte lactamlöslichkeit
CN108024939A (zh) 2015-08-20 2018-05-11 荷兰联合利华有限公司 包封的内酰胺
CN110691839B (zh) 2017-05-30 2021-09-24 联合利华知识产权控股有限公司 液体洗涤剂组合物
EP3814467A1 (de) * 2018-06-26 2021-05-05 The Procter & Gamble Company Flüssige waschmittelzusammensetzung
US20220186144A1 (en) * 2020-12-15 2022-06-16 Henkel IP & Holding GmbH Unit Dose Laundry Detergent Compositions Containing Soil Release Polymers

Family Cites Families (49)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2182306A (en) 1935-05-10 1939-12-05 Ig Farbenindustrie Ag Polymerization of ethylene imines
US2208095A (en) 1937-01-05 1940-07-16 Ig Farbenindustrie Ag Process of producing insoluble condensation products containing sulphur and nitrogen
US2553696A (en) 1944-01-12 1951-05-22 Union Carbide & Carbon Corp Method for making water-soluble polymers of lower alkylene imines
US2806839A (en) 1953-02-24 1957-09-17 Arnold Hoffman & Co Inc Preparation of polyimines from 2-oxazolidone
BE615597A (de) 1958-06-19
GB1296839A (de) 1969-05-29 1972-11-22
CA989557A (en) 1971-10-28 1976-05-25 The Procter And Gamble Company Compositions and process for imparting renewable soil release finish to polyester-containing fabrics
US3959230A (en) 1974-06-25 1976-05-25 The Procter & Gamble Company Polyethylene oxide terephthalate polymers
DK187280A (da) 1980-04-30 1981-10-31 Novo Industri As Ruhedsreducerende middel til et fuldvaskemiddel fuldvaskemiddel og fuldvaskemetode
US4702857A (en) 1984-12-21 1987-10-27 The Procter & Gamble Company Block polyesters and like compounds useful as soil release agents in detergent compositions
DE3536530A1 (de) 1985-10-12 1987-04-23 Basf Ag Verwendung von pfropfcopolymerisaten aus polyalkylenoxiden und vinylacetat als vergrauungsinhibitoren beim waschen und nachbehandeln von synthesefasern enthaltendem textilgut
JPS6356289A (ja) 1986-07-30 1988-03-10 Res Dev Corp Of Japan β−マンナナ−ゼおよびその製法
JPS6336775A (ja) 1986-07-31 1988-02-17 Res Dev Corp Of Japan β―マンナナーゼおよびβ―マンノシダーゼ生産能を有するアルカリ性バチルス属新菌株
US5776757A (en) 1988-03-24 1998-07-07 Novo Nordisk A/S Fungal cellulase composition containing alkaline CMC-endoglucanase and essentially no cellobiohydrolase and method of making thereof
EP0406314B1 (de) 1988-03-24 1993-12-01 Novo Nordisk A/S Cellulosezubereitung
GB8906089D0 (en) 1989-03-16 1989-04-26 Monsanto Europe Sa Improved detergent compositions
JPH0347076A (ja) 1989-08-25 1991-02-28 Res Dev Corp Of Japan β―マンナナーゼおよびその製法
AU8060091A (en) 1990-05-29 1991-12-31 Chemgen Corporation Hemicellulase active at extremes of ph and temperature and the means for the production thereof
EP0511456A1 (de) 1991-04-30 1992-11-04 The Procter & Gamble Company Flüssiges Reinigungsmittel mit einem aromatischen Boratester zur Inhibierung des proteolytischen Enzyms
PL170474B1 (pl) 1991-04-30 1996-12-31 Procter & Gamble C iekla kom pozycja detergentow a PL PL PL
JP2626662B2 (ja) 1991-10-09 1997-07-02 科学技術振興事業団 新規なβ−マンナナーゼとその製造方法
FI931193A0 (fi) 1992-05-22 1993-03-17 Valtion Teknillinen Mannanasenzymer, gener som kodar foer dem och foerfaranden foer isoleringav generna samt foerfarande foer blekning av lignocellulosahaltig massa
DK72992D0 (da) 1992-06-01 1992-06-01 Novo Nordisk As Enzym
DK48693D0 (da) 1993-04-30 1993-04-30 Novo Nordisk As Enzym
JPH09503664A (ja) 1993-10-13 1997-04-15 ノボ ノルディスク アクティーゼルスカブ Ｈ▲下２▼ｏ▲下２▼安定ペルオキシダーゼ変異体
BR9507229A (pt) 1994-03-29 1997-09-16 Novo Nordisk As Amilase composição detergente aditivo detergente uso de um detergente e de uma amilase construç~o de dna vetor de expressão recombinante célula e processo para produzir amilase
CN1182451A (zh) 1995-03-17 1998-05-20 诺沃挪第克公司 新的内切葡聚糖酶
DE69628656D1 (de) 1995-09-20 2003-07-17 Genencor Int Mannase von bacillus amyloliquefaciens und methode zu ihrer preparation
US5728671A (en) 1995-12-21 1998-03-17 The Procter & Gamble Company Soil release polymers with fluorescent whitening properties
EP0906402A1 (de) 1996-06-19 1999-04-07 Unilever N.V. Bleichmittelaktivierung
CN100362100C (zh) 1996-09-17 2008-01-16 诺沃奇梅兹有限公司 纤维素酶变体
AU730286B2 (en) 1996-10-08 2001-03-01 Novo Nordisk A/S Diaminobenzoic acid derivatives as dye precursors
ATE295408T1 (de) 1997-03-07 2005-05-15 Procter & Gamble Bleichmittelzusammensetzungen
ZA981883B (en) 1997-03-07 1998-09-01 Univ Kansas Catalysts and methods for catalytic oxidation
BR9815007A (pt) 1997-11-24 2000-10-03 Novo Nordisk As Liase de pectato, molécula de polinucleotìdeo isolada codificando um polipeptìdeo, vetor de expressão, célula cultivada em que se introduziu um vetor de expressão, polipeptìdeos isolado, e fundido, preparação de enzima, processos para produzir um polipeptìdeo apresentando atividade de liase de pectato, para a limpeza de uma superfìcie dura, para o tratamento de tecidos à máquina, para aperfeiçoar as propriedades de fibras celulósicas, fio, tecido urdidurado ou não-urdidurado, para a degradação ou modificação de material de planta, para preparar alimento animal, e para processar vinho ou suco, enzima isolada apresentando atividade de liase de pectato, e, composição detergente
US6124127A (en) 1997-11-24 2000-09-26 Novo Nordisk A/S Pectate lyase
WO1999027083A1 (en) 1997-11-24 1999-06-03 Novo Nordisk A/S PECTIN DEGRADING ENZYMES FROM $i(BACILLUS LICHENIFORMIS)
AU755850B2 (en) 1998-06-10 2002-12-19 Novozymes A/S Novel mannanases
WO2000029537A1 (en) 1998-11-13 2000-05-25 The Procter & Gamble Company Bleach compositions
CA2364538A1 (en) 1999-03-02 2000-09-08 The Procter & Gamble Company Bleach compositions comprising cross-bridged macropolycyclic transition metal bleach catalysts and a stabilizing agent
ES2532606T3 (es) 1999-03-31 2015-03-30 Novozymes A/S Polipéptidos con actividad de alfa-amilasa alcalina y ácidos nucleicos que los codifican
EP1305408B1 (de) 2000-07-19 2009-01-21 Novozymes A/S Zellwandabbauende enzymvarianten
DE10043604A1 (de) 2000-09-02 2002-03-28 Rwe Dea Ag Fließfähige, amphiphile und nichtionische Oligoester
GB0030673D0 (en) 2000-12-15 2001-01-31 Unilever Plc Ligand and complex for catalytically bleaching a substrate
US8293695B2 (en) 2003-08-06 2012-10-23 Basf Se Shading composition
WO2009153184A1 (en) 2008-06-16 2009-12-23 Unilever Plc Improvements relating to fabric cleaning
GB0810881D0 (en) * 2008-06-16 2008-07-23 Unilever Plc Improvements relating to fabric cleaning
BRPI0922587B1 (pt) * 2008-12-17 2019-04-09 Unilever N.V. Composição Detegente Para Lavagem
WO2011151170A1 (en) 2010-06-03 2011-12-08 Unilever Nv Laundry detergent composition

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ES2546003T3 (es) 2015-09-17
CN103517975B (zh) 2015-11-25
BR112013028716A2 (pt) 2017-01-24
EP2707472A1 (de) 2014-03-19
ZA201308383B (en) 2015-03-25
WO2012156250A1 (en) 2012-11-22

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