AU2009327141A1

AU2009327141A1 - Laundry detergent composition

Info

Publication number: AU2009327141A1
Application number: AU2009327141A
Authority: AU
Inventors: Ian Howell; Anthony Mckee
Original assignee: Unilever PLC
Current assignee: Unilever Global IP Ltd
Priority date: 2008-12-17
Filing date: 2009-12-15
Publication date: 2010-06-24
Anticipated expiration: 2029-12-15
Also published as: WO2010069957A1; BRPI0922587B1; CN102257109B; ES2731593T3; AU2009327141B2; CA2745559A1; BRPI0922587A2; CN102257109A; TR201906017T4; PL2358852T3; ZA201103716B; EP2358852A1; EP2358852B1

Description

WO 2010/069957 PCT/EP2009/067193 LAUNDRY DETERGENT COMPOSITION The present invention relates to the use of hydroxamic acid and its corresponding salts in laundry detergent compositions with low levels of zeolite and phosphate builder, leading 5 to improved detergency and stain removal. Improvement of stain removal is one of the constant goals of the detergents industry, as this may lead to savings on the use of chemicals in detergent compositions, or may lead to washing at lower temperature, and/or for shorter times, and therewith saving energy. 10 Therefore there is still an interest to improve the detergency effect, especially the primary detergency effect of laundry detergent compositions on textile stains, for example particulate stains, such as stains comprising soils or clay, or plant based stains, such as grass. Especially particulate stains are difficult to remove during the laundering process. 15 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: C /OH R1 N H (Formula 1) 20 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 hydroxamates may conveniently be formed from the corresponding hydroxamic acid by substitution of the acid hydrogen atom by a cation: 25 WO 2010/069957 PCT/EP2009/067193 -2 LOH R C OH R O0 L H H (Formula 2) L' is a monovalent cation such as for example the alkali metals (e.g. potassium, sodium), or ammonium or a substituted ammonium. 5 Hydroxamic acids and hydroxamates are known to be useful as metal chelators. They have also been used in detergent compositions in order to improve bleaching performance, as well as use as a builder substance. 10 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. Hydroxamic acids as in formula 1 are disclosed, wherein R 1 represents an optionally substituted straight- or branched chain C5-C21 alkyl or C5-C21 alkenyl group or an optionally-substituted phenyl group, and R 2 represents 15 hydrogen, or an optionally substituted C1-C6 alkyl 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, which is about 143 milligram calcium per litre). The examples use C12 linear, C12 branched, C13 branched and C18 hydroxamates in detergent formulations comprising 20 mixtures of anionic surfactant and nonionic surfactant. In examples 1, 11 and IV there is an excess of nonionic surfactant of at least 1.25 to 1 and in example Ill there is 100% anionic surfactant. The liquids also contain at least 6 wt% ethanol, which assists in solubilising the long chain hydroxamates. 25 EP 384 912 A2 discloses the use of hydroxamic acids and their derivatives as stabilizers for peroxygen bleach compounds in built, mainly granular, detergent compositions. Fully formulated detergent powder examples with 20 wt% zeolite used C12, C13 and C12 branched hydroxamates. C18 was also used.

WO 2010/069957 PCT/EP2009/067193 -3 US 4,874,539 discloses polymeric carboxy hydroxamic acids useful as detergent additives, especially as metal ion chelating agents, and also leading to improved tea stain removal from a test cloth, as compared to a detergent powder without a metal ion chelating agent. 5 US 4,863,636 discloses liquid detergent compositions comprising one or more detersive surfactants and one or more of N-hydroxyimide or carboxy hydroxamic acid detergent additives. These compounds serve as active metal ion chelants, leading to improved stain removal. 10 WO 97/48786 discloses a multicomponent system for use with detergent substances, containing an oxidation catalyst, a suitable oxidant, at least one mediator that has been selected from the group of, among others, hydroxamic acids and hydroxamic acid derivatives, a co-mediator, and optionally a low quantity of at least one free amine of each 15 inserted mediator. This system leads to improved bleach function of the detergent, and less consumption of a mediator. GB 1317445 discloses detergent compositions comprising an alkali-metal salt of a hydroxamic acid. The function of this salt is to prevent the corrosion of copper and copper 20 alloys that is utilised in the construction of the washing machines. We have now surprisingly found that the primary detergency effect, especially on red clay particulate soil, can be improved by incorporating specific hydroxamic acids and/or hydroxamates in specific laundry detergent compositions. 25 Laundry detergents need to be able to remove everyday dirt and stains that are commonly found in a wash load. Two particular stains that are problematic, especially when children's wear or sport's wear is being washed, are clay soil stains and grass stains. One type of clay that is particularly resistant to removal by surfactants alone is red 30 clay, such as red pottery clay or Red Georgia clay. This is a particulate soil stain.

WO 2010/069957 PCT/EP2009/067193 -4 Accordingly, the present invention provides a laundry detergent composition comprising a) 0.5 to 20, preferably 0.5 to 6, wt% hydroxamic acid or its corresponding hydroxamate of the structure: 0 OH C,- /OH RI N 5 R 2 ,formula 3 wherein R 1 is a straight or branched C4-C20 alkyl, or a straight or branched substituted C4-C20 alkyl, or a straight or branched C4-C20 alkenyl, or 10 a straight or branched substituted C4-C20 alkenyl, or an alkyl ether group CH 3

(CH

2 )n (EO)m wherein n is from 2 to 20 and m is from 1 to 12, or a substituted alkyl ether group CH 3

(CH

2 )n (EO)m wherein n is from 2 to 20 and m is from 1 to 12, and the types of substitution include one or more of -NH 2 , -OH, -S-, -0-, -COOH, and C OH || I 15 -C

-N

and R 2 is selected from hydrogen and a moiety that forms part of a cyclic structure with a branched R 1 group b) a detersive surfactant system at a concentration from 3 to 80 wt%; the detersive 20 surfactant system comprising (i) anionic surfactant; and (ii) nonionic surfactant Wherein the ratio of (i) to (ii) lies in the range 1:1.1 to 19:1 and the weight ratio of a) to b) lies in the range 1:5 to 1:15 25 c) optionally, other ingredients to 100 wt%, provided that zeolite and phosphate builders are present at less than 5 wt% and ethanol is present at a level of less than 5 wt%.

WO 2010/069957 PCT/EP2009/067193 -5 It should be understood that 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. 5 Soap is not included in the calculation of anionic surfactant amounts and ratios. It is undesirable to have ethanol present at all as it is an explosion hazard during manufacture, and subsequently. Due to the relatively high levels of hydroxamate that are 10 present in the formulation, if a high level of surfactant is present, it is necessary to seek alternative hydrotrope systems. We prefer a hydrotrope system comprising propylene glycol and glycerol at levels of at least 6 wt%, more preferably at least 10 wt%. By using high levels of hydroxamate and surfactant in the composition, it is possible to use less composition per wash, which has consequential benefits for the storage and 15 transportation of the resulting concentrated formulation. Such concentrated formulations comprise at least 20 wt% of the detersive surfactant system, preferably at least 30 wt% and more preferably over 40 wt%. The preferred hydroxamates are those where R 2 is Hydrogen and R 1 is C8 to C14 alkyl, 20 preferably normal alkyl, most preferably saturated. The detergent composition is preferably used in an aqueous wash liquor, but may comprise one or more solvents suitable for use for domestic laundry purposes. Preferably, the improved stain removal occurs during the main wash of the laundry 25 process, i.e. preferably the laundry detergent composition in which the hydroxamates are used is a main wash product. The wash liquor is preferably free of formate salts. Furthermore, it is preferably free from bleach, especially peroxygen bleach. The composition may comprise from 1 to 15 wt% soap. The preferred soaps are made 30 from saturated fatty acids.

WO 2010/069957 PCT/EP2009/067193 -6 Especially preferred compositions comprise at least 0.5 wt% of soil release polymer. This improves the multiwash performance of the detergent system for the removal of the clay. Inclusion of at least 0.5 wt% anti redeposition polymer is also beneficial due to the very high efficiency of primary detergency soil removal meaning that there is an increased 5 level of soil in the wash liquor, which must then be prevented from redeposition onto the same or a different piece of fabric. The preferred ratio of hydroxamate to detersive surfactant system for optimum particulate red clay soil removal lies in the range 1:7 to 1:13. An even more preferred range of ratios 10 being 1:9 to 1:11 parts by weight. The preferred ratio of anionic to nonionic surfactant for particulate red clay soil removal is at least 1:1, more preferably at least 3:2. Preferably, it is at most 9:1. So a most preferred range is 1:1 to 9:1, or 3:2 to 9:1. 15 The compositions are particularly suitable for use on particulate stains such as soils and clays, especially red clay, and also surprisingly grass. The invention also extends to the use of 0.5 to 20 wt% hydroxamic acid or its 20 corresponding hydroxamate of the structure: 0 OH /C\ /OH RI N R2 (3) wherein R 1 is a C8 normal alkyl group, and R 2 is a hydrogen atom, in a laundry detergent composition, for improving the particulate soils stain removal from a textile substrate, wherein the composition further comprises a detersive surfactant system comprising 25 anionic surfactant and nonionic surfactant at a concentration from 3 to 80 wt%; and optionally other ingredients to 100 wt%.

WO 2010/069957 PCT/EP2009/067193 -7 The hydroxamate may be incorporated within the laundry detergent compositions in any suitable fashion within the knowledge of a person of ordinary skill in the art. 5 Detailed Description of the Invention Whenever either the term 'hydroxamic acid' or 'hydroxamate' is used in this specification, this encompasses both hydroxamic acid and the corresponding hydroxamate (salt of hydroxamic acid), unless indicated otherwise. 10 All percentages mentioned herein are by weight calculated on the total composition, unless specified otherwise. The abbreviation 'wt%' is to be understood as % by weight of the total composition. 15 The stained fabric is treated with the laundry detergent composition comprising hydroxamate according to the invention and the primary detergency is the measured stain removal by the laundry composition on the stain. This is a separate process to so-called soil release using a polymer, which is treatment of fabric with a polymer (through a wash or other such treatment), with subsequent staining of the fabric, the soil release polymer 20 having the effect of the easier removal of the stain. The following definitions pertain to chemical structures, molecular segments and substituents: 25 Molecular weights of monomers and polymers are expressed as weight average molecular weights, except where otherwise specified. The textile/fabric substrates used can be any typical textile/fabric substrate, such as cotton (woven, knitted & denim), polyester (woven, knitted & micro fibre), nylon, silk, 30 polycotton (polyester/cotton blends), polyester elastane, cotton elastane, viscose rayon, acrylic or wool. Particularly suitable textile/fabric substrates are cotton, polycotton and polyester substrates.

WO 2010/069957 PCT/EP2009/067193 -8 Particulate stains are stains comprising for example dirt, soil, clay, mud or soot. They are predominately solid in nature and come into contact with fabrics in the course of their regular use. 5 Hydroxamic acid and derivatives The general structure of a hydroxamic acid in the context of the present invention has been indicated in formula 3, and R 1 , is as defined above. When R 1 , is an alkyl ether group CH 3

(CH

2 )n (EO)m wherein n is from 2 to 20 and m is from 1 to 12 then the alkyl 10 moiety terminates this side group. Preferably, R 1 is chosen from the group consisting of C4, C5, C6, 7 C8, C9, C10, C11, or C12 or C14 normal alkyl group, most preferably R 1 is at least a C814 normal alkyl group. When the C8 material is used this is called octyl hydroxamic acid. The potassium salt is particularly useful. H N OH octanohydroxarnic acid K salt 15 However, other hydroxamic acids, whilst less preferred, are suitable for use in the present invention. Such suitable compounds include, but are not limited to, the following compounds: WO 2010/069957 PCT/EP2009/067193 -9 r ~ NH 2

NH

2 O. NH OH Lysine Hydroxamate*HCI

NH

2 HN H H NH 2 H > H Methionine Hydroxamate Norvaline Hydroxamate Such hydroxamic acids are commercially available. 15 Without wishing to be bound by theory, we believe that the hydroxamate acts 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 R1 20 minus any branching that folds back onto the amate Nitrogen via group R 2 . The tail is selected to have an affinity for the surfactant system. This means that 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 25 fixed to the particulates via their binding to the metal ions embedded in the clay type particulates. The detersive surfactants will adhere to the hydroxamate, leading overall to more surfactants interacting with the fabric, leading to better soil release. Therewith the hydroxamic acids act 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 30 detergency.

WO 2010/069957 PCT/EP2009/067193 -10 This enhancing of the primary detergency of surfactant systems is especially relevant when using concentrated liquid detergent compositions, as the pH during the laundering process is relatively low (pH 7.5-8) as compared to traditional laundering processes with particulate detergent compositions (pH 9-10.5). The lower pH during the laundering 5 process with liquid detergent compositions may lead to reduced soil release, as the surface charges of the soils are less negative as compared to the higher pH during the conventional well built and buffered laundering processes, achieved with conventional zeolite or phosphate built powder products. This surface charge of the soil may lead to increased repellence of the surfactants by the soil, possibly leading to reduced release of 10 the soil. Hence, in a preferred embodiment, the hydroxamates are used in liquid detergent compositions, and more preferred the detersive surfactant concentration in said liquid detergent compositions is from 20 to 80 wt%. The hydroxamates have a higher affinity for transition metals, like iron, than for alkaline 15 earth metals like calcium and magnesium, therefore the hydroxamic acid primarily acts to improve the removal of soil on fabric, especially particulate soils, and not additionally as a builder for calcium and magnesium. This selectively is especially beneficial if the laundering composition is underbuilt; especially when it comprises less than 5 wt% zeolite or phosphate builder. 20 Surfactants The laundry detergent composition in which the hydroxamate is used comprises a detersive surfactant system at a concentration from 3 to 80 wt%. By a detersive 25 surfactant system, we mean that the surfactants therein provide a detersive, i.e. cleaning effect to textile fabrics treated as part of a laundering process. Other surfactants, which are not detersive surfactants, can be used as part of the composition. Preferably, the detersive surfactant is present at a level of from 5 to 60 wt%, more 30 preferably from 10 to 50 wt%. Even more preferably, the detersive surfactant system comprises at least 20, or 30 or even 40 wt% of the composition.

WO 2010/069957 PCT/EP2009/067193 - 11 In general, any surfactant may be used as detersive surfactants, including anionic, nonionic, cationic, and amphoteric or zwitterionic surfactants, or combinations of these, provided that there is anionic and nonionic surfactant present in the range of ratios specified above. 5 Cationic surfactant may optionally be present as part of the detersive surfactant. Anionic surfactant is present at a level of from 0.1 to 50 wt%, preferably from 1 to 40 wt%, more preferably from 1.5 to 25 wt%. Nonionic surfactant is incorporated at a level of from 10 0.1 to 50 wt%, preferably from 1 to 40 wt%, more preferably from 1.5 to 25 wt%. The ratio of anionic surfactant to nonionic surfactant is from 19:1 to 1:1.1, more preferably from 9:1 to 1:1. In general, the nonionic and anionic surfactants of the surfactant system may be chosen 15 from the surfactants described in 'Surface Active Agents' Vol. 1, by Schwartz & Perry, Interscience 1949, Vol. 2 by Schwartz, Perry & Berch, Interscience 1958, in the current edition of 'McCutcheon's Emulsifiers and Detergents' published by Manufacturing Confectioners Company or in 'Tenside-Taschenbuch', H. Stache, 2nd Edn., Carl Hauser Verlag, 1981. 20 Nonionic surfactant For the purposes of this disclosure, 'nonionic surfactant' shall be defined as amphiphilic molecules with a molecular weight of less than about 10,000, unless otherwise noted, which are substantially free of any functional groups that exhibit a net charge at the 25 normal wash pH of 6-11. Any type of nonionic surfactant may be used, although preferred materials are further discussed below. Highly preferred are fatty acid alkoxylates, especially ethoxylates, having an alkyl chain of from C 8

-C

35 , preferably C 8

-C

30 , more preferably C 10

-C

24 , 30 especially C 1 0

-C

1 8 carbon atoms, for example, the Neodol range from Shell (The Hague, The Netherlands); ethylene oxide/propylene oxide block polymers which may have molecular weight from 1,000 to 30,000, for example, Pluronic (trademark) from BASF WO 2010/069957 PCT/EP2009/067193 - 12 (Ludwigshafen, Germany); and alkylphenol ethoxylates, for example Triton X-100, available from Dow Chemical (Midland, Mich., USA). Other nonionic surfactants should also be considered within the scope of this invention. 5 These include condensates of alkanolamines with fatty acids, such as cocamide DEA, polyol-fatty acid esters, such as the Span series available from Uniqema (Gouda, The Netherlands), ethoxylated polyol-fatty acid esters, such as the Tween series available from Uniqema (Gouda, The Netherlands), alkylpolyglucosides, such as the APG line available from Cognis (DOsseldorf, Germany) and n-alkylpyrrolidones, such as the 10 Surfadone series of products marketed by ISP (Wayne, N.J., USA). Furthermore, nonionic surfactants not specifically mentioned above, but within the definition, may also be used. The more preferred nonionic surfactants are the fatty acid ethoxylates with an average 15 degree of ethoxylation of 7, alkoxylates with one propylene oxide and multiple ethylene oxide units, seed oil based surfactant, such as Ecosurf SA7 or SA9 available from Dow Chemical, APGs, and branched alcohol Guerbet nonionics. Anionic surfactant 20 'Anionic surfactants' are defined herein as amphiphilic molecules comprising one or more functional groups that exhibit a net anionic charge when in aqueous solution at the normal wash pH of between 6 and 11. Preferred anionic surfactants are the alkali metal salts of organic sulphur reaction 25 products having in their molecular structure an alkyl radical containing from about 6 to 24 carbon atoms and a radical selected from the group consisting of sulphonic and sulphuric acid ester radicals. Although any anionic surfactant hereinafter described can be used, such as alkyl ether 30 sulphates, soaps, fatty acid ester sulphonates, alkyl benzene sulphonates, sulphosuccinate esters, primary alkyl sulphates, olefin sulphonates, paraffin sulphonates and organic phosphate; preferred anionic surfactants are the alkali and alkaline earth WO 2010/069957 PCT/EP2009/067193 -13 metal salts of fatty acid carboxylates, fatty alcohol sulphates, preferably primary alkyl sulfates, more preferably they are ethoxylated, for example alkyl ether sulphates; alkylbenzene sulphonates, alkyl ester fatty acid sulphonates, especially methyl ester fatty acid sulphonates and mixtures thereof. 5 Cationic, amphoteric surfactants and/or zwitterionic surfactants Also cationic, amphoteric surfactants and/or zwitterionic surfactants may be present in the laundry detergent compositions in which the hydroxamate is used as cosurfactant according to the invention. 10 Preferred cationic surfactants are quaternary ammonium salts of the general formula

R

1

R

2

R

3

R

4 N' X-, for example where R 1 is a C12-C14 alkyl group, R 2 and R 3 are methyl groups, R 4 is a 2-hydroxyethyl group, and X- is a chloride ion. This material is available commercially as Praepagen (Trade Mark) HY from Clariant GmbH, in the form of a 40% 15 by weight aqueous solution. In a preferred embodiment the laundry detergent composition in which the hydroxamate is used according to the invention further comprises an amphoteric or zwitterionic surfactant. Amphoteric surfactants are molecules that contain both acidic and basic 20 groups and will exist as zwitterions at the normal wash pH of between 6 and 11. Preferably an amphoteric or zwitterionic surfactant is present at a level of from 0.1 to 20% by weight, more preferably from 0.25 to 15% by weight, even more preferably from 0.5 to 10% by weight. 25 Suitable zwitterionic surfactants are exemplified as those which can be broadly described as derivatives of aliphatic quaternary ammonium, sulfonium and phosphonium compounds with one long chain group having about 8 to about 18 carbon atoms and at least one water solubilizing radical selected from the group consisting of sulfate, sulfonate, carboxylate, phosphate or phosphonate. A general formula for these 30 compounds is:

R

1

(R

2 )xY*R 3

Z-

WO 2010/069957 PCT/EP2009/067193 - 14 wherein R 1 contains an alkyl, alkenyl or hydroxyalkyl group with 8 to 18 carbon atoms, from 0 to 10 ethylene-oxy groups or from 0 to 2 glyceryl units; Y is a nitrogen, sulphur or phosphorous atom; R 2 is an alkyl or hydroxyalkyl group with 1 to 3 carbon atoms; x is 1 when Y is a sulphur atom and 2 when Y is a nitrogen or phosphorous atom; R 3 is an alkyl 5 or hydroxyalkyl group with 1 to 5 carbon atoms and Z is radical selected from the group consisting of sulfate, sulfonate, carboxylate, phosphate or phosphonate. Preferred amphoteric surfactants are amine oxides, for example coco dimethyl amine oxide. 10 Preferred zwitterionic surfactants are betaines, and especially amidobetaines. Preferred betaines are C8 to C18 alkyl amidoalkyl betaines, for example coco amido betaine. These may be included as co-surfactants, preferably present in an amount of from 0 to 10 wt %, more preferably 1 to 5 wt %, based on the weight of the total composition. Other betaines 15 that may be employed are sulfatobetaines, such as 3-(dodecyldimethylammonium)-1 propane sulfate; and 2-(cocodimethylammonium)-1 -ethane sulfate. Sulfobetaines, such as: 3-(dodecyldimethyl-ammonium)-2-hydroxy-1 -propane sulfonate; 3-(tetradecyl dimethylammonium)-1 -propane sulfonate; 3-(C12-C14 alkyl amidopropyldimethylammonium)-2-hydroxy-1 -propane sulfonate; and 3 20 (cocodimethylammonium)-1 -propane sulfonate. Carboxybetaines, such as (dodecyldimethylammonium) acetate (also known as lauryl betaine); (tetradecyldimethylammonium) acetate (also known as myristyl betaine); (cocodimethylammonium) acetate (also known as coconut betaine); (oleyldimethylammonium) acetate (also known as oleyl betaine); 25 (dodecyloxymethyldimethylammonium) acetate; and (cocoamido propyldimethylammonium) acetate (also known as cocoamido-propyl betaine or CAPB). The sulfoniumbetaines, such as: (dodecyldimethylsulfonium) acetate; and 3 (cocodimethyl-sulfonium)-1 -propane sulfonate. 30 The phosphoniumbetaines, such as 4-(trimethylphosphonium)-1-hexadecane sulfonate; 3-(dodecyldimethylphosphonium)-1-propanesulfonate; and 2-(dodecyldimethylphosphonium)-1 -ethane sulfate.

WO 2010/069957 PCT/EP2009/067193 -15 The laundry detergent compositions preferably comprise carboxybetaines or sulphobetaines as amphoteric or zwitterionic surfactants, or mixtures thereof. Especially preferred is lauryl betaine. The betaines and hydroxamates may provide even further enhanced particulate soil removal when used together in the compositions according to 5 the invention. Detergency builders The laundry detergent compositions in which the hydroxamate is used preferably 10 comprise low levels of detergency builder, based on the weight of the total composition. The amounts of the inorganic builders zeolite and phosphate are less than 5 wt%. These builders are considered to be harmful to the environment when used in large quantities. Furthermore they need to be used at high levels to have a significant building effect and this is inconsistent with the modern concentrated highly weight efficient laundry detergent 15 formulations. Preferably the builder is selected from the group of alkali and alkaline earth metal carbonates (e.g. sodium carbonate), silicates (e.g. layered silicate), and organic builders such as citrates (e.g. sodium citrate), succinates, sulphamates and malonates, and any 20 combination of these. The organic builders are preferred. They may be used at levels of 1 wt% or more, up to, say, 50 wt%. Organic builders that may be present include polycarboxylate polymers such as polyacrylates and acrylic/maleic copolymers; polyaspartates; monomeric 25 polycarboxylates such as citrates, gluconates, oxydisuccinates, glycerol mono-di- and trisuccinates, carboxymethyloxysuccinates, carboxy-methyloxymalonates, dipicolinates, hydroxyethyliminodiacetates, alkyl- and alkenylmalonates and succinates; and sulphonated fatty acid salts. 30 Organic builders may be used in minor amounts Especially preferred organic builders are citrates, suitably used in amounts of from 1 to 30 wt%, preferably from 1.5 to 10 wt%; and WO 2010/069957 PCT/EP2009/067193 -16 acrylic polymers, more especially acrylic/maleic copolymers, suitably used in amounts of from 0.5 to 15 wt%, preferably from 1 to 10 wt%. Builders, both inorganic and organic, are preferably present in alkali metal salt, especially 5 sodium salt, form. Other optional Ingredients In addition to the essential components detailed in the claims, the formulation may 10 include one or more optional ingredients to enhance performance and properties. While it is not necessary for these elements to be present in order to practice this invention, the use of such materials is often very helpful in rendering the formulation acceptable for consumer use. 15 Examples of optional components include, but are not limited to: hydrotropes, fluorescent whitening agents, photobleaches, fibre lubricants, reducing agents, enzymes, enzyme stabilising agents (such as borates and polyols), powder finishing agents, defoamers, bleaches, bleach catalysts, soil release agents, especially soil release polymers for cotton or polyester or both, antiredeposition agents, especially antiredeposition polymers, dye 20 transfer inhibitors, buffers, colorants, fragrances, pro-fragrances, rheology modifiers, anti ashing polymers, preservatives, insect repellents, soil repellents, water-resistance agents, suspending agents, aesthetic agents, structuring agents, sanitisers, solvents, including aqueous and non-aqueous solvents, fabric finishing agents, dye fixatives, wrinkle reducing agents, fabric conditioning agents and deodorizers. 25 These optional ingredients may include, but are not limited to, any one or more of the following: soap, peroxyacid and persalt bleaches, bleach activators, sequestrants, cellulose ethers and esters, other antiredeposition agents, sodium sulphate, sodium silicate, sodium chloride, calcium chloride, sodium bicarbonate, other inorganic salts, 30 fluorescers, photobleaches, polyvinyl pyrrolidone, other dye transfer inhibiting polymers, foam controllers, foam boosters, acrylic and acrylic/maleic polymers, proteases, lipases, WO 2010/069957 PCT/EP2009/067193 -17 cellulases, amylases, other detergent enzymes, citric acid, soil release polymers, fabric conditioning compounds, coloured speckles, and perfume. The laundry detergent composition may suitably contain a bleach system based on 5 peroxy bleach compounds, for example, inorganic persalts or organic peroxyacids, capable of yielding hydrogen peroxide in aqueous solution. Suitable peroxy bleach compounds include organic peroxides such as urea peroxide, and inorganic persalts such as the alkali metal perborates, percarbonates, perphosphates, persilicates and persulphates. Preferred inorganic persalts are sodium perborate monohydrate and 10 tetrahydrate, and sodium percarbonate. Especially preferred is sodium percarbonate having a protective coating against destabilisation by moisture. Sodium percarbonate having a protective coating comprising sodium metaborate and sodium silicate is disclosed in GB 2 123 044B (Kao). 15 The peroxy bleach compound is suitably present in an amount of from 5 to 35% by weight, preferably from 10 to 25% by weight. The peroxy bleach compound may be used in conjunction with a bleach activator (bleach precursor) to improve bleaching action at low wash temperatures. The bleach precursor is 20 suitably present in an amount of from 1 to 8% by weight, preferably from 2 to 5% by weight. Preferred bleach precursors are peroxycarboxylic acid precursors, more especially peracetic acid precursors and peroxybenzoic acid precursors; and peroxycarbonic acid 25 precursors. An especially preferred bleach precursor suitable for use in the present invention is N,N,N',N'-tetracetyl ethylenediamine (TAED). Also of interest are peroxybenzoic acid precursors, in particular, N,N,N-trimethylammonium toluoyloxy benzene sulphonate. 30 A bleach stabiliser (heavy metal sequestrant) may also be present. Suitable bleach stabilisers include ethylenediamine tetraacetate (EDTA) and the polyphosphonates such as Dequest (Trade Mark), EDTMP.

WO 2010/069957 PCT/EP2009/067193 -18 However, notwithstanding the above it is preferred for the composition to contain no bleach and to rely on the improved clay stain removal derived from the novel hydroxamate and surfactant combination. This is particularly the case for liquid compositions. 5 The detergent compositions may also contain one or more enzymes. Suitable enzymes include the proteases, amylases, cellulases, oxidases, peroxidases and lipases usable for incorporation in detergent compositions. 10 In particulate detergent compositions, detergency enzymes are commonly employed in granular form in amounts of from about 0.1 to about 3.0 wt%. However, any suitable physical form of enzyme may be used in any effective amount. Antiredeposition agents, for example cellulose esters and ethers, for example sodium 15 carboxymethyl cellulose, may also be present. The compositions may also contain soil release polymers, for example sulphonated and unsulphonated PET/POET polymers, both end-capped and non-end-capped, and polyethylene glycol/polyvinyl alcohol graft copolymers such as Sokolan (Trade Mark) 20 HP22. Especially preferred soil release polymers are the sulphonated non-end-capped polyesters described and claimed in WO 95 32997A (Rhodia Chimie). Product form and preparation 25 A product according to the invention may take any suitable form, such as a solid, liquid or paste composition, for example as particulates (powders, granules), tablets or bars. Preferably, the product is in a concentrated liquid with a surfactant concentration of at least 30wt%. Such compositions require the presence of hydrotropes to solubilise the ingredients. Ethanol is preferably avoided. Preferred hydrotropes are propylene glycol 30 and glycerol. Based on this teaching the skilled person will be able to select other hydrotropes that avoid the use of highly volatile solvents like ethanol without the need for inventive activity.

WO 2010/069957 PCT/EP2009/067193 -19 According to a second embodiment of the invention, the detergent composition is in particulate form. The ratio of anionic to nonionic surfactant in the detersive surfactant system is then preferably at least 3:2, preferably at least 7:2. 5 Powders of low to moderate bulk density may be prepared by spray-drying slurry, and optionally post dosing (dry-mixing) further ingredients. Routes available for powder manufacture include spray drying, drum drying, fluid bed drying, and scraped film drying devices such as the wiped film evaporator. A preferred form of scraped film device is a wiped film evaporator. One such suitable wiped film evaporator is the 'Dryex system' 10 based on a wiped film evaporator available from Ballestra S.p.A.. Alternative equipment would be the Chemithon the 'Turbo Tube' dryer system wherein a high active surfactant paste is heated and metering to a multi tube, steam-jacketed drying vessel. 'Concentrated' or 'compact' powders may be prepared by mixing and granulating 15 processes, for example, using a high-speed mixer/granulator, or other non-tower processes. Tablets may be prepared by compacting powders, especially 'concentrated' powders. 20 The invention will now be further described with reference to the following non-limiting examples. EXAMPLES 25 Measurement of Soil Release Index (SRI) SRI is a measure of how much of a stain on textile is removed during a washing process. The intensity of any stain can be measured by means of a reflectometer in terms of the difference between the stain and a clean cloth giving AE* for each stain. It is defined as AE* and is calculated as: 30 AE* = V(L*tain before - Lclean cloth )2 + (atain before - aclean-cloth )2 + ( b;,ta, before - bean cloh2 WO 2010/069957 PCT/EP2009/067193 - 20 L*, a*, and b* are the coordinates of the CIE 1976 (L*, a*, b*) colour space, determined using a standard reflectometer. AE* can be measured before and after the stain is washed, to give AE*bw (before wash) and AE*aW (after wash). SRI is then defined as: 5 SR/=100- AEw A SRI of 100 means complete removal of a stain. AE after wash is the difference in L a b colour space between the clean (unwashed) fabric 10 and the stain after wash. So a AE after wash of zero means a stain that is completely removed. Therefore, a SRlaw of 100 is a completely removed stain. The clean (or virgin) fabric is an "absolute standard" which is not washed. For each experiment, it refers to an identical piece of fabric to that which the stain is applied. Therefore, its point in L a b colour space stays constant. 15 Example 1: Preparation of octyl hydroxamate (potassium salt) The potassium salt of octyl hydroxamate was prepared by the method disclosed by Raghavan and Fuerstenau (Journal of Colloid and Interface Science, 1975, Vol. 50, p. 319-330). 20 Example 2: Removal of red clay stains on knitted polyester (2:1) A wash liquor was formulated, containing as surfactants primary alkyl sulfate (PAS, anionic, ex Kao Emal PH10) and alcohol ethoxylate (nonionic C 12 -7EO, Neodol 25-7 ex Shell), as shown in table 1 at the indicated concentrations. Additionally the wash liquor 25 contained NaCl at a concentration of 5 mM. Water hardness was 6 0 FH (soft water, about 24 milligram calcium per litre), and water temperature was 30'C. No builder or sequestrants were added to the composition, as these ingredients were not required due to the soft water used.

WO 2010/069957 PCT/EP2009/067193 -21 Table 1 Concentrations of surfactants and hydroxamate in wash liquors. Ingredient Formulation 1 Formulation 2 concentration in wash liquor (g/L) primary alcohol sulfate 0.33 0.33 alcohol ethoxylate (C12 0.16 0.16 7EO) octyl hydroxamate 0.00 0.05 (potassium salt) prepared in example 1 The following results were obtained for the removal of red clay stains from knitted polyester cloth, as measured in the following standard protocol, called the soft water 5 Tergotometer wash protocol, using a Tergotometer washing machine. The red clay used is a form of pottery clay. Soft water Tergotometer wash protocol: 1. Measurement of the colour of the stain on the textile cloth 10 2. Set Tergotometer to 25'C. 3. Add water and formulation stock solutions to each pot, agitate for 1 minute. 4. Add stain cloths and ballast, switch on Tergotometer. 5. Leave to wash for 12 minutes 6. Rinse cloths in 6' French hard water for 1 minute, repeat rinse. 15 7. Dry cloths overnight. 8. Measurement of the colour of the stain on the textile cloth Table 2 Stain removal index (SRI) for red clay stains on knitted polyester Formulation SRI red clay stains on knitted polyester 1 (comparative) 88.0 2 97.2 WO 2010/069957 PCT/EP2009/067193 - 22 This experiment shows that the formulation comprising octyl hydroxamate leads to substantially better removal of red clay stains from knitted polyester in soft water. As this is an experiment in soft water, the mechanism by which the hydroxamic acid acts is not as a builder, therefore the builder effect is excluded as a mechanism of action for 5 improvement of the detergency effect. Example 3: Removal of Georgia clay stains from knitted polyester and grass stains from woven cotton 10 Two liquid detergents were formulated. The surfactants used were sodium alkyl benzene sulphonate (Na LAS, anionic), alcohol ethoxylate (nonionic C 12 -7EO, Neodol 25-7 ex Shell) and a neutralised saturated soap (coco fatty acid (Prifac 5908 ex Uniqema)) as shown in table 3 at the indicated concentrations. Also used were standard compounds of a laundry liquid detergent (builder (sodium citrate), hydrotrope (5% glycerol and 9% 15 propylene glycol), buffer and sequestrant (Dequest 2066 phosphonate), enzyme (Savinase Ultra 16L protease). Two wash liquors were prepared using formulations 3 and 4, respectively, as outlined in table 3, to give surfactant and hydroxamate levels as shown in table 4. The water hardness in the liquors was 26 0 FH (median water, about 104 milligram calcium per litre), and water temperature was 40'C. The pH was buffered to 20 between 7 and 8.

WO 2010/069957 PCT/EP2009/067193 - 23 Table 3 Formulations used Ingredient Formulation 3 Formulation 4 % in Product Na LAS 27.6 27.6 alcohol ethoxylate (C12 12.5 12.5 7EO) Nasoap 8 8 octyl hydroxamate 4 (potassium salt) prepared in example 1 Dequest 2066 0.5 0.5 sodium citrate 2 2 triethanol amine 3.2 3.2 hydrotropes, enzymes & 14 14 minors water 32.2 Table 4 Concentrations of surfactants and hydroxamates in wash liquors based on the 5 formulations in table 3. Ingredient Formulation 3 Formulation 4 in wash level (g/L) Na LAS 0.72 0.72 alcohol ethoxylate (C12 0.33 0.33 7EO) Na soap 0.24 0.24 octyl hydroxamate 0.00 0.12 (potassium salt) prepared in example 1 WO 2010/069957 PCT/EP2009/067193 - 24 The following results were obtained for the removal of Georgia clay stains from knitted polyester cloth and the removal of grass stains from woven cotton, as measured in the following standard protocol, called the LinitestTM wash protocol, using a LinitestTM washing machine. 5 LinitestTM wash protocol 1. Read before wash stains. 2. Switch on LinitesterTM and leave to heat to 400C. 3. Dose product into pots, add water to pots. 10 4. Place stains, ballast and 50 ball bearings in pots. 5. Start LinitesterM and leave to wash for 30 minutes. 6. Rinse ballast and cloths for 5 minutes. 7. Repeat rinse. 8. Dry stains overnight. 15 9. Read after wash stains. Table 5 Stain removal index (SRI) for Georgia clay stains on knitted polyester and woven cotton and grass on knitted polyester Formulation SRI SRI SRI Georgia clay on Grass on knitted Georgia clay on knitted polyester polyester woven cotton 3 (comparative) 79.4 90.1 66.4 4 89.1 92.1 70.7 20 This experiment shows that the use of the hydroxamate acid leads to better removal of Georgia clay as well as grass on knitted polyester and improved removal of Georgia clay from woven cotton. Although Savinase is present in the detergent composition, which improves grass stain 25 removal, grass stain removal is further improved by the addition of the hydroxamate.

WO 2010/069957 PCT/EP2009/067193 - 25 Example 4. Typical examples of detergent compositions Some typical detergent compositions according to the present invention are given in table 6. 5 Table 6 Typical detergent compositions according to the invention. Ingredient Powder Liquid Concentrated Formulation Detergent Liquid (concentration in Formulation Detergent final product (concentration in (concentration in [weight %]) final product final product [weight %]) [weight %]) linear alkyl benzene 15 16 24 sulphonate alcohol ethoxylate 5 8 12 Sodium sulphate 40 Sodium carbonate 20 enzymes 1 1 2 whitening agent 0.1 0.1 0.1 hydroxamate 1 2 3 sodium citrate 5 5 sodium chloride 2 2 sodium hydroxide 1 1 dispersant 1 2 perfume, foam control balance balance balance & other minors WO 2010/069957 PCT/EP2009/067193 - 26 Example 5 Hydroxamates with various alky chain lengths The following results were obtained for the removal of Georgia Clay stains from woven cotton cloth, as measured in the following standard protocol, called the Tergotometer hard water wash protocol, using a Tergotometer washing machine. Different 5 hydroxamates were used according to table 7. Terqotometer hard water wash protocol: Measurement of the colour of the stain on the textile cloth 10 Set Tergotometer to 30'C. Add water and formulation stock solutions to each pot, agitate for 1 minute. Add stain cloths and ballast, switch on Tergotometer. Leave to wash for 12 minutes Rinse cloths in 26' French hard water for 1 minute, repeat rinse. 15 Dry cloths overnight. Measurement of the colour of the stain on the textile cloth WO 2010/069957 PCT/EP2009/067193 - 27 Table 7 Ingredient Formulation Formulation Formulation Formulation Formulation 5 6 7 8 9 wt% in Product Na LAS 14.3 14.3 14.3 14.3 14.3 alcohol 20.11 20.11 20.11 20.11 20.11 ethoxylate (C12 7EO) Na soap 8.02 8.02 8.02 8.02 8.02 SLES 6.7 6.7 6.7 6.7 6.7 Sodium Citrate 1 1 1 1 1 Triethanolamine 3.2 3.2 3.2 3.2 3.2 Sequestrant 0.5 0.5 0.5 0.5 0.5 (Dequest 2066) Hydrotropes, 14 14 14 14 14 enzymes and minors Hexyl 5 Hydroxamate Octyl 5 Hydroxamate Decyl 5 hydroxamate Dodecyl 5 hydroxamate Water Balance Balance Balance Balance Balance WO 2010/069957 PCT/EP2009/067193 - 28 Table 8 Formulation Dose of Formulation in SRlaw Georgia Clay from wash Woven Cotton (g/L) 5 (control) 1.42 69.4 6 (hexyl hydroxamate, 1.42 71.0 potassium salt) 7 (Octyl hydroxamate, 1.42 72.7 potassium salt) 5 Table 9 Formulation Dose of Formulation SRlaw Georgia Clay in wash from knitted polyester (g/L) 5 (control) 2.72 71.4 7 (Octyl hydroxamate, 2.72 72.7 potassium salt 8 (Decyl Hydroxamate, 2.72 81.9 potassium salt) 9 (Dodecyl Hydroxamate, 2.72 79.5 potassium salt) Tables 8 and 9 summarise the results on the different cloths.

WO 2010/069957 PCT/EP2009/067193 - 29 Example 6: Effect of Anionic Nonionic ratio Table 10 Formulations A to F (Comparative - without Octyl Hydroxamate) Ingredient A B C D E F In Wash Level (g/L) NaLAS 1 0.8 0.67 0.5 0.25 0 Neodol 25-7 0 0.2 0.33 0.5 0.75 1 (nonionic surfactant Ex Shell) Sodium salt 0.2 0.2 0.2 0.2 0.2 of Prifac 5908 Table 11 Formulations with Octyl hydroxamate Ingredient AOH B_OH COH D_OH E_OH FOH In Wash Level (g/L) Na LAS 1 0.8 0.67 0.5 0.25 0 (anionic surfactant) Neodol 25-7 0 0.2 0.33 0.5 0.75 1 (nonionic surfactant) (ex Shell) Octyl 0.12 0.12 0.12 0.12 0.12 0.12 Hydroxamate Sodium salt 0.2 0.2 0.2 0.2 0.2 of Prifac 5908 (soap) 5 This example shows the effect of varying the ration of anionic to nonionic surfactant for the removal of Georgia Clay stains from knitted polyester, as measured in the WO 2010/069957 PCT/EP2009/067193 - 30 Tergotometer hard wash protocol described above. The formulations are given in table 11 and the comparative formulations without the hydroxamate are given in table 10. The results are summarised in table 12. Formulations A-OH, E-OH and F-OH are 5 comparative. Table 12 Formulation Anionic:nonionic SRaw SRaw (with % increase (no hydroxamate) hydroxamate) SRI A / AOH 1 to 0 67.3 68.4 1.63 B / BOH 4 to 1 73.8 80.2 8.67 C / COH 2 to 1 73.8 80.4 8.94 D / DOH 1 to 1 68.9 78.0 13.21 E / EOH 1 to 3 66.3 69.7 5.13 F / FOH 0 to 1 66.6 66.2 -0.60 10 Example 7 - Higher Anionic to Nonionic ratios (Georgia Clay removal from woven cotton) A number of Anionic/Nonionic formulations were made where the anionic to nonionic surfactant ratio was at least 4:1. A set of comparative formulations without hydroxamate 15 was first made up as per table 13. Then a set of corresponding formulations comprising 5 wt% of octyl hydroxamate was made up as per table 14.

WO 2010/069957 PCT/EP2009/067193 - 31 Table 13 (Comparative formulations) Ingredient G H I J wt% in formulation Na LAS 32.9 37.0 39.0 41.1 alcohol 8.2 4.1 2.1 0 ethoxylate (C12 7EO) Na soap 8.02 8.02 8.02 8.02 Sodium Citrate 1 1 1 1 Triethanolamine 3.2 3.2 3.2 3.2 Sequestrant 0.5 0.5 0.5 0.5 (Dequest 2066) Hydrotropes, 14 14 14 14 enzymes and minors Water Balance Balance Balance Balance The soap used was Prifac 5908. The hydrotropes were glycerol and propylene glycol.

WO 2010/069957 PCT/EP2009/067193 - 32 Table 14 Ingredient GOH HOH IOH JOH wt% in formulation Na LAS 32.9 37.0 39.0 41.1 alcohol 8.2 4.1 2.1 0 ethoxylate (C12 7EO) Na soap 8.02 8.02 8.02 8.02 Sodium Citrate 1 1 1 1 Triethanolamine 3.2 3.2 3.2 3.2 Sequestrant 0.5 0.5 0.5 0.5 (Dequest 2066) Octyl 5 5 5 5 hydroxamate (potassium salt) Hydrotropes, 14 14 14 14 enzymes and minors Water Balance Balance Balance Balance The following results were obtained for the removal of Georgia Clay stains from woven 5 cotton, as measured using the standard hard water Tergotometer wash protocol described above and with an In wash formulation concentration of 2.6 g/L for each of the formulations in tables 13 and 14. The results are given in table 15. Example J-OH is comparative.

WO 2010/069957 PCT/EP2009/067193 - 33 Table 15 Formulations Anionic:nonionic SRaw SRaw (with % (no hydroxamate) increase hydroxamate) SRI G / GOH 4 to 1 67 72.9 8.81 H / HOH 9 to 1 68.2 70.6 3.52 / I_OH 19 to 1 67.2 68.6 2.08 J J_OH 1 too 68.8 68.6 -0.29 5 Example 8: Alternative Anionic: Primary Alkyl sulphate Table 16 (comparative formulations) Ingredient K L M N 0 P Primary Alkyl 0 27.5 32.9 41.1 20.55 10.3 Sulphate Alcohol 41.1 13.6 8.2 0 20.55 30.8 ethoxylate (C12 7EO) Na soap 8.02 8.02 8.02 8.02 8.02 8.02 Sodium Citrate 1 1 1 1 1 1 Triethanolamine 3.2 3.2 3.2 3.2 3.2 3.2 Sequestrant 0.5 0.5 0.5 0.5 0.5 0.5 (Dequest 2066) Hydrotropes, 14 14 14 14 14 14 enzymes and minors Water Balance Balance Balance Balance Balance Balance WO 2010/069957 PCT/EP2009/067193 - 34 Table 17 (formulations with hydroxamate) Ingredient KOH LOH MOH NOH OOH POH Primary Alkyl 0 27.5 32.9 41.1 20.55 10.3 Sulphate Alcohol 41.1 13.6 8.2 0 20.55 30.8 ethoxylate (C12 7EO) Na soap 8.02 8.02 8.02 8.02 8.02 8.02 Sodium Citrate 1 1 1 1 1 1 Triethanolamine 3.2 3.2 3.2 3.2 3.2 3.2 Sequestrant 0.5 0.5 0.5 0.5 0.5 0.5 (Dequest 2066) Octyl 5 5 5 5 5 5 hydroxamate (potassium salt) Hydrotropes, 14 14 14 14 14 14 enzymes and minors Water Balance Balance Balance Balance Balance Balance The following results in table 18 were obtained for the removal of Georgia Clay stains from knitted polyester, as measured using the hard water Tergotometer wash protocol 5 using 2.6 g/L formulation in wash. The comparative formulations without hydroxamate are given in table 16 and the hydroxamate containing formulations are given in table 17. The hydrotrope system, as usual, comprised 5 wt% glycerol and 9 wt% propylene glycol. Compositions N-OH and P-OH are comparative as the ratio of anionic to nonionic is outside of the claimed range.

WO 2010/069957 PCT/EP2009/067193 - 35 Table 18 Formulation Anionic:nonionic SRIaw SRIaw (with % increase (no hydroxamate) SRI hydroxamate) K / KOH 0 to 1 73.6 75.4 2.45 P / POH 1 to 3 74.0 73.4 -0.81 0 /OOH 1 to 1 74.1 75.6 2.02 L /L_OH 2 to 1 73.4 77.2 5.18 M /M_OH 4 to 1 73.9 77.7 5.14 N /N_OH 1 too 73 74.7 2.33

Claims

1 ) A laundry detergent composition comprising b) 0.5 to 20, preferably 6, wt% hydroxamic acid or its corresponding hydroxamate of the structure:

o

/\ /'

R² wherein R¹ is a straight or branched C₄-C₂O alkyl, or a straight or branched substituted C₄-C₂₀ alkyl, or a straight or branched C₄-C₂₀ alkenyl, or a straight or branched substituted C₄-C₂₀ alkenyl, or an alkyl ether group CH₃ (CH₂)_n (EO)_m wherein n is from 2 to 20 and m is from 1 to 12, or a substituted alkyl ether group CH₃ (CH₂)_n (EO)_m wherein n is from 2 to 20 and m is from 1 to 12, and the types of substitution include one or more of -NH₂, -OH, -S-, -O-, -COOH, and

C OH Il I - C - N - and R² is selected from hydrogen and a moiety that forms part of a cyclic structure with a branched R¹ group, b) 3 to 80 wt% of detersive surfactant system comprising

(i) anionic surfactant; and

(ii) nonionic surfactant wherein the ratio of (i) to (ii) lies in the range 1 :1.1 to 19:1 , and the weight ratio a) to b) lies in the range 1 :5 to 1 :15 c) optionally, other ingredients to 100 wt% provided that zeolite and phosphate builders are present at less than 5 wt% and ethanol is present at a level of less than 5 wt%. 2) Composition according to claim 1 , wherein R¹ is chosen from the group consisting of C₄, C₅, C₆, C₇, C₈, C₉, Cio, Cii, Ci2 or Ci₄ normal alkyl group and R² is hydrogen.

3) Composition according to claim 1 or 2, wherein R¹ is a C_8--_I4 normal alkyl group.

4) A composition according to any of claims 1 to 3, wherein the composition comprises detergency builder at a concentration from 1 to 50 wt%.

5) A composition according to any preceding claim which comprises at least 20 wt% of the detersive surfactant system, preferably at least 30 wt% and more preferably over

40 wt%.

6) A composition according to any preceding claim which comprises from 1 to 15 wt% soap, preferably made from saturated fatty acids.

7) A composition according to any preceding claim comprising at least 0.5 wt% of soil release polymer.

8) A composition according to any preceding claim comprising at least 0.5 wt% anti redeposition polymer.

9) A composition according to any preceding claim wherein the ratio of hydroxamate to detersive surfactant system lies in the range 1 :7 to 1 :13, preferably 1 :9 to 1 :11 parts by weight.

10)A composition according to any preceding claim in which the ratio of anionic to nonionic surfactant is at least 1 :1 , preferably at least 3:2.

1 1 )A composition according to claim 10 in which the ratio of anionic to nonionic surfactant is 1 :1 to 9:1 , preferably 3:2 to 9:1. 12)A composition according to any preceding claim in which the composition is a liquid composition.

13) A composition according to claim 12 comprising a hydrotrope system comprising propylene glycol and glycerol at levels of at least 6 wt%.

14)A composition according to claim 12 or 13, which is a liquid composition, comprising detersive surfactant at a concentration from 20 to 80% by weight of the total composition.

15) Use of a composition according to any preceding claim for removal of particulate soils, preferably red clay, most preferably Georgia clay, from polyester and cotton fabrics.

16) Use of 0.5 to 20 wt% hydroxamic acid or its corresponding hydroxamate of the structure: o

Il

C /OH

R1 N

R²

(3) wherein R¹ is a Cs normal alkyl group, and R² is a hydrogen atom, in a laundry detergent composition, for improving the particulate soils stain removal from a textile substrate, wherein the composition further comprises a detersive surfactant system comprising anionic surfactant and nonionic surfactant at a concentration from 3 to 80 wt%; and optionally other ingredients to 100 wt%.