CA2265899A1 - Detergent compositions - Google Patents

Abstract

The present invention relates to granular detergent compositions or components thereof, which comprise a hydrophobic organic peroxyacid bleaching system, capable of providing a hydrophobic organic peroxyacid compound and one or more cationic compounds, which are cationic, (partially) quaternized ethoxylated (poly)amine compounds with clay-soil removal/anti-redeposition properties, for use in laundry and dishwashing processes.

Description

CA 02265899 l999-03- 16WO 98/13449 PCT/U S97/ 17077Detergent CompositionsTechnical FieldThe present invention relates to granular detergent compositions orcomponents thereof containing cationic compounds withparticulate/clay-soil removal/anti-redeposition properties and ahydrophobic organic peroxyacid bleaching system for use in laundryand dish washing processes.Background to the InventionA particularly important property of a detergent composition is itsability to remove particulate type soils from a variety of fabrics duringlaundering. Perhaps the most important particulate soils are the clay-type soils. Clay soil particles generally comprise negatively chargedlayers of aluminosilicates and positively charged cations (e.g. calcium)which are positioned between and hold together the negatively chargedlayers.A variety of models can be proposed for compounds which would haveparticulate/ clay-soil removal properties. One model requires that thecompound have two distinct characteristics. The first is the ability ofthe compound to adsorb onto the negatively charged layers of the clayparticle. The second is the ability of the compound, once adsorbed, topush apart (swell) the negatively charged layers so that the clay particleloses its cohesive force and can be removed in the wash water.In addition to clay soil removal, there is a need to keep the removedsoil in suspension during the laundering (or dish washing) cycle. Soilwhich is removed from the fabric and suspended in the wash water canredeposit on the surface of the fabric. This redeposited soil causes adulling or "greying" effect which is especially noticeable on whitefabrics. To minimise this problem, anti—redeposition agents can beincluded in the detergent composition.CA 02265899 l999-03- 16WO 98113449 PCT/US97/170772For example EP—B-1 11 965 disclose the use in detergents of cationiccompounds, which have both clay-soil removal and anti—redepositionproperties.US 4,659,802 and US 4,664,848 describe quaternized amines whichhave clay-soil removal and anti—redeposition properties and which canbe used in combination with anionic surfactants.A model proposed for the anti—redeposition action of the positivelycharged anti—redeposition compounds is as follows. Adsorption of thepositively charged molecule on the surface of clay particles in the washwater gives the particles the dispersancy properties of the molecule. Asmore and more of these compounds adsorb onto the suspended claysoil particles, the latter become encased within a hydrophilic layerprovided by the attached ethoxy units. As such the hydrophilicallyencased soil is prevented from redepositing on fabrics, in particularhydrophobic fabrics such as polyester, during the laundering or dishwashig cycle.Another component traditionally used in detergent is bleach, to removebleachable stains or soils from the fabric.A disadvantage of the use of most bleaches is that various otherdetergent components are bleach sensitive and that they can be oxidisedby the bleach, whereby their original properties can be diminished.Thus, not all detergent components are b1each- compatible.The Applicants have found that cationic, (partially) quaternizedethoxylated (poly) amines which have clay-soil removal/anti-redeposition properties, are fully compatible with bleaches formulatedtherewith.It also has been found that the use in detergent compositions (orcomponents thereof) of (oxygen—releasing) bleach in combination withfully quaternised ethoxylated (poly) amines provides a betterimprovement in cleaning or whiteness maintenance than the use of(oxygen releasing) bleach in combination with partially quaternisedethoxylated (poly) amines. However, even the partially quaternisedethoxylated (poly) amines provide an improvement in cleaning orwhiteness maintenance in combination with bleach.CA 02265899 l999-03- 16W0 98/ 13449 PCT/US97/17077Without wishing to be bound by theory, the bleach—compatibility of thecationic, quaternized ethoxylated (poly) amines can be explained asfollows. The quaternization of the nitrogen groups of these moleculesis believed to have a dual purpose. It provides a cationic charge on themolecule, improving adsorption onto clay particles either on the fabricsurface or dispersed in wash water, and it removes the oxidisable lonepair on the nitrogen groups from attack by bleaching species, thusmaking the molecule stable in a bleach containing laundry detergents.Recently developed bleach species are bleaching systems based onhydrophobic peroxyacids.It has been found that a problem with hydrophobic bleaches is thatdespite their tendency to migrate to the (hydrophobic) fabric surface,they do not necessarily interact fully with the bleachable stain or soilcomponents. It has been found that the hydrophobic bleaches can beprevented from migration onto hydrophobic bleachable stainsl soils bydeposited clay-soil particulates on the fabric. Thereby, their bleachingperformance can be diminished. This result in a lessening of thebleachable/ dingy soil cleaning performance of the hydrophobicbleach.The Applicants have found that this problem can be ameliorated by theinclusion of one or more which have clay-soil removal/anti-redeposition properties (as mentioned above) in a detergentcomposition, comprising a hydrophobic bleach. It has been found thatin detergent compositions comprising both components the bleachefficacy of the hydrophobic organic peroxyacid bleaching system isenhanced. Thereby, the overall cleaning performance of the detergentis improved, which is especially noticeable on fabric stained withorganic clay-soil particules, such as peat stains.All documents cited in the present description are, in relevant part,incorporated herein by reference.CA 02265899 l999-03- 16WO 98/13449 PCT/US97/ 170774Summary of the inventionThe present invention relates to granular detergent compositions orcomponents thereof, which comprise a hydrophobic organicperoxyacid bleaching system, capable of providing a hydrophobicorganic peroxyacid compound and one or more cationic compounds,which are cationic, (partially) quaternized ethoxylated (poly) aminecompounds with particulatel clay-soil removal / anti—redepositionproperties.In more detail, the present invention relates to granular detergentcompositions or components thereof, which comprise(a) a hydrophobic organic peroxyacid bleaching system, capable ofproviding a hydrophobic organic peroxyacid compound; and(b) a water-soluble cationic compoundhaving clay soil removal/anti-redeposition properties, which isselected from the group consisting of:1) ethoxylated cationic monoamines having the formula:R2R2—-N+ —L~— XR22) ethoxylated cationic diamines having the formula:CA 02265899 l999-03- 16W0 98/ 13449 PCT/US97/170775<R3>d R3 (R3)d R3X—L-—M17R1-W/N+~L-— X or R3 -*M1—WR1-~**N+~-R orL/ L/ L L LX X X X X(R3>d R3(X-—L--—)2~—I\‘/IZVWRI-—M2~—R2R2wherein M1 is an N + or N group; each M2 is an N+ or N group,and at least one M2 is an N + group;3) ethoxylated cationic polyamines having the formula:(R3)dR4—~; [(A1)q—»v(R5)t eeee ~ M2 ~L- X]pR24) mixtures thereof;CA 02265899 l999-03- 16W0 93/13449 PCT/US97/170776o o o o 0wherein A1 is—~Nc—, —-Nco—, ~NcN—-, ——cN—, -—ocN—,R R R R R RO Q o o o—-co—, —-oco—-, --oc—, —-CNc——-or——o—,RR is H or C1-C4 alkyl or hydroxyalkyl, R1 is C2-C12 alkylene,hydroxyalkylene, alkenylene, arylene or alkarylene, or a C2-C3oxyalkylene moiety having from 2 to about 20 oxyalkylene unitsprovided that no O-N bonds are formed; each R3 is C1-C4 alkyl orhydroxyalkyl, the moiety -L—X, or two R2 together form the moiety -(CH2)r-A2-(CH2),-, wherein A2 is -0- or -CH2-, r is 1 or 2, s is 1 or2 and r + sis 3 or 4; each R3 is C1-C3 alkyl or hydroxyalkyl,benzyl, the moiety L-X, or two R3 or one R2 and one R3 togetherform the moiety -(CH2),-A2—(cH2);—; R4 is a substituted C3-C12alkyl, hydroxyalkyl, alkenyl, aryl or alkaryl group having psubstitution sites; R5 is C1-C12 alkenyl, hydroxyalkylene, alkenylene,arylene or alkarylene, or a C2-C3 oxyalkylene moiety having from 2 toabout 20 oxyalkylene units provided that no 0-0 or O-N bonds areformed; X is a nonionic group selected from the group consisting ofH, C1-C4 alkyl or hydroxyalkyl ester or ether groups, and mixturesthereof; L is a hydrophilic chain which contains the polyoxyalkylenemoiety-[(R5O),,,(CH2CI-I2O),,]—; wherein R6 is C3-C4 alkylene orhydroxyalkylene and In and n are numbers such that the moiety-(CH2CH2O),,- comprises at least about 50% by weight of saidpolyoxyalkylene moiety; d is 1 when M2 is N+ and is 0 when M2 isN; n is at least about 16 for said cationic monoamines, is at least about6 for said cationic diamines and is at least about 3 for said cationicpolyamines; p is from 3 to 8; q is 1 or O; t is 1 or 0, provided that t is 1when q is 1.CA 02265899 l999-03- 16W0 98/ 13449 PCT/US97/170777In a preferred aspect said hydrophobic organic peroxyacid bleachingsystem comprises (i) a hydrogen peroxide source and (ii) ahydrophobic organic peroxyacid bleach precursor compound.Detailed description of the inventionAn essential feature of the present invention is a water—soluble cationiccompound which has particulatel clay—soil removal/anti-redepositionproperties and which is selected from the group consisting of cationicmono—di— and polyamines.In detergent compositioms, the water—soluble cationic compound ispreferably present at a level of from 0.01% to 30%, more preferablyfrom 0.1% to 15% , most preferably from 0.2% to 3.0% by weight ofthe detergent composition.Cationic aminesThe water—soluble cationic compounds of the present invention usefulin the granular detergent compositions or components thereof in accordwith the present invention include ethoxylated cationic monoamines,ethoxylated cationic diamines and ethoxylated cationic polyamines aspreviously defined.In the preceding formulas for the cationic amines, R1 can be branched(e.g.CA 02265899 l999-03- 16W0 98/ 13449 PCT/US97/17077O0CH3—cH2—¢H——,——CH2——-CH———);C3 \Vcyclic (e.g. -0-’ ),or most preferably linearalkylene, hydroxyalkylene, alkenylene, alkarylene or oxyalkylene. R1is preferably C2-C5 alkylene for the ethoxylated cationic diamines.Each R2 is preferably methyl or the moiety -L-X; each R3 ispreferably C1-C4 alkyl or hydroxyalkyl, and most preferably methyl.The positive charge of the N+ groups is offset by the appropriatenumber of counter anions. Suitable counter anions include Cl-, Br-,SO3—2, P04-2, MeOSO3- and the like. Particularly preferred counteranions are C1~ and Br-.X can be a nonionc group selected from hydrogen (H), C1-C4 alkyl orhydroxyalkyl ester or ether groups, or mixtures thereof. Preferredesters or ethers are the acetate ester and methyl ether, respectively.. The particularly preferred nonionic groups are H and the methyl ether.In the preceding formulas, hydrophilic chain L usually consists entirely ofthe polyoxyalkylene moiety -[(R5O),,,(CH2CH2-O,,)-]. The moieties -(R5O)m- and -(CH2CH2O)n- of the polyoxyalkylene moiety can bemixed together or preferably form blocks of -(R5O),,,- and -(CH2CH2O),,-moieties. R5 is preferably C3H5 (propylene); m is preferably from O toabout 5 and is most preferably 0, i.e. the polyoxyalkylene moiety consistsCA 02265899 l999-03- 16WO 98/13449 PCT/U S97/ 170779entirely of the moiety —(CH2CH2O),,-. The moiety -(CH2CH2O),,—preferably comprises at least about 85 % by weight of the polyoxyalkylenemoiety and most preferably 100% by weight (In is O).In the preceding formulas, M1 and each M2 are preferably an N+group for the cationic diamines and polyamines.Preferred ethoxylated cationic monoamines and diamines have theformula:CH3 CH3X{—OCH2CH2)n N+-—CH2—CH2-(—CH2)a N+~— CH2CH2O%nXb(CH2CH2OfifiX (CH2CH2O~)-EXwherein X and n are defined as before, a is from 0 to 20, preferably 0to 4 (e. g. ethylene, propylene, hexamethylene) b is 1 or 0. Forpreferred cationic monoamines (b=O), n is preferably at least about16, with a typical range of from about 20 to about 35. For preferredcationic diamines (b= 1), n is at least about 12 with a typical range offrom about 12 to about 42.In the preceding formula for the ethoxylated cationic polyamines, R4(linear, branched, or cyclic) is preferably a substituted C3-C6 alkyl,hydroxyalkyl or aryl group; A1 is preferably0**"—CN—~;Hn is preferably at least about 12, with a typical range of from about 12to about 42; p is preferably from 3 to 6. When R4 is a substitutedaryl or alkaryl group, q is preferably 1 and R5 is preferably C2-C3alkylene. When R4 is a substituted alkyl, hydroxyalkyl, or alkenylCA 02265899 1999-03-16wo 93/13449 PCT/US97/1707710group, and when q is O, R5 is preferably a C2-C3 oxyalkylene moiety;when q is 1, R5 is preferably C2-C3 alkylene.These ethoxylated cationic polyamines can be derived from polyaminoamides such as:9H;'C';1'—(’,C3H6“)‘NH2ii’ if1HO I~CN—(-C3H6—)—NH2 or O CN(C3H6—)-NH2’ H HQ 3H-CN—(-C3H6—fNH2HThese ethoxylated cationic polyamines can also be derived frompolyaminopropyleneoxide derivatives such as:!—{OC3H6)c-—NH2CH3 (OC3H6)c —— NH2IIIIL(OC3H6)c —-NH2wherein each c is a number from 2 to about 20.Hydrophobic organic pgrozgyacjg bleaching systemAn essential feature of detergent compositions or components thereofin accord with the invention is a hydrophobic organic peroxyacidbleaching system, capable of providing a hydrophobic organicperoxyacid compound. By hydrophobic organic peroxyacid compoundCA 02265899 l999-03- 16W0 98/ 13449 PCTIUS97/1707711it is meant herein an organic peroxyacid whose parent carboxylic acidhas a critical micelle concentration less than 0.5 moles/litre andwherein said critical micelle concentration is measured in aqueoussolution at 20°-50°C.Preferably the hydrophobic organic peroxyacid bleaching systemcomprises a hydrogen peroxide source and a hydrophobic organicperoxyacid bleach precursor compound. The production of thehydrophobic organic peroxyacid occurs by an in situ reaction of theprecursor with a source of hydrogen peroxide. Preferred sources ofhydrogen peroxide include inorganic perhydrate bleaches. In analternative preferred execution the hydrophobic organic peroxyacidbleaching system comprises a preformed hydrophobic organicperoxyacid, which is incorporated directly into the composition.Compositions containing mixtures of a hydrogen peroxide source andhydrophobic organic peroxyacid precursor in combination with apreformed hydrophobic organic peroxyacid are also envisaged.Preferably, the hydrophobic organic peroxyacid contains at least 7carbon atoms, more preferably at least 9 carbon atoms, mostpreferably at least 11 carbon atoms. In a preferred aspect theperoxyacid has an alkyl chain comprising at least 7 carbon atoms,more preferably at least 8 carbon atoms, most preferably at least 9carbon atoms.Inorganic perhydrate bleachesInorganic perhydrate salts are a preferred source of hydrogenperoxide. These salts are normally incorporated in the form of thealkali metal, preferably sodium salt at a level of from 1% to 40% byweight, more preferably from 2% to 30% by weight and mostpreferably from 5 % to 25 % by weight of the compositions.Examples of inorganic perhydrate salts include perborate,percarbonate, perphosphate, persulfate and persilicate salts. Theinorganic perhydrate salts are normally the alkali metal salts. Theinorganic perhydrate salt may be included as the crystalline solidCA 02265899 l999-03- 16W0 98/13449 PCT/US97/1707712without additional protection. For certain perhydrate salts however,the preferred executions of such granular compositions utilise a coatedform of the material which provides better storage stability for theperhydrate salt in the granular product. Suitable coatings compriseinorganic salts such as alkali metal silicate, carbonate or borate salts ormixtures thereof, or organic materials such as waxes, oils, or fattysoaps.Sodium perborate is a preferred perhydrate salt and can be in the formof the monohydrate of nominal formula NaBO2H202 or thetetrahydrate NaBO2H202.3H20.Alkali metal percarbonates, particularly sodium percarbonate arepreferred perhydrates herein. Sodium percarbonate is an additioncompound having a formula corresponding to 2Na2CO3.3H2O2, andis available commercially as a crystalline solid.Potassium peroxymonopersulfate is another inorganic perhydrate saltof use in the detergent compositions herein.Peroxyacid bleach precursorPeroxyacid bleach precursors are compounds which react withhydrogen peroxide in a perhydrolysis reaction to produce a peroxyacid.Generally peroxyacid bleach precursors may be represented asOX-C—Lwhere L is a leaving group and X is essentially any functionality, suchthat on perhydrolysis the structure of the peroxyacid produced isOX-C~OOHFor the purposes of the present invention X will thus contain at least 6carbon atoms.CA 02265899 l999-03- 16W0 98/13449 PCT/US97/1707713The hydrophobic peroxyacid bleach precursor compounds arepreferably incorporated at a level of from 0.05 % to 20% by weight,more preferably from 0.1% to 15% by weight, most preferably from0.2% to 10% by weight of the detergent compositions.Suitable hydrophobic peroxyacid bleach precursor compounds typicallycontain one or more N— or O—acyl groups, which precursors can beselected from a wide range of classes. Suitable classes includeanhydrides, esters, imides, lactams and acylated derivatives ofimidazoles and oximes. Examples of useful materials within theseclasses are disclosed in GB-A—1586789. Suitable esters are disclosed inGB—A—836988, 864798, 1147871, 2143231 and EP-A-0170386.Leaving groupsThe leaving group, hereinafter L group, must be sufficiently reactivefor the perhydrolysis reaction to occur within the optimum time frame(e. g., a wash cycle). However, if L is too reactive, this activator willbe difficult to stabilize for use in a bleaching composition.Preferred L groups are selected from the group consisting of: _. Y R3 R5Y/*//"Q;/f //~93/\_’ —-o—*’\ F , ~o~a./ /}~/Y and e~o~—<T ,\//l.’ \"\\J_//v’ ’ \\'\\‘ // //\ 0vN——C—R1, —»1~f N , —N—~C—Cl-l-R4,Y$3 T-O—~C H=C—C H=C H2 -O—CH=C-CH=CH2CA 02265899 l999-03- 16WO 98/13449 PCT/US97/1707714o(H) Y no CH2-C )—c\ II IIo o$3 E.’ T—o—c=cHR4 ,and —f?l-|Sl—CH—R43 oand mixtures thereof, wherein R1 is an alkyl, aryl, or alkaryl groupcontaining from 1 to 14 carbon atoms, R is an alkyl chain containingfrom 1 to 8 carbon atoms, R4 is H or R3, R5 is an alkylene chaincontaining from 1 to 8 carbon atoms and Y is H or a solubilizinggroup. Any of R1, R3 and R4 may be substituted by essentially anyfunctional group including, for example alkyl, hydroxy, alkoxy,halogen, amine, nitrosyl, amide and ammonium or alkyl ammmoniumgroupsThe preferred solubilizing groups are —SO3”M+, -CO2'M+,-SO4'M + , —N +(R3)4X’ and O < --N(R3)3 and most preferably-SO3'M+ and —CO2'M+wherein R3 is an alkyl chain containing from 1 to 4 carbon atoms, Mis a cation which provides solubility to the bleach activator and X is ananion which provides solubility to the bleach activator. Preferably, Mis an alkali metal, ammonium or substituted ammonium cation, withsodium and potassium being most preferred, and X is a halide,hydroxide, methylsulfate or acetate anion.Amide substituted all_<yl peroxyacid precursorsPreferred peroxyacid precursors are amide substituted alkyl peroxyacidprecursor compounds, including those of the following generalformulae:CA 02265899 l999-03- 16W0 98/13449 PCT/US97/1707715R1-—C--N——-R2--C—--L R1-—N——C-—R2--C---L R5 or R5 0 0wherein R1 is an aryl or alkaryl group with from about 1 to about 14carbon atoms, R2 is an alkylene, arylene, and alkarylene groupcontaining from about 1 to 14 carbon atoms, and R5 is H or an alkyl,aryl, or alkaryl group containing 1 to 10 carbon atoms and L can beessentially any leaving group. R1 preferably contains from about 6 to12 carbon atoms. R2 preferably contains from about 4 to 8 carbonatoms. R1 may be straight chain or branched alkyl, substituted aryl oralkylaryl containing branching, substitution, or both and may besourced from either synthetic sources or natural sources including forexample, tallow fat. Analogous structural variations are permissiblefor R2. R2 can include alkyl, aryl, wherein said R2 may also containhalogen, nitrogen, sulphur and other typical substituent groups ororganic compounds. R5 is preferably H or methyl. R1 and R5 shouldnot contain more than 18 carbon atoms total. Amide substituted bleachactivator compounds of this type are described in EP-A-0170386.Preferred examples of bleach precursors of this type include amidesubstituted peroxyacid precursor compounds selected from (6-octanamido-caproyl)oxybenzenesulfonate, (6-decanamido—caproyl)oxybenzene- sulfonate, and the highly preferred (6-nonanamidocaproyl)oxy benzene sulfonate, and mixtures thereof asdescribed in EP-A-0170386.Begoxgin organic peroxyacid precursorsAlso suitable are precursor compounds of the benzoxazin-type, asdisclosed for example in EP-A-332,294 and EP-A—482,807,particularly those having the formula:CA 02265899 l999-03- 16W0 98/13449 PCT/US97/1707716,/C-R1@E Y‘)Nwherein R1 is an alkyl, alkaryl, aryl, or arylalkyl containing at least 5carbon atoms.Al ercarbox lic a id b ursorsAlkyl percarboxylic acid bleach precursors form percarboxylic acidson perhydrolysis. Preferred alkyl percarboxylic precursor compoundsof the imide type include the N-,N,N1N1 tetra acetylated alkylenediamines wherein the alkylene group contains at least 7 carbon atoms.Other preferred alkyl percarboxylic acid precursors include sodium. 3,5,5-tri-methyl hexanoyloxybenzene sulfonate (iso-NOBS) andsodium nonanoyloxybenzene sulfonate (NOBS).N-acylatgg lactgn pmgursorsStill another class of hydrophobic bleach activators are the N-acylatedprecursor compounds of the lactam class disclosed generally in GB-A-955735. Preferred materials of this class comprise the caprolactams.Suitable caprolactam bleach precursors are of the formula:9ll0 C"‘—'CH2——'CI-I2H l \R1—— c—N /\cnzwherein R1 is an alkyl, aryl, alkoxyaryl or alkaryl group containingfrom 6 to 12 carbon atoms. Preferred hydrophobic N-acyl caprolactambleach precursor materials are selected from benzoyl caprolactam,CA 02265899 l999-03- 16wo 98/13449 PCT/US97/1707717octanoyl caprolactam, nonanoyl caprolactam, decanoyl caprolactam,undecenoyl caprolactam, 3,5,5-trimethylhexanoyl caprolactam andmixtures thereof. A most preferred is nonanoyl caprolactam.Suitable valero lactams have the formula:cu, -—— c1-12wherein R1 is an alkyl, aryl, alkoxyaryl or alkaryl group containingfrom 6 to 12 carbon atoms. More preferably, R1 is selected fromphenyl, heptyl, octyl, nonyl, 2,4,4-trimethylpentyl, decenyl andmixtures thereof.Mixtures of any of the peroxyacid bleach precursor, herein beforedescribed, may also be used.Peo e ' ox 'dThe organic peroxyacid bleaching system may contain, in addition to,or as an alternative to, an organic peroxyacid bleach precursorcompound, a preformed hydrophobic organic peroxyacid , typically ata level of from 0.05% to 20% by weight, more preferably from 1% to10% by weight of the composition.A preferred class of hydrophobic organic peroxyacid compounds arethe amide substituted compounds of the following general formulae:R1——c——N—R2——c—ooH‘. I?o R5 0 orR1——N~—c~—R2——c——ooH' i! ,3éefib oCA 02265899 l999-03- 16WO 98/13449 PCT/US97l1707718wherein R1 is an aryl or alkaryl group with from about 1 to about 14carbon atoms, R2 is an alkylene, arylene, and alkarylene groupcontaining from about 1 to 14 carbon atoms, and R5 is H or an alkyl,aryl, or alkaryl group containing 1 to 10 carbon atoms. R1 preferablycontains from about 6 to 12 carbon atoms. R2“’preferably containsfrom about 4 to 8 carbon atoms. R1 may be straight chain or branchedalkyl, substituted aryl or alkylaryl containing branching, substitution,or both and may be sourced from either synthetic sources or naturalsources including for example, tallow fat. Analogous structuralvariations are permissible for R2. R2 can include alkyl, aryl, whereinsaid R2 may also contain halogen, nitrogen, sulphur and other typicalsubstituent groups or organic compounds. R5 is preferably H ormethyl. R1 and R5 should not contain more than 18 carbon atomstotal. Amide substituted bleach activator compounds of this type aredescribed in EP-A—0170386. Suitable examples of this class of agentsinclude (6-octylamino)-6-0xo-caproic acid, (6-nonylamino)-6-oxo-caproic acid, (6—decylamino)-6—oxo-caproic acid, magnesiummonoperoxyphthalate hexahydrate, the magnesium salt of metachloroperbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid anddiperoxydodecanedioic acid. Such bleaching agents are disclosed inU.S. 4,483,781, U.S. 4,634,551, EP 0,133,354, U.S. 4,412,934 andEP 0,170,386. A preferred hydrophobic preformed peroxyacid bleachcompound for the purpose of the invention is monononylamidoperoxycarboxylic acid.Other suitable organic peroxyacids include diperoxyalkanedioc acidshaving more than 7 carbon atoms, such as diperoxydodecanedioc acid,diperoxytetradecanedioc acid and diperoxyhexadecanedioc acid.Other suitable organic peroxyacids include diamino peroxyacids, whicharedisclosed in W0 95/ 03275, with the following general formula:0 o o oMOCR-(R1N)n—C (NR2)n' —R3—{R2N)m-—C (NR1)mv RCOOMwherein:CA 02265899 l999-03- 16W0 98/ 13449 PCT/US97/ 1707719R is selected from the group consisting of C1-C12 alkylene, C5—C12cycloalkylene, C5—C12 arylene and radical combinations thereof;R1 and R2 are independently selected from the group consisting of H,C1-C15 alkyl and C5—C12 aryl radicals and a radical that can form aC3-C1; ring together with R3 and both nitrogens; R3 is selected fromthe group consisting of C1—C12 allcylene, C5-C12 cycloalkylene andC5-C1; arylene radicals; n and 11' each are an integer chosen such thatthe sum thereof is 1; m and In‘ each are an integer chosen such that thesum thereof is 1; andM is selected from the group consisting of H, alkali metal, alkalineearth metal, ammonium, alkanolammonium cations and radicals andcombinations thereof.Other suitable organic peroxyacids are include the amido peroxyacidswhich are disclosed in W0 95/ 16673, with the following generalstructure:X—Ar-CO~ NY—R(Z)-CO—OOHin which X represents hydrogen or a compatible substituent, Ar is anaryl group, R represents (CH2)n in which n = 2 or 3, and Y and Zeach represent independently a substituent selected from hydrogen oran alkyl or aryl or alkaryl group or an aryl group substituted by acompatible substituent provided that at least one of Y and Z is nothydrogen if n = 3. The substituent X on the benzene nucleus ispreferably a hydrogen or a meta or para substituent, selected from thegroup comprising halogen, typically chlorine atom, or some other non-released non-interfering species such as an alkyl group, convenientlyup to C6 for example a methyl, ethyl or propyl group. Alternatively, Xcan represent a second amido-percarboxylic acid substituent offormula:-—CO—NY—R(Z)4CO—OOHin which R, Y, Z and n are as defined above.CA 02265899 l999-03- 16WO 98/13449 PCT/US97/1707720MOOC-R1CO-NR2-R3-NR4-CO—R5COOOMwherein Rlis selected from the group consisting of C1-C1; alkylene,C5-C1; cycloalkylene, C6—C12 arylene and radical combinationsthereof; RCationic polymersThe detergent composition or component thereof can compriseadditional polymeric cationic ethoxylated amine compounds withparticulate/ clay-soil removal/ anti-redeposition, selected from thegroup consisting of water—soluble cationic polymers. These polymerscomprise a polymer backbone, at least 2M groups and at least one L-Xgroup, wherein M is a cationic group attached to or integral with thebackbone; X is a nonionic group selected from the group consisting ofH, C1 -C4 alkyl or hydroxyalkyl ester or ether groups, and mixturesthereof; and L is a hydrophilic chain connecting groups M and X orconnecting X to the polymer backbone.The polymeric cationic ethoxylated amine compounds can be present indetergent compositions at a level of from 0.01% to 30% , morepreferably from 0.1% to 15%, most preferably from 0.2% to 3% byweight of the detergent composition.As used herein, the term "polymer backbone" refers to the polymericmoiety to which groups M and L-X are attached or are integral with.Included within this term are oligomer backbones (2 to 4 units), andtrue polymer backbones (5 or more units).As used herein, the term "attached to " means that the group is pendentfrom the polymer backbone, examples of such attachment beingrepresented by the following general structures A and B:CA 02265899 l999-03- 16W0 98/13449 ‘ PCT/US97/1707721M M LL X)|(A BAs used herein, the term "integral with" means that the group formspart of the polymer backbone, examples of which are represented bythe following general structures C and D:CAny polymer backbone can be used as long as the cationic polymerformed is water-soluble and has clay soil removal/anti-redepositionproperties. Suitable polymer backbones can be derived from thepolyurethanes, the polyesters, the polyethers, the polyamides, thepolyirnides and the like; the polyacrylates, the polyacrylamides, thepolyvinylethers, the polyethylenes, the polypropylenes and likepolyalkylenes, the polystyrenes and like polyalkarylenes, thepolyalkyleneamines, the polyalkyleneimines, the polyvinylamines, thepolyalylarnines, the polydiallylamines, the polyvinylpyridines, thepolyarninotriazoles, polyvinyl alcohol, the arninopolyureylenes, andmixtures thereof.M can be any compatible cationic group which comprises an N+(quarternary), positively charged center. The quarternary positivelycharged center can be represented by the following general structuresE and F:CA 02265899 l999-03- 16W0 98/13449 PCT/US97l1707722Particularly preferred M groups are those containing a quartemarycenter represented by general structure E. The cationic group ispreferably positioned close to or integral with the polymer backbone.The positive charge of the N''' centres is offset by the appropriatenumber of counter anions. Suitable counter anions include Cl’, Br,S032", S042‘, PO42’, MeOSO3' and the like. Particularly preferredcounter anions are C1‘ and Br.X can be a nonionic group selected from hydrogen (I-I), C1-C4 alkyl orhydroxyalkyl ester or ether groups, and mixtures thereof. Thepreferred ester or ether groups are the acetate ester and methyl ether,respectively; The particularly preferred nonionic groups are H and themethyl ether.The cationic polymers suitable for use in granular detergentcompositions or components thereof in accord with the presentinventions normally have a ratio of cationic groups M to nonionicgroups X of from about 1:1 to about 1:2. However, for example, byappropriate copolymerization of cationic, nonionic (i.e. containing thegroup L-X), and mixed cationic/nonionic monomers, the ratio ofcationic groups M to nonionic groups X can be varied. The ratio ofgroups M to groups X can usually range from about 2:1 to about 1:10.In preferred cationic polymers, the ratio is from about 1:1 to about1:5. The polymers formed from such copolymerization are typicallyrandom, i.e. the cationic, nonionic and mixed cationc/nonionicmonomers copolymerize in a nonrepeating sequence.CA 02265899 l999-03- 16W0 98/ 13449 PCT/US97/1707723The units which contain groups M and groups L—X can comprise 100%of the cationic polymers of the present invention. However, inclusionof other units (preferably nonionic) in the polymers is also permissible.Examples of other units include acrylamides, vinyl ethers and thosecontaining unquaternized tertiary amine groups (M1) containing an Ncentre. These other units can comprise from 0% to about 90% of thepolymer (from about 10% to 100% of the polymer being unitscontaining M and L-X groups, including M1-L-X groups). Normally,these other units comprise from 0% to about 50% of the polymer (fromabout 50% to 100% of the polymer being units containing M and L-Xgroups) .The number of groups M and L-X each usually ranges from about 2 toabout 200. Typically the number of groups M and L—X are each fromabout 3 to about 100. Preferably, the number of groups M and L-Xare each from about 3 to about 40.Other than moieties for connecting groups M and X, or for attachmentto the polymer backbone, hydrophilic chain L usually consists entirelyof the polyoxyalkylene moiety -[(R’O),,,(CH2CH2O),,]-. The moieties-(R'O),,,— and -(CH2CH20),,- of the polyoxyalkylene moiety can bemixed together, or preferably form blocks of -(R'O),,,- and -(CH2CH2O),,— moieties. R‘ is preferably C3H5 (propylene); m ispreferably from O to about 5, and most preferably 0; i.e. thepolyoxyalkylene moiety consists entirely of the moiety -(CI-I2CH20),,-.The moiety —(CH2CH2O),,- preferably comprises at least about 85% byweight of the polyoxyalkylene moiety, and most preferably 100% byweight (In is 0). For the moiety -(CH2CH2O),,-, n is usually fromabout 3 to about 100. Preferably, n is from about 12 to about 42.A plurality (2 or more) of moieties -L—X can also be hooked togetherand attached to group M or to the polymer backbone, examples ofwhich are represented by the following general structures G and H:CA 02265899 l999-03- 16W0 98/13449 I-CT/Us97/1707724><~ t-*--xG HStructures such as G and H can be formed, for example, by reactingglycidol with group M or with the polymer backbone, and ethoxylatingthe subsequently formed hydroxy groups.Representative classes of cationic polymers of the present invention areas follows:A. Polyurethane, Polyester, Polyether, Polyamide or like Polymers.One class of suitable cationic polymers are derived frompolyurethanes, polyesters, polyethers, polyarnides and the like. Thesepolymers comprise units selected from those having formulas I, II andIII:CA 02265899 l999-03- 16wo 98ll3449 PCT/US97l1707725R4(A1_R1__A1)x__R2_.N+__R3XiR5)k—-[<c3H6o)m<cH2CH20)n1-x$R62)k(A1--R1— A1)x-R2 —~N+—R3 11yR7 IIIi(A1~~R1—A1)x——R2——-c;~» R3IIiR5)k—— [(C3H6O)m(CH2CH2O)n] —— xwherein A1 is. | 0 H :2 H H HX is 0 or 1; R is H or C1-C4 alkyl or hydroxyalkyl; R1 is C2-C12alkylene, hydroxyalkylene, alkenylene, cycloalkylene, arylene oralkarylene, or a C2-C3 oxyalkylene moiety having from 2 to abut 20oxyalkylene units provided that no 0-0 or O-N bonds are formed withA1; when x is 1, R2 is -R5- except when A1 isCA 02265899 l999-03- 16W0 98/13449 PCT/US97l17077__C__,or is -(OR3),- or -OR5- provided that no 0-0 or N—O bonds areformed with A1, and R3 is -R5- except when A1 isor is -(R30)-y or -R5O- provided that no 0-0 or O-N bonds areformed with A1; when x is 0, R2 is——(oR8)y—,-0115-,——ooR5—,—ocR5——,—~ot:R5,1. H :5o 0 0—-I§I(:,R5——,-—1§I1C3OR5—-,--("ZITIR5-F, or —~—o$:1T1R5~—,1:6 no ()1: 61‘;and R3 is -115-; R4 is C1-C4 alkyl or hydroxyalkyl, or the moiety -(R5),,—[(C3H5O),,,(CH2CH2O),,]-X; R5 is C1-C12 alkylene,hydroxyalkylene, alkenylene, arylene, or alkarylene; each R5 is C1-C4 alkyl or hydroxyalkyl, or the moiety —(CH2),-A2-(CH2)s-, whereinA2 is -0- or -CH2-; R7 is H or R4; R8 is C2-C3 alkylene orhydroxyalkylene; X is H,OH__CR9,-R9 or a mixture thereof, wherein R9 is C1-C4 alkyl or hydoxyalkyl;k is 0 or 1; In and n are numbers such that the moiety —(CH2CH20),,-comprises at least‘ about 85 % by weight of the moiety -[(C3H5O),,,(CH2CH20),,]-; In is from O to about 5; n is at least aboutCA 02265899 l999-03- 16W0 98113449 PCT/US97/17077273; ris 1 or2, sis 1or2, andr + sis3or4; yisfrom2toabout20;the number of u, v and w are such that there are at least 2 N+ centersand at least 2 X groups.In the above formulas, A1 is preferably9 0‘.2 itITC 01' CN ;lR RA2 is preferably -0-; x is preferably 1; and R is preferably H. R1can be linear (e.g. -CH2-CH2-CH2-,CH3——CH2—-CH—) or branched (e.g.—~cH2—cH—~—,—~cH2~——c;H——)E CH /\ 3 O\/ \/alkylene, hydroxyalkylene, alkenylene, cycloalkylene, alkarylene oroxyalkylene; when R1 is a C2-C3 oxyalkylene moiety, the number ofoxyalkylene units is preferably from about 2 to about 12; R1 ispreferably C2-C5 alkylene or phenylene, and most preferably C2-C5alkylene (e.g. ethylene, propylene, hexamethylene). R2 is preferably -OR5- or —(oR8),—; R3 is preferably -R50- or -(OR3),-; R4 and R6are preferably methyl. Like R1, R5 can be linear or branched, and ispreferably C2-C3 alkylene; R7 is preferably H or C1-C3 alkyl; R3 ispreferably ethylene; R9 is preferably methyl; X is preferably H ormethyl; k is preferably 0; m is preferably 0, r and s are eachpreferably 2; y is preferably from 2 to about 12.In the above formulas, n is preferably at least about 6 when thenumber of N‘‘' centers and X groups is 2 or 3; n is most preferably atleast about 12, with a typical range of about 12 to about 42 for allranges of u + v + w. For homopolymers (v and w are 0), u isCA 02265899 l999-03- 16W0 98/13449 PCTlUS97l1707728preferably from about 3 to about 20. For random compolymers (u is atleast 1 or preferably 0), V and w are each preferably from about 3 toabout 40.B. Polyacrylate, Polyacrylamide, Polyvinylether orLike PolymersAnother class of suitable cationic polymers are derived frompolyacrylates, polyacrylamides, polyvinylethers and the like. Thesepolymers comprise units selected from those having formulas IV, Vand VI.CA 02265899 l999-03- 16wo 98/13449 PCT/US97/1707729-1-1+11(A1)-/ J(R2)j(R3)2 -N+ —- (R2)k — [(C3H6O)m(CH2CH20)n] ~— xIV+51% Jptur(41); 11 w‘2 2 /(A )jN*—(R4)3V VI0 CI) 0 O 0li ii ii ifwheremA1is———o—,—-171c—,~—N O-—~,—CNC—-,-—CN——,I i 3R R R R(‘Q o o ('3 o! 5% 11 5 E—ocN— ———oc—,—oco-,——co——,or -NéN—_;5 . 5R R RR is H or C1-C4 alkyl or hydroxyalkyl; R1 is substituted C2-C12alkylene, hydroxyalkylene, alkenylene, arylene or alkarylene, or C2-C3 oxyalkylene; each R2 is C1—C12 alkylene, hydroxyalkylene,alkenylene, arylene or alkarylene; each R3 is C1-C4 alkyl orhydroxyalkyl, the moiety -(R2)k-[(C3H5O),,,(CH2CH2O),,]-X, ortogether form the moiety -(CH2),-A2-(CH2)s-, wherein A2 is -0- or -CH2-; each R4 is C1-C4 alkyl or hydroxyalkyl, or two R4 togetherform the moiety -(CH2),-A2-(CH2);-; x is H,CA 02265899 l999-03- 16“'0 93/134” PCT/US97/1707730O-R5 or mixture thereof, wherein R5 is C1-C4 alkyl or hydroxalkyl; jis 1 or 0; k is 1 or O; m and n are numbers such that the moiety -(CH2CH2O),,- comprises at least about 85 % by weight of the moiety -[(C3H5O),,,(CH2CH2O),,]-; m is from 0 to about 5; n is at least about3; ris 1 or2, sis 1 or2andr + sis3or4; thenumberofu, vandw are such that there are at least 2N+ centres and at least 2 X groups.In the above formulas, A1 is preferably9 at1!CN , CO or —-O—-;lRA2 is preferably -0-; R is preferably H. R1 can be linear(e.g. — CH2 —- CH“- CH2 — , ——CH2CH —) or/\\\//E9H3branched (e. g. —— CH2 —— —— , — CHZCH —- ,i ECH3 ‘/W(EH3 \'©——CH2C|?——, —CH2C-—)1ICHE2\/CA 02265899 l999-03- 16wo 98/13449 PCT/US97l170773 1substituted alkylene, hydroxyalkylene, allcenylene, alkarylene oroxyalkylene; R1 is preferably substituted C2-C6 alkylene orsubstituted C2-C3 oxyalkylene, and most preferablyCH3——cH2c;H—or———cH2-—C——.l %Each R2 is preferably C2-C3 alkylene, each R3 and R4 are preferablymethyl; R5 is preferably methyl; X is preferably H or methyl; j ispreferably 1; k is preferably 0; m is preferably 0; r and s are eachpreferably 2.In the above formulas, n, u, v and w can be varied according to then,u, v and w for the polyurethane and like polymers.C. Polyalkyleneamine, Polyalkyleneimine or like polymers.Another class of suitable cationic polymers are derived frompolyalkyleneamines, polyalkyleneimines and the like. These polymerscomprise units selected from those having formulas VII and VIII andIX.CA 02265899 l999-03- 16W0 98/ 13449 PCT/US97/1707732(R2)d(R1__M. _t xfR2’dI y{R3)k—— [(C3H6O)m(CH2CH2O)n) — x(.R2)d _.___ M!"i Z{R3)k - [(C3H6O)m(CH2CH2O)n] ~— Xwherein R1 is C2—C12’a1kylene, hydroxyalkylene, alkenylene,cycloalkylene, arylene or alkarylene, or a C2-C3 oxyalkylene moietyhaving from 2 to about 20 oxyalkylene units provided that no O—Nbonds are formed; each R2 is C1-C4 alkyl or hydroxyalkyl, or themoiety -(R3)k-[(C3H5O),,,(CH2CH2O),,]-X; R3 is C1-C12 alkylene,hydroxyallcylene, alkenylene, arylene or alkarylene; M‘ is an N+ orN centre; X is H,__ FR4,6-R4 or mixture thereof, wherein R4 is C1-C4 alkyl or hydroxyalkyl; dis 1 when M‘ is N+ and is 0 when M‘ is N; e is 2 when M‘ is N+CA 02265899 l999-03- 16WO 98113449 PCT/US97l1707733and is 1 when M’ is N; k is 1 or 0; m and n are numbers such that themoiety-(CH2CH2O),,- comprises at least about 85% by weight of the moiety-[(C3H6O),,,(CH2CH2O),,]-; m is from O to about 5; n is at leastabout 3; the number of x, y and z are such that there are at least 2M’groups, at least 2N+ centres and at least 2 X groups.In the above formulas, R1 can be varied like R1 of the polyuretheneand like polymers; each R2 is preferably methyl or the moiety -(R3)k-[(C3H5O),,,(CH2CH2O),,]-X; R3 is preferably C2-C3 alkylene; R4 ispreferably methyl; X is preferably H; k is preferably 0; m ispreferably 0.In the above formulas, n is preferably at least about 6 when thenumber of M’ and X groups is 2 or 3; n is most preferably at leastabout 12, with a typical range of from about 12 to about 42 for allranges of x + y + 2. Typically, x + y + 2 is from 2 to about 40 andpreferably from 2 to about 20. For short chain length polymers, x + y+ 2 can range from 2 to 9 with from 2 to 9 N + centres and from 2 to11 X groups. For long chain length polymers, x + y + z is at least10, with a preferred range of from 10 to about 42. For the short andlong chain length polymers, the M’ groups are typically a mixture offrom about 50 to 100% N+ centres and from 0 to about 50% Ncentres.Preferred cationic polymers within this class are derived from the C2-C3 polyalkyleneamines (x + y + z is from 2 to 9) andpolyalkyleneimines (x + y + z is at least 10, preferably from 10 toabout 42). Particularly preferred cationic polyalkyleneamines andpolyalkyleneimines are the cationic polyethyleneamines (PEA's) andpolyethyleneimines (PEI's). These preferred cationic polymerscomprise units having the general formula:CA 02265899 l999-03- 16WO 98113449 PCT/US97/1707734(R2), (R2),[M-]a— — [CH2 ——cH2M']X‘<R2>d (R2),~—— [CH2CH2M']y——~ ~— [CH2CH2M']z,1 :(CH2CH2O)n—X [(cH2cH2o)n~x]2wherein R2 (preferably methyl), M‘, X, (1, x, y, z and n are defined asbefore; a is 1 or 0.Prior to ethoxylation, the PEAS used in preparing cationic polymers ofthe present invention have the following general formula:[H2N]a—~ -—[CH2CH2I§I]x* e~*[CH2CH2N]y-—- ~%CH2CH2NH2]Z‘ Hwherein x + y + z is from 2 to 9, and a is O or 1 (molecular weight offrom about 100 to about 400). Each hydrogen atom attached to eachnitrogen atom represents an active site for subsequent ethoxylation.For preferred PEAS, x + y + z is from about 3 to about 7 (molecularweight is from about 140 to about 310). These PEA's can be obtainedby reactions involving ammonia and ethylene dichloride, followed byfractional distillation. The common PEA's obtained aretriethylenetetramine (TETA) and tetraethylenepentamine (TEPA).Above the pentamines, i.e., the hexamines, heptamines, octamines andpossibly nonamines, the cogenerically derived mixture does not appearto separate by distillation and can include other materials such as cyclicamines and particularly piperazines. There can also be present cyclicamines with side chains in which nitrogen atoms appear. See US Pat.No. 2,792,372 to Dickson, issues May 14, 1957, which describes thepreparation of PEAs.CA 02265899 l999-03- 16W0 98/ 13449 PCT/US97/ 1707735The minimum degree of ethoxylation required for preferred clay soilremoval/anti-redeposition performance can vary depending upon thenumber of units in the PEA. Where y + z is 2 or 3, n is preferably atleast about 6. Where y + 2 is from 4 to 9, suitable benefits areachieved when n is at least about 3. For preferred cationic PEAS, n isat least about 12, with a typical range of about 12 to about 42.The PEIs used in preparing the polymers of the present invention havea molecular weight of at least about 440 prior to ethoxylation, whichrepresents at least about 10 units. Preferred PEIs used in preparingthese polymers have a molecular weight of from about 600 to about1800. The polymer backbone of these PEIs can be represented by thegeneral formula:Hwherein the sum of x, y, and z represents a number of sufficientmagnitude to yield a polymer having the molecular weights previouslyspecified. Although linear polymer backbones are possible, branchchains can also occur. The relative proportions of primary, secondaryand tertiary amine groups present in the polymer can vary, dependingon the manner of preparation. The distribution of amine groups istypically as follows:‘—’” —' 3 0%-"" CH2CH2 — NH —— 40%4”‘ T N ‘——" 30%Each hydrogen atom attached to each nitrogen atom of the PEIrepresents an active site for subsequent ethoxylation. These PEIs canCA 02265899 l999-03- 16W0 98/ 13449 PCT/US97/1707736be prepared, for example, by polymerizing ethyleneimine in thepresence of a catalyst such as carbon dioxide, sodium bisulfite, sulfuricacid, hydrogen peroxide, hydrochloric acid, acetic acid, etc. Specificmethods for preparing PEIs are disclosed in US Pat. No. 2,182,306 toUlrich et al., issued Dec. 5, 1939; US Pat No. 3,033,746 to Mayle etal., issued May 8, 1962; US Pat. No. 2,208,095 to Esselmann et al.,issued July 16, 1940; US Pat. No. 2,806,839 to Crowther, issuedSept. 17, 1957; and US Pat. No. 2,533,696 to Wilson, issued May21, 1951 (all herein incorporated by reference).As defined in the preceding formulas, n is at least about 3 for thecationic PEIs. However, it should be noted that the minimum degreeof ethoxylation required for suitable clay soil removal/anti-redepositionperformance can increase as the molecular weight of the PEI increases,especially much beyond about 1800. Also, the degree of ethoxyalationfor preferred polymers increases as the molecular weight of the PEIincreases. For PEIS having a molecular weight of at least about 600, nis preferably at least about 12, with a typical range of from about 12 toabout 42. For PEIs having a molecular weight of at least 1800, n ispreferably at least about 24, with a typical range of from about 24 toabout 42.D. Diallylamine PolymersAnother class of suitable cationic polymers are those derived from thediallylamines. These polymers comprise units selected from thosehaving formulas X and XI:CA 02265899 l999-03- 16W0 98’ 13449 PCT/US97/1707737(CH2) (CH2 —-—’\_‘(CH2)x_/X\/\r\/ uR1 (R2)k--[(C3H6O)m(CH2CH2O)n]—-X(CH2)’\—«=H2>»«~—/1/\(R3);wherein R1 is C1-C4 alkyl or hydroxyalkyl, or the moiety -(R2)k-[(C3H5O),,,(CH2CH2O),,]-X; R2 is C1-C1; alkylene,hydroxyalkylene, alkylene, arylene or alkarylene; each R3 is C1-C4alkyl or hydroxyalkyl, or together form the moiety —(CH2),-A-(CH2),-,wherein A is -0- or —CH2-; X is H,__?R4,‘E0-R4 or mixture thereof, wherein R4 is C1-C4 alkyl or hydroxyalkyl; kis 1 or O; In and n are numbers such that the moiety -(CH2CH2O),,-comprises at least about 85 % by weight of the moiety -[(C3H5O),,,(CH2CH2O),,]-; m is from 0 to about 5; n is at least about3; ris1or2,sis1or2,andr + sis3or4; xis1orO;yis1whenx is O and 0 when x is 1; the number of u .and v are such that there areat least 2N+ centres and at least 2 X groups.CA 02265899 l999-03- 16W0 98/ 13449 PCT /US97/1707738In the above formulas, A is preferably -0-; R1 is preferably methyl;each R2 is preferably C2-C3 alkylene; each R3 is preferably methyl;R4 is preferably methyl; X is preferably H; k is preferably O; In ispreferably 0; r and s are each preferably 2.In the above formulas, n is preferably at least about 6 when thenumber of N+ centres and X groups are each 2 or 3, n is preferably atleast 12, with a typical range of from about 12 to about 42 for all rangeof u + v. Typically, v is 0, and u is from 2 to about 40, andpreferably from 2 to about 20.Additional detergent componentsThe detergent compositions or components thereof in accord with theinvention may also contain additional detergent components. Theprecise nature of these additional components, and levels ofincorporation thereof will depend on the physical form of thecomposition or component, and the precise nature of the washingoperation for which it is to be used.The compositions or components thereof, of the invention preferablycontain one or more additional detergent components selected fromadditional surfactants, additional bleaches, bleach catalysts, alkalinitysystems, builders, organic polymeric compounds, enzymes, sudssuppressors, lime soap dispersants, additional soil suspension and anti-redeposition agents soil releasing agents, perfumes and corrosioninhibitors.Additional surfactantThe detergent compositions or components thereof in accord with theinvention preferably contain an additional surfactant selected fromanionic, nonionic, cationic, ampholytic, amphoteric and zwitterionicsurfactants and mixtures thereof.CA 02265899 1999- 03 - 16WO 93/13449 PCT/US97/1707739A typical listing of anionic, nonionic, ampholytic, and zwitterionicclasses, and species of these surfactants, is given in U.S.P. 3,929,678issued to Laughlin and Heuring on December 30, 1975. Furtherexamples are given in "Surface Active Agents and Detergents" (Vol. Iand II by Schwartz, Perry and Berch). A list of suitable cationicsurfactants is given in U.S.P. 4,259,217 issued to Murphy on March31, 1981.Where present, ampholytic, amphoteric and zwitteronic surfactants aregenerally used in combination with one or more anionic and/ornonionic surfactants.Anionic surfactantThe detergent compositions or compositions thereof in accord with thepresent invention preferably comprise an additional anionic surfactant.Essentially any anionic surfactants useful for detersive purposes can becomprised in the detergent composition. These can include salts(including, for example, sodium, potassium, ammonium, andsubstituted ammonium salts such as mono—, di- and triethanolaminesalts) of the anionic sulfate, sulfonate, carboxylate and sarcosinatesurfactants. Anionic sulfate surfactants are preferred.Other anionic surfactants include the isethionates such as the acylisethionates, N-acyl taurates, fatty acid amides of methyl tauride, alkylsuccinates and sulfosuccinates, monoesters of sulfosuccinate (especiallysaturated and unsaturated C12-C18 monoesters) diesters ofsulfosuccinate (especially saturated and unsaturated C6-C14 diesters),N-acyl sarcosinates. Resin acids and hydrogenated resin acids are alsosuitable, such as rosin, hydrogenated rosin, and resin acids andhydrogenated resin acids present in or derived from tallow oil.Anionic sulfate surfactantAnionic sulfate surfactants suitable for use herein include the linearand branched primary and secondary alkyl sulfates, alkylethoxysulfates, fatty oleoyl glycerol sulfates, alkyl phenol ethyleneCA 02265899 l999-03- 16W0 98/134419 PCT/US97/1707740NOT FURNISHED AT TIME OF PUBLICATIONCA 02265899 l999-03- 16W0 98/ 13449 PCT/US97/1707741soaps (‘alkyl carboxyls'), especially certain secondary soaps asdescribed herein.Suitable alkyl ethoxy carboxylates include those with the formulaRO(CH2CH20)x CH2CO0'M 4' wherein R is a C6 to‘C1g alkyl group,x ranges from O to 10, and the ethoxylate distribution is such that, ona weight basis, the amount of material where x is O is less than 20 %and M is a cation. Suitable alkyl polyethoxy polycarboxylatesurfactants include those having the formula R0-(CHR1-CHR2-O)-R3wherein R is a C5 to C13 alkyl group, x is from 1 to 25, R1 and R2are selected from the group consisting of hydrogen, methyl acidradical, succinic acid radical, hydroxysuccinic acid radical, andmixtures thereof, and R3 is selected from the group consisting ofhydrogen, substituted or unsubstituted hydrocarbon having between 1and 8 carbon atoms, and mixtures thereof.Suitable soap surfactants include the secondary soap surfactants whichcontain a carboxyl unit connected to a secondary carbon. Preferredsecondary soap surfactants for use herein are water-soluble membersselected from the group consisting of the water-soluble salts of 2-methyl-1-undecanoic acid, 2-ethyl-1-decanoic acid, 2-propyl-1-nonanoic acid, 2—butyl-1-octanoic acid and 2—pentyl—1—heptanoic acid.Certain soaps may also be included as suds suppressors.Alkali metal sarcosinate surfactantOther suitable anionic surfactants are the alkali metal sarcosinates offormula R-CON (R1) CH2 COOM, wherein R is a C5-C17 linear orbranched alkyl or alkenyl group, R1 is a C1-C4 alkyl group and M isan alkali metal ion. Preferred examples are the myristyl and oleoylmethyl sarcosinates in the form of their sodium salts.Alkoxylated nonionic surfactantEssentially any alkoxylated nonionic surfactants are suitable herein.The ethoxylated and propoxylated nonionic surfactants are preferred.CA 02265899 l999-03- 16W0 98/ 13449 PCT/US97/ 1707742Preferred alkoxylated surfactants can be selected from the classes ofthe nonionic condensates of alkyl phenols, nonionic ethoxylatedalcohols, nonionic ethoxylated/propoxylated fatty alcohols, nonionicethoxylate/propoxylate condensates with propylene glycol, and thenonionic ethoxylate condensation products with propyleneoxide/ ethylene diamine adducts.Nonionic alkoxylated alcohol surfactantThe condensation products of aliphatic alcohols with from 1 to 25moles of alkylene oxide, particularly ethylene oxide and/or propyleneoxide, are suitable for use herein. The alkyl chain of the aliphaticalcohol can either be straight or branched, primary or secondary, andgenerally contains from 6 to 22 carbon atoms. Particularly preferredare the condensation products of alcohols having an alkyl groupcontaining from 8 to 20 carbon atoms with from 2 to 10 moles ofethylene oxide per mole of alcohol.Nonionic polyhydroxy fatty acid amide surfactantPolyhydroxy fatty acid amides suitable for use herein are those havingthe structural formula R2coNR1z wherein ; R1 is H, C1-C4hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl, ethoxy, propoxy, ora mixture thereof, preferable Cl-C4 alkyl, more preferably C1 or C2alkyl, most preferably C1 alkyl (i.e., methyl); and R2 is a C5—C31hydrocarbyl, preferably straight-chain C5-C19 alkyl or alkenyl, morepreferably straight-chain C9—C17 alkyl or alkenyl, most preferablystraight-chain C11—C17 alkyl or alkenyl, or mixture thereof; and Z is apolyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least3 hydroxyls directly connected to the chain, or an alkoxylatedderivative (preferably ethoxylated or propoxylated) thereof. Zpreferably will be derived from a reducing sugar in a reductiveamination reaction; more preferably Z is a glycityl.Nonionic fat_ty acid amide surfactantCA 02265899 l999-03- 16W0 98/13449 PCT /US97/1707743Suitable fatty acid amide surfactants include those having the formula:R6CON(R7)2 wherein R6 is an alkyl group containing from 7 to 21 ,preferably from 9 to 17 carbon atoms and each R7 is selected from thegroup consisting of hydrogen, C1-C4 alkyl, C1-C4 hydroxyalkyl, and —(C2H4O)xH, where x is in the range of from 1 to 3.Nonionic allgylpolysaccharide surfactantSuitable alkylpolysaccharides for use herein are disclosed in U.S.Patent 4,565,647, Llenado, issued January 21, 1986, having ahydrophobic group containing from 6 to 30 carbon atoms and apolysaccharide, e.g., a polyglycoside, hydrophilic group containingfrom 1.3 to 10 saccharide units.Preferred alkylpolyglycosides have the formulaR20(CnH2nO)t(g1Y°05Y1)xwherein R2 is selected from the group consisting of alkyl, alkylphenyl,hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which thealkyl groups contain from 10 to 18 carbon atoms; 11 is 2 or 3; t is fromO to 10, and x is from 1.3 to 8. The glycosyl is preferably derivedfrom glucose.Amphoteric surfactantSuitable amphoteric surfactants for use herein include the amine oxidesurfactants and the alkyl amphocarboxylic acids.Suitable amine oxides include those compounds having the formulaR3(OR4)xN0(R5)2 wherein R3 is selected from an alkyl,hydroxyalkyl, acylamidopropoyl and alkyl phenyl group, or mixturesthereof, containing from 8 to 26 carbon atoms; R4 is an allcylene orhydroxyalkylene group containing from 2 to 3 carbon atoms, ormixtures thereof; x is from O to 5, preferably from O to 3; and each R5is an alkyl or hydroxyalkyl group containing from 1 to 3, or apolyethylene oxide group containing from 1 to 3 ethylene oxideCA 02265899 l999-03- 16WO 98113449 PCT/US97/1707744groups. Preferred are C10-C13 alkyl dimethylamine oxide, and C10_1gacylamido alkyl dimethylamine oxide.A suitable example of an alkyl aphodicarboxylic acid is Mirano1(TM)C2M Conc. manufactured by Miranol, Inc., Dayton, NJ.Zwitterionic surfactantZwitterionic surfactants can also be incorporated into the detergentcompositions or components thereof in accord with the invention.These surfactants can be broadly described as derivatives of secondaryand tertiary amines, derivatives of heterocyclic secondary and tertiaryamines, or derivatives of quaternary ammonium, quaternaryphosphonium or tertiary sulfonium compounds. Betaine and sultainesurfactants are exemplary zwitterionic surfactants for use herein.Suitable betaines are those compounds having the formulaR(R')2N +R2COO' wherein R is a C6-C13 hydrocarbyl group, eachR1 is typically C1-C3 alkyl, and R2 is a C1-C5 hydrocarbyl group.Preferred betaines are C12_1g dimethyl-ammonio hexanoate and theC10-1g acylamidopropane (or ethane) dimethyl (or diethyl) betaines.Complex betaine surfactants are also suitable for use herein.Cationic surfactantsSuitable cationic surfactants to be used in the detergent compositions orcomponents thereof herein include the quaternary ammoniumsurfactants selected from mono C5—C16, preferably C6-C10 N-alkyl oralkenyl ammonium surfactants wherein the remaining N positions aresubstituted by methyl, hydroxyethyl or hydroxypropyl groups.Another suitable group of cationic surfactants which can be used in thedetergent compositions or components thereof herein are cationic estersurfactants.The cationic ester surfactant is a, preferably water dispersible,compound having surfactant properties comprising at least one ester(i.e. —COO-) linkage and at least one cationically charged group.CA 02265899 l999-03- 16W0 98/ 13449 PCT/US97/ 1707745Suitable cationic ester surfactants, including choline ester surfactants,have for example been disclosed in US Patents No.s 4228042, 4239660and 4260529.In one preferred aspect the ester linkage and cationically charged groupare separated from each other in the surfactant molecule by a spacergroup consisting of a chain comprising at least three atoms (i.e. ofthree atoms chain length), preferably from three to eight atoms, morepreferably from three to five atoms, most preferably three atoms. Theatoms forming the spacer group chain are selected from the groupconsisting of carbon, nitrogen and oxygen atoms and any mixturesthereof, with the proviso that any nitrogen or oxygen atom in saidchain connects only with carbon atoms in the chain. Thus spacergroups having, for example, -O-O- (i.e. peroxide), -N-N—, and -N—O—linkages are excluded, whilst spacer groups having, for example -CH2-O- CH2— and -CH2—NH—CH2- linkages are included. In a preferredaspect the spacer group chain comprises only carbon atoms, mostpreferably the chain is a hydrocarbyl chain.Water-soluble builder compoundThe detergent compositions or components thereof in accord with thepresent invention preferably contain a water-soluble builder compound,typically present in detergent compositions at a level of from 1% to80% by weight, preferably from 10% to 70% by weight, mostpreferably from 20% to 60% by weight of the composition.Suitable water-soluble builder compounds include the water solublemonomeric polycarboxylates, or their acid forms, homo orcopolymeric polycarboxylic acids or their salts in which thepolycarboxylic acid comprises at least two carboxylic radicalsseparated from each other by not more that two carbon atoms, borates,phosphates, and mixtures of any of the foregoing.CA 02265899 l999-03- 16WO 98/13449 PCT/US97/1707746The carboxylate or polycarboxylate builder can be momomeric oroligomeric in type although monomeric polycarboxylates are generallypreferred for reasons of cost and performance.Suitable carboxylates containing one carboxy group include the watersoluble salts of lactic acid, glycolic acid and ether derivatives thereof.Polycarboxylates containing two carboxy groups include the water-soluble salts of succinic acid, malonic acid, (ethylenedioxy) diaceticacid, maleic acid, diglycolic acid, tartaric acid, tartronic acid andfumaric acid, as well as the ether carboxylates and the sulfinylcarboxylates. Polycarboxylates containing three carboxy groupsinclude, in particular, water-soluble citrates, aconitrates andcitraconates as well as succinate derivatives such as thecarboxymethyloxysuccinates described in British Patent No. 1,379,241,lactoxysuccinates described in British Patent No. 1,389,732, andaminosuccinates described in Netherlands Application 7205873, andthe oxypolycarboxylate materials such as 2-oxa-1,1,3-propanetricarboxylates described in British Patent No. 1,387,447.Polycarboxylates containing four carboxy groups includeoxydisuccinates disclosed in British Patent No. 1,261,829, 1,l,2,2—ethane tetracarboxylates, 1,1,3,3-propane tetracarboxylates and1,1,2,3—propane tetracarboxylates. Polycarboxylates containing sulfosubstituents include the sulfosuccinate derivatives disclosed in BritishPatent Nos. 1,398,421 and 1,398,422 and in U.S. Patent No.3,936,448, and the sulfonated pyrolysed citrates described in BritishPatent No. 1,439,000. Preferred polycarboxylates arehydroxycarboxylates containing up to three carboxy groups permolecule, more particularly citrates.The parent acids of the monomeric or oligomeric polycarboxylatechelating agents or mixtures thereof with their salts, e.g. citric acid orcitrate/citric acid mixtures are also contemplated as useful buildercomponents.CA 02265899 l999-03- 16WO 98/13449 PCT/US97/1707747Borate builders, as well as builders containing borate—forrningmaterials that can produce borate under detergent storage or washconditions are useful water-soluble builders herein.Suitable examples of water-soluble phosphate builders are the alkalimetal tripolyphosphates, sodium, potassium and ammoniumpyrophosphate, sodium and potassium and ammonium pyrophosphate,sodium and potassium orthophosphate, sodium polymeta/phosphate inwhich the degree of polymerization ranges from about 6 to 21, andsalts of phytic acid.Partially soluble or insoluble builder compoundThe detergent compositions or compositions thereof in accord with thepresent invention may contain a partially soluble or insoluble buildercompound, typically present in detergent compositions at a level offrom 1% to 80% by weight, preferably from 10% to 70% by weight,most preferably from 20% to 60% weight of the composition.Examples of largely water insoluble builders include the sodiumaluminosilicates.Suitable aluminosilicate zeolites have the unit cell formulaNaZ[(A1O2)z(SiO2)y]. xH2O wherein z and y are at least 6; the molarratio of z to y is from 1.0 to 0.5 and x is at least 5, preferably from 7.5to 276, more preferably from 10 to 264. The aluminosilicate materialare in hydrated form and are preferably crystalline, containing from10% to 28%, more preferably from 18% to 22% water in bound form.The aluminosilicate zeolites can be naturally occurring materials, butare preferably synthetically derived. Synthetic crystallinealuminosilicate ion exchange materials are available under thedesignations Zeolite A, Zeolite B, Zeolite P, Zeolite X, Zeolite HS andmixtures thereof. Zeolite A has the formulaNa 12 [A102) 12 (Si02)12]. xH20CA 02265899 l999-03- 16W0 98/125449 PCT/US97/ 1707748wherein x is from 20 to 30, especially 27. Zeolite X has the formulaNags [(A102)s6(SiO2)1o6]. 276 H20-Another preferred aluminosilicate zeolite is zeolite MAP builder.The zeolite MAP can be present at a level of from 1% to 80% ,more preferably from 15% to 40% by weight of the compositions.Zeolite MAP is described in EP 38407OA (Unilever). It isdefined as an alkali metal a1umino—si1icate of the zeolite P typehaving a silicon to aluminium ratio not greater than 1.33,preferably within the range from 0.9 to 1.33 and more preferablywithin the range of from 0.9 to 1.2.Of particular interest is zeolite MAP having a silicon toaluminium ratio not greater than 1.15 and, more particularly, notgreater than 1.07.In a preferred aspect the zeolite MAP detergent builder has aparticle size, expressed as a d5() value of from 1.0 to 10.0micrometres, more preferably from 2.0 to 7.0 micrometres, mostpreferably from 2.5 to 5.0 micrometres.The d5() value indicates that 50% by weight of the particles havea diameter smaller than that figure. The particle size may, inparticular be determined by conventional analytical techniquessuch as microscopic determination using a scanning electronmicroscope or by means of a laser granulometer. Other methodsof establishing d50 values are disclosed in EP 38407OA.Heavy metal ion seguestrantThe detergent compositions of the invention preferably contain as anoptional component a heavy metal ion sequestrant. By heavy metal ionsequestrant it is meant herein components which act to sequester(chelate) heavy metal ions. These components may also have calciumand magnesium chelation capacity, but preferentially they showCA 02265899 l999-03- 16wo 98/13449 PCT/US97/1707749selectivity to binding heavy metal ions such as iron, manganese andcopper.Heavy metal ion sequestrants are generally present at a level of from0.005% to 20%, preferably from 0.1% to 10%, more preferably from0.25% to 7.5% and most preferably from 0.5 % to 5% by weight of thecompositions.Suitable heavy metal ion sequestrants for use herein include organicphosphonates, such as the amino alkylene poly (alkylenephosphonates), alkali metal ethane 1-hydroxy disphosphonates andnitrilo trimethylene phosphonates.Preferred among the above species are diethylene triamine penta(methylene phosphonate), ethylene diamine tri (methylenephosphonate) hexamethylene diamine tetra (methylene phosphonate)and hydroxy-ethylene 1,1 diphosphonate.Other suitable heavy metal ion sequestrant for use herein includenitrilotriacetic acid and polyaminocarboxylic acids such asethylenediaminotetracetic acid, ethylenetriamine pentacetic acid,ethylenediamine disuccinic acid, ethylenediamine diglutaric acid, 2-hydroxypropylenediamine disuccinic acid or any salts thereof.Especially preferred is ethylenediamine-N,N'-disuccinic acid (EDDS)or the alkali metal, alkaline earth metal, ammonium, or substitutedammonium salts thereof, or mixtures thereof.Other suitable heavy metal ion sequestrants for use herein areiminodiacetic acid derivatives such as 2—hydroxyethyl diacetic acid orglyceryl imino diacetic acid, described in EP—A—317,542 and EP-A-399,133. The iminodiacetic acid-N—2—hydroxypropyl sulfonic acid andaspartic acid N-carboxymethyl N—2—hydroxypropyl-3-sulfonic acidsequestrants described in EP-A-516, 102 are also suitable herein. The B-alanine-N,N'—diacetic acid, aspartic acid-N,N'-diacetic acid, asparticacid—N-monoacetic acid and iminodisuccinic acid sequestrantsdescribed in EP-A-509,382 are also suitable.CA 02265899 l999-03- 16WO 98113449 PCT/US97l1707750EP-A-476,257 describes suitable amino based sequestrants. EP-A-510,331 describes suitable sequestrants derived from collagen, keratinor casein. EP—A-528,859 describes a suitable alkyl iminodiacetic acidsequestrant. Dipicolinic acid and 2-phosphonobutane-1,2,4-tricarboxylic acid are alos suitable. Glycinamide—N,N'—disuccinic acid(GADS), etl1ylenediamine—N-N'-diglutaric acid (EDDG) and 2-hydroxypropylenediamine-N-N'-disuccinic acid (HPDDS) are alsosuitable.Bleach catalystThe oxygen—releasing bleach system can contain a transition metalcontaining bleach catalyst.One suitable type of bleach catalyst is a catalyst system comprising atransition metal cation of defined bleach catalytic activity, such ascopper, iron or manganese cations, an auxiliary metal cation havinglittle or no bleach catalytic activity, such as zinc or aluminum cations,and a sequestrant having defined stability constants for the catalytic andauxiliary metal cations, particularly ethylenediaminetetraacetic acid,ethylenediaminetetra(methylenephosphonic acid) and water—solublesalts thereof. Such catalysts are disclosed in U.S. Pat. 4,430,243.Other types of bleach catalysts include the manganese-based complexesdisclosed in U.S. Pat. 5,246,621 and U.S. Pat. 5,244,594. Preferredexamples of these catalysts include MnIV2(u-O)3(1,4,7—trimethyl—1,4,7-triazacyclononane)2-(PF5)2, Mnm2(u-O)1(u—OAc)2(1,4,7-trimethyl-1 ,4,7—triazacyclononane)2-(ClO4)2, MnIV4(u—O)5(1 ,4,7-triazacyclononane)4—(ClO4)2, MnmMnIV4(u-O)1(u-OAc)2_(1 ,4,7-trimethyl—1,4,7—triazacyclononane)2—(ClO4)3, and mixtures thereof.Others are described in European patent application publication no.549,272. Other ligands suitable for use herein include 1,5,9—trimethyl-1,5,9-triazacyclododecane, 2—methyl—1,4,7—triazacyclononane, 2-methyl—1 ,4,7—triazacyclononane, 1,2,4,7-tetramethyl—1 ,4,7-triazacyclononane, and mixtures thereof.CA 02265899 l999-03- 16W0 98/ 13449 PCT/US97/ 1707751The bleach catalysts useful herein may also be selected as appropriatefor the present invention. For examples of suitable bleach catalysts seeU.S. Pat. 4,246,612 and U.S. Pat. 5,227,084. See also U.S. Pat.5,194,416 which teaches mononuclear manganese (IV) complexes suchas Mn(1 ,4 ,7-trimethyl—1,4,7—triazacyclononane)(OCH3)3_(PF5).Still another type of bleach catalyst, as disclosed in U.S. Pat.5,114,606, is a water-soluble complex of manganese (111), and/or (IV)with a ligand which is a non-carboxylate polyhydroxy compoundhaving at least three consecutive C-OH groups. Preferred ligandsinclude sorbitol, iditol, dulsitol, mannitol, xylithol, arabitol, adonitol,meso-erythritol, meso-inositol, lactose, and mixtures thereof.U.S. Pat. 5,114,611 teaches a bleach catalyst comprising a complex oftransition metals, including Mn, Co, Fe, or Cu, with an non~(macro)—cyclic ligand. Said ligands are of the formula:R2 R3R1-N=C-B-C=N-R4wherein R1, R2, R3, and R4 can each be selected from H, substitutedalkyl and aryl groupssuch that each R1-N=C-R2 and R3-C=N-R4form a five or six—membered ring. Said ring can further besubstituted. B is a bridging group selected from O, S. CR5R6, NR7and C=O, wherein R5, R5, and R7 can each be H, alkyl, or arylgroups, including substituted or unsubstituted groups. Preferredligands include pyridine, pyridazine, pyrimidine, pyrazine, imidazole,pyrazole, and triazole rings. Optionally, said rings may be substitutedwith substituents such as alkyl, aryl, alkoxy, halide, and nitro.Particularly preferred is the ligand 2,2‘-bispyridylamine. Preferredbleach catalysts include Co, Cu, Mn, Fe,—bispyridylmethane and —bispyridylamine complexes. Highly preferred catalysts includeCo(2,2'—bispyridylamine)Cl2, Di(isothiocyanato)bispyridylamine-cobalt (II), trisdipyridylamine—cobalt(II) perchlorate, Co(2,2—bispyridylamine)2O2ClO4, Bis-(2,2'-bispyridylamine) copper(II)CA 02265899 l999-03- 16W0 98l13449 PCT/US97/1707752perchlorate, tris(di—2-pyridylamine) iron(II) perchlorate, and mixturesthereof.Other examples include binuclear Mn complexed with tetra-N—dentateand bi—N-dentate ligands, including N4Mnm(u—O)2MnIVN4)+ and[BipyzMn1H<u-o>2Mn1Vbipy2i-<c1o4>3.Other bleach catalysts are described, for example, in European patentapplication, publication no. 408,131 (cobalt complex catalysts),European patent applications, publication nos. 384,503, and 306,089(metallo-porphyrin catalysts), U.S. 4,728,455 (manganese/multidentateligand catalyst), U.S. 4,711,748 and European patent application,publication no. 224,952, (absorbed manganese on aluminosilicatecatalyst), U.S. 4,601,845 (aluminosilicate support with manganese andzinc or magnesium salt), U.S. 4,626,373 (manganese/ligand catalyst),U.S. 4,119,557 (ferric complex catalyst), German Pat. specification2,054,019 (cobalt chelant catalyst) Canadian 866,191 (transition metal-containing salts), U.S. 4,430,243 (chelants with manganese cations andnon—catalytic metal cations), and U.S. 4,728,455 (manganese gluconatecatalysts). 'The bleach catalyst is typically used in a catalytically effective amountin the compositions and processes herein. By "catalytically effectiveamount" is meant an amount which is sufficient, under whatevercomparative test conditions are employed, to enhance bleaching andremoval of the stain orstains of interest from the target substrate. Thetest conditions will vary, depending on the type of washing applianceused and the habits of the user. Some users elect to use very hot water;others use warm or even cold water in laundering operations. Ofcourse, the catalytic performance of the bleach catalyst will be affectedby such considerations, and the levels of bleach catalyst used in fully-formulated detergent and bleach compositions can be appropriatelyadjusted. As a practical matter, and not by way of limitation, thecompositions and processes herein can be adjusted to provide on theorder of at least one part per ten million of the active bleach catalystspecies in the aqueous washing liquor, and will preferably providefrom about 1 ppm to about 200 ppm of the catalyst species in the washCA 02265899 l999-03- 16W0 98/ 13449 PCT/US97/1707753liquor. To illustrate this point further, on the order of 3 micromolarmanganese catalyst is effective at 40°C, pH 10 under Europeanconditions using perborate and a bleach precursor. An increase inconcentration of 3-5 fold may be required under U.S. conditions toachieve the same results.Enz meAnother preferred ingredient useful in the detergent compositions orcomponents thereof is one or more additional enzymes.Preferred additional enzymatic materials include the commerciallyavailable lipases, cutinases, amylases, neutral and alkaline proteases,cellulases, endolases, esterases, pectinases, lactases and peroxidasesconventionally incorporated into detergent compositions. Suitableenzymes are discussed in US Patents 3,519,570 and 3,533,139.Preferred commercially available protease enzymes include those soldunder the tradenames Alcalase, Savinase, Primase, Durazym, andEsperase by Novo Industries A/S (Denmark), those sold under thetradename Maxatase, Maxacal and Maxapem by Gist-Brocades, thosesold by Genencor International, and those sold under the tradenameOpticlean and Optimase by Solvay Enzymes. Protease enzyme may beincorporated into the compositions in accordance with the invention ata level of from 0.0001 % to 4% active enzyme by weight of thecomposition.Preferred amylases include, for example, on-amylases obtained from aspecial strain of B licheniformis, described in more detail in GB-1,269,839 (Novo). Preferred commercially available amylases includefor example, those sold under the tradename Rapidase by Gist-Brocades, and those sold under the tradename Terrnamyl and BAN byNovo Industries A/S. Amylase enzyme may be incorporated into thecomposition in accordance with the invention at a level of from0.0001% to 2% active enzyme by weight of the composition.CA 02265899 l999-03- 16W0 98/ 13449 PCT/US97/1707754Lipolytic enzyme may be present at levels of active lipolytic enzyme offrom 0.0001 % to 2% by weight, preferably 0.001% to 1% by weight,most preferably from 0.001% to 0.5 % by weight of the compositions.The lipase may be fungal or bacterial in origin being ‘obtained, forexample, from a lipase producing strain of Humicola sp.,Thermomyces sp. or Pseudomonas sp. including Pseudomonaspseudoalcaligenes or Pseudomas fluorescens. Lipase from chemicallyor genetically modified mutants of these strains are also useful herein.A preferred lipase is derived from Pseudomonas pseudoalcaligenes,which is described in Granted European Patent, EP-B-0218272.Another preferred lipase herein is obtained by cloning the gene fromHumicola lanuginosa and expressing the gene in Aspergillus orgy, ashost, as described in European Patent Application, EP—A-0258 068,which is commercially available from Novo Industri A/S, Bagsvaerd,Denmark, under the trade name Lipolase. This lipase is also describedin U.S. Patent 4,810,414, Huge—Jensen et al, issued March 7, 1989.Organic polymeric compoundOrganic polymeric compounds are preferred additional components ofthe detergent compositions or components thereofin accord with theinvention, and are preferably present as components of any particulatecomponents where they may act such as to bind the particulatecomponent together. By organic polymeric compound it is meantherein essentially any polymeric organic compound commonly used asdispersants, and anti—redeposition and soil suspension agents indetergent compositions, including any of the high molecular weightorganic polymeric compounds described as clay flocculating agentsherein, not being an quaternised ethoxylated (poly) amine clay—soilremoval/ anti—redeposition agent in accord with the invention.Organic polymeric compound is typically incorporated in the detergentcompositions of the invention at a level of from 0.1% to 30% ,preferably from 0.5% to 15%, most preferably from 1% to 10% byweight of the compositions.CA 02265899 l999-03- 16W0 98/ 13449 PCT /US97/1707755Examples of organic polymeric compounds include the water solubleorganic homo- or co-polymeric polycarboxylic acids or their salts inwhich the polycarboxylic acid comprises at least two carboxyl radicalsseparated from each other by not more than two carbon atoms.Polymers of the latter type are disclosed in GBIA-1,596,756.Examples of such salts are polyacrylates of MWt 1000-5000 and theircopolymers with maleic anhydride, such copolymers having amolecular weight of from 2000 to 100,000, especially 40,000 to80,000.The polyamino compounds are useful herein including those derivedfrom aspartic acid such as those disclosed in EP-A-305282, EP-A-305283 and EP-A—35l629.Terpolymers containing monomer units selected from maleic acid,acrylic acid, polyaspartic acid and vinyl alcohol, particularly thosehaving an average molecular weight of from 5,000 to 10,000, are alsosuitable herein.Other organic polymeric compounds suitable for incorporation in thedetergent compositions herein include cellulose derivatives such asmethylcellulose, carboxymethylcellulose,hydroxypropylmethylcellulose and hydroxyethylcellulose.Further useful organic polymeric compounds are the polyethyleneglycols, particularly those of molecular weight 1000-10000, moreparticularly 2000 to 8000 and most preferably about 4000.Suds suppressing systemThe detergent compositions of the invention, when formulated for usein machine washing compositions, preferably comprise a sudssuppressing system present at a level of from 0.01% to 15 %,preferably from 0.05% to 10%, most preferably from 0.1% to 5% byweight of the composition.CA 02265899 l999-03- 16W0 98/13449 PCTIUS97/1707756Suitable suds suppressing systems for use herein may compriseessentially any known antifoam compound, including, for examplesilicone antifoam compounds and 2-alkyl alcanol antifoam compounds.By antifoam compound it is meant herein any compound or mixtures ofcompounds which act such as to depress the foaming or sudsingproduced by a solution of a detergent composition, particularly in thepresence of agitation of that solution.Particularly preferred antifoam compounds for use herein are siliconeantifoam compounds defined herein as any antifoam compoundincluding a silicone component. Such silicone antifoam compoundsalso typically contain a silica component. The term "silicone" as usedherein, and in general throughout the industry, encompasses a varietyof relatively high molecular weight polymers containing siloxane_unitsand hydrocarbyl group of various types. Preferred silicone antifoamcompounds are the siloxanes, particularly the polydimethylsiloxaneshaving trimethylsilyl end blocking units.Other suitable antifoam compounds include the monocarboxylic fattyacids and soluble salts thereof. These materials are described in USPatent 2,954,347, issued September 27, 1960 to Wayne St. John. Themonocarboxylic fatty acids, and salts thereof, for use as sudssuppressor typically have hydrocarbyl chains of 10 to 24 carbon atoms,preferably 12 to 18 carbon atoms. Suitable salts include the alkalimetal salts such as sodium, potassium, and lithium salts, andammonium and alkanolammonium salts.Other suitable antifoam compounds include, for example, highmolecular weight fatty esters (e.g. fatty acid triglycerides), fatty acidesters of monovalent alcohols, aliphatic C13-C40 ketones (e. g.stearone) N—a1kylated amino triazines such as tri— to hexa-alkylmelamines or di- to tetra alkyldiamine chlortriazines formed asproducts of cyanuric chloride with two or three moles of a primary orsecondary amine containing 1 to 24 carbon atoms, propylene oxide, bisstearic acid amide and monostearyl di-alkali metal (e.g. sodium,potassium, lithium) phosphates and phosphate esters.CA 02265899 l999-03- 16W0 98/13449 PCT/US97/1707757A preferred suds suppressing system comprises(a) antifoam compound, preferably silicone antifoam compound,most preferably a silicone antifoam compound comprising incombination(i) polydimethyl siloxane, at a level of from 50% to 99%,preferably 75% to 95% by weight of the silicone antifoamcompound; and(ii) silica, at a level of from 1% to 50%, preferably 5% to25 % by weight of the silicone/silica antifoam compound;wherein said silica/silicone antifoam compound is incorporated at alevel of from 5% to 50%, preferably 10% to 40% by weight;(b) a dispersant compound, most preferably comprising a siliconeglycol rake copolymer with a polyoxyalkylene content of 72-78% and an ethylene oxide to propylene oxide ratio of from120.9 to 1:1.1, at a level of from 0.5% to 10%, preferably 1%to 10% by weight; a particularly preferred silicone glycol rakecopolymer of this type is DCO544, commercially available fromDOW Corning under the tradename DCO544;(c) an inert carrier fluid compound, most preferably comprising aC16-C18 ethoxylated alcohol with a degree of ethoxylation offrom 5 to 50, preferably 8 to 15, at a level of from 5% to 80% ,preferably 10% to 70%, by weight;A highly preferred particulate suds suppressing system is described inEP-A-0210731 and comprises a silicone antifoam compound and anorganic carrier material having a melting point in the range 50°C to85°C, wherein the organic carrier material comprises a monoester ofglycerol and a fatty acid having a carbon chain containing from 12 to20 carbon atoms. EP—A-0210721 discloses other preferred particulatesuds suppressing systems wherein the organic carrier material is a fattyCA 02265899 l999-03- 16W0 98/13449 PCT/US97/1707758acid or alcohol having a carbon chain containing from 12 to 20 carbonatoms, or a mixture thereof, with a melting point of from 45°C to80°C.Polymeric dye transfer inhibiting agentsThe detergent compositions herein may also comprise from 0.01% to10 %, preferably from 0.05% to 0.5 % by weight of polymeric dyetransfer inhibiting agents.The polymeric dye transfer inhibiting agents are preferably selectedfrom polyamine N-oxide polymers, copolymers of N—vinylpyrrolidoneand N-vinylimidazole, polyvinylpyrrolidonepolymers or combinationsthereof, whereby these polymers can be cross—linked polymers.a) Polyamine N-oxide polymersPolyamine N-oxide polymers suitable for use herein contain unitshaving the following structure formula :P(|) AxRwherein P is a polymeriisable unit, andQ 0 OA is CO, -0-, —S-, -N-; x is O or1;R are aliphatic, ethoxylated aliphatics, aromatic, heterocyclic oralicyclic groups or any combination thereof whereto the nitrogen ofthe N—O group can be attached or wherein the nitrogen of the N—Ogroup is part of these groups.The N—O group can be represented by the following generalstructures :CA 02265899 l999-03- 16W0 98/ 1 3449 PCT/US97/1707759OA0(R1) x -N-<R2)y ‘(R3); N—(R1)xOI‘wherein R1, R2, and R3 are aliphatic groups, aromatic, heterocyclic oralicyclic groups or combinations thereof, x or/and y or/and z is 0 or 1and wherein the nitrogen of the N-O group can be attached or whereinthe nitrogen of the N-O group forms part of these groups. The N-Ogroup can be part of the polymerisable unit (P) or can be attached tothe polymeric backbone or a combination of both.Suitable polyamine N—oxides wherein the N-O group forms part of thepolymerisable unit comprise polyamine N-oxides wherein R is selectedfrom aliphatic, aromatic, alicyclic or heterocyclic groups. One class ofsaid polyamine N-oxides comprises the group of polyamine N—oxideswherein the nitrogen of the N-O group forms part of the R-group.Preferred polyamine N-oxides are those wherein R is a heterocyclicgroup such as pyrridine, pyrrole, imidazole, pyrrolidine, piperidine,quinoline, acridine and derivatives thereof.Other suitable polyamine N—oxides are the polyamine oxides wheretothe N -0 group is attached to the polymerisable unit. A preferred classof these polyamine N-oxides comprises the polyamine N—oxides havingthe general formula (I) wherein R is an aromatic,heterocyclic oralicyclic groups wherein the nitrogen of the N -0 functional group ispart of said R group. Examples of these classes are polyamine oxideswherein R is a heterocyclic compound such as pyrridine, pyrrole,imidazole and derivatives thereof.The polyamine N-oxides can be obtained in almost any degree ofpolymerisation. The degree of polymerisation is not critical providedthe material has the desired water-solubility and dye-suspendingCA 02265899 1999-03-16W0 98/ 13449 PCT/US97/ 1707760power. Typically,9the average molecular weight is within the range of500 to 1000,000.bj Conolvmers of N—vinvlDvrrolidone and N-vinvlimidazoleSuitable herein are coploymers of N-vinylimidazole and N-vinylpyrrolidone having an average molecular weight range of from5,000, to 50,000. The preferred copolymers have a molar ratio of N-vinylimidazole to N—vinylpyrrolidone from 1 to 0.2.CA 02265899 l999-03- 16W0 98/13449 PCTlUS97/ 1707761c) PolyvinylpyrrolidoneThe detergent compositions herein may also utilizepolyvinylpyrrolidone ("PVP") having an average molecular weight offrom 2,500 to 400,000. Suitable polyvinylpyrrolidones arecommercially vailable from ISP Corporation, New York, NY andMontreal, Canada under the product names PVP K-15 (viscositymolecular weight of 10,000), PVP K-30 (average molecular weight of40,000), PVP K-60 (average molecular weight of 160,000), and PVPK-90 (average molecular weight of 360,000). PVP K-15 is alsoavailable from ISP Corporation. Other suitable polyvinylpyrrolidoneswhich are commercially available from BASF Cooperation includeSokalan HP 165 and Sokalan HP 12.d) PolyvinyloxazolidoneThe detergent compositions herein may also utilizepolyvinyloxazolidones as polymeric dye transfer inhibiting agents. Saidpolyvinyloxazolidones have an average molecular weight of from2,500 to 400,000.e) PolyvinylimidazoleThe detergent compositions herein may also utilize polyvinylimidazoleas polymeric dye transfer inhibiting agent. Said polyvinylimidazolespreferably have an average molecular weight of from 2,500 to400,000.Optical brightenerThe detergent compositions herein also optionally contain from about0.005 % to 5 % by weight of certain types of hydrophilic opticalbrighteners.Hydrophilic optical brighteners useful herein include those having thestructural formula:CA 02265899 l999-03- 16WO 98/13449 PCT/US97/1707762R1 R2>—N 1.“: HN OH =6 I.“-<ON>-—N H H N —<R2 SO3M S03M R1wherein R1 is selected from anilino, N—2-bis—hydroxyethyl and NH—2-hydroxyethyl; R2 is selected from N—2—bis-hydroxyethyl, N—2—hydroxyethyl-N-methylamino, morphilino, chloro and amino; and M isa salt-forming cation such as sodium or potassium.When in the above formula, R1 is anilino, R2 is N-2—bis—hydroxyethyland M is a cation such as sodium, the brightener is 4,4‘ ,-bis[(4-anilino-6—(N-2-bis-hydroxyethyl)—s—triazine-2-yl)amino]-2,2'-stilbenedisulfonicacid and disodium salt. This particular brightener species iscommercially marketed under the tradename Tinopal-UNPA-GX byCiba-Geigy Corporation. Tinopal-UNPA-GX is the preferredhydrophilic optical brightener useful in the detergent compositionsherein.When in the above formula, R1 is anilino, R2 is N—2~hydroxyethyl-N-2-methylamino and M is a cation such as sodium, the brightener is4,4'-bis[(4—anilino-6—(N-2-hydroxyethyl-N—methylamino)-s—triazine—2—yl)amino]2,2'-stilbenedisulfonic acid disodium salt. This particularbrightener species is commercially marketed under the tradenameTinopal 5BM—GX by Ciba-Geigy Corporation.When in the above formula, R1 is anilino, R2 is morphilino and M is acation such as sodium, the brightener is 4,4'-bis[(4—anilino-6-morphilino-s-triazine-2-y1)amino]2,2'-stilbenedisulfonic acid, sodiumsalt. This particular brightener species is commercially marketedunder the tradename Tinopal AMS-GX by Ciba Geigy Corporation.Polymeric Soil Release AgentKnown polymeric soil release agents, hereinafter "SRA", canoptionally be employed in the present detergent compositions. IfCA 02265899 l999-03- 16WO 98113449 PCT /US97/1707763utilized, SRA's will generally comprise from 0.01% to 10.0%,typically from 0.1% to 5%, preferably from 0.2% to 3.0% by weight,of the compositions.Preferred SRA's typically have hydrophilic segments to hydrophilizethe surface of hydrophobic fibers such as polyester and nylon, andhydrophobic segments to deposit upon hydrophobic fibers and remainadhered thereto through completion of washing and rinsing cycles,thereby serving as an anchor for the hydrophilic segments. This canenable stains occurring subsequent to treatment with the SRA to bemore easily cleaned in later washing procedures.Preferred SRA's include oligomeric terephthalate esters, typicallyprepared by processes involving at least onetransesterification/oligomerization, often with a metal catalyst such as atitanium(IV) alkoxide. Such esters may be made using additionalmonomers capable of being incorporated into the ester structurethrough one, two, three, four or more positions, without, of course,forming a densely crosslinked overall structure.Suitable SRA's include a sulfonated product of a substantially linearester oligomer comprised of an oligomeric ester backbone ofterephthaloyl and oxyalkyleneoxy repeat units and allyl—derivedsulfonated terminal moieties covalently attached to the backbone, forexample as described in U.S. 4,968,451, November 6, 1990 to J .J .Scheibel and E.P. Gosselink. Such ester oligomers can be preparedby: (a) ethoxylating allyl alcohol; (b) reacting the product of (a) withdimethyl terephthalate ("DMT") and 1,2-propylene glycol ("PG") in atwo-stage transesterification/oligomerization procedure; and (c)reacting the product of (b) with sodium metabisulfite in water. OtherSRA's include the nonionic end—capped 1,2—propylene/polyoxyethyleneterephthalate polyesters of U.S. 4,711,730, December 8, 1987 toGosselink et al., for example those produced bytransesterification/oligomerization of poly(ethyleneglycol) methylether, DMT, PG and poly(ethyleneglycol) ("PEG"). Other examplesof SRA's include: the partly— and fully- anionic—end—capped oligomericesters of U.S. 4,721,580, January 26, 1988 to Gosselink, such asCA 02265899 l999-03- 16WO 98/13449 PCT/US97/1707764oligomers from ethylene glycol ("EG"), PG, DMT and Na—3,6-dioxa—8-hydroxyoctanesulfonate; the nonior1ic—capped block polyesteroligomeric compounds of U.S. 4,702,857, October 27, 1987 toGosselink, for example produced from DMT, methyl (Me)—cappedPEG and EG and/or PG, or a combination of DMT, EG and/or PG,Me—capped PEG and .Na-dimethyl-5-sulfoisophthalate; and the anionic,especially sulfoaroyl, end—capped terephthalate esters of U.S.4,877,896, October 31, 1989 to Maldonado, Gosselink et al., the latterbeing typical of SRA's useful in both laundry and fabric conditioningproducts, an example being an ester composition made from m-sulfobenzoic acid monosodium salt, PG and DMT, optionally butpreferably further comprising added PEG, e.g., PEG 3400.SRA's also include: simple copolymeric blocks of ethyleneterephthalate or propylene terephthalate with polyethylene oxide orpolypropylene oxide terephthalate, see U.S. 3,959,230 to Hays, May25, 1976 and U.S. 3,893,929 to Basadur, July 8, 1975; cellulosicderivatives such as the hydroxyether cellulosic polymers available asMETHOCEL from Dow; the C1-C4 alkyl celluloses and C4hydroxyalkyl celluloses, see U.S. 4,000,093, December 28, 1976 toNicol, et al.; and the methyl cellulose ethers having an average degreeof substitution (methyl) per anhydroglucose unit from about 1.6 toabout 2.3 and a solution viscosity of from about 80 to about 120centipoise measured at 20°C as a 2% aqueous solution. Such materialsare available as METOLOSE SMIOO and METOLOSE SM200, whichare the trade names of methyl cellulose ethers manufactured by Shin-etsu Kagaku Kogyo KK.Additional classes of SRA's include: (I) nonionic terephthalates usingdiisocyanate coupling agents to link polymeric ester structures, seeU.S. 4,201,824, Violland et al. and U.S. 4,240,918 Lagasse et al.;and (II) SRA's with carboxylate terminal groups made by addingtrimellitic anhydride to known SRA's to convert terminal hydroxylgroups to trimellitate esters. With the proper selection of catalyst, thetrimellitic anhydride forms linkages to the terminals of the polymerthrough an ester of the isolated carboxylic acid of trimellitic anhydriderather than by opening of the anhydride linkage. Either nonionic orCA 02265899 l999-03- 16W0 98/13449 PCT/US97/1707765anionic SRA's may be used as starting materials as long as they have_hydroxyl terminal groups which may be esterified. See U.S.4,525,524 Tung et al.. Other classes include: (III) anionicterephthalate-based SRA's of the urethane-linked variety, see U.S.4,201,824, Violland et al.;Other optional ingredientsOther optional ingredients suitable for inclusion in the compositions ofthe invention include perfumes, colours and filler salts, with sodiumsulfate being a preferred filler salt.Near neutral wash pH dergent formulationWhile the detergent compositions of the present invention are operativewithin a wide range of wash pHs (e. g. from about 5 to about 12), theyare particularly suitable when formulated to provide a near neutralwash pH, i.e. an initial pH of from about 7.0 to about 10.5 at aconcentration of from about 0.1 to about 2% by weight in water at20°C. Near neutral wash pH formulations are better for enzymestability and for preventing stains from setting. In such formulations,the wash pH is preferably from about 7.0 to about 10.5, morepreferably from about 8.0 to about 10.5, most preferably from 8.0 to9ØPreferred near neutral wash pH detergent formulations are disclosed toEuropean Patent Application 83.200688.6, filed May 16, 1983,J.H.M. Wertz and P.C.E. Goffinet.Highly preferred compositions of this type also preferably contain fromabout 2 to about 10% by weight of citric acid and minor amounts (e.g.,less than about 20% by weight) of neutralizing agents, bufferingagents, phase regulants, hydrotropes, enzymes, enzyme stabilizingagents, polyacids, suds regulants, opacifiers, anti-oxidants,bactericides, dyes, perfumes and brighteners, such as those describedin US Patent 4,285,841 to Barrat et al., issued August 25, 1981 (hereinincorporated by reference).CA 02265899 l999-03- 16W0 98/134419 PCT/US97l1707766Form of the compositionsThe detergent component of the invention can be made via a variety ofmethods, including dry-mixing and agglomerating of the variouscompounds comprised in the detergent component. AThe detergent component preferably forms part of a detergentcomposiiton.The compositions in accordance with the invention can take a varietyof physical forms including granular, tablet, flake, pastille and barforms. The compositions are particularly the so-called concentratedgranular detergent compositions adapted to be added to a washingmachine by means of a dispensing device placed in the machine drumwith the soiled fabric load.The compositions in accord with the present invention can also be usedin or in combination with bleach additive compositions, for examplecomprising chlorine bleach._In general, granular detergent compositions in accordance with thepresent invention can be made via a variety of methods including drymixing, spray drying, agglomeration and granulation. The quaternisedclay—soil removal/ anti—redeposition agent in accord with the presentinvention can be added to the other detergent components by dry-mixing, agglomeration (preferably combined with a carrier material) oras a spray-dried component.The mean particle size of the components of granular compositions inaccordance with the invention, comprising the water-soluble cationicclay—soil removal/anti—redeposition compounds, should preferably besuch that no more that 15% of the particles are greater than 1.8mm indiameter and not more than 15 % of the particles are less than 0.25mmin diameter. Preferably the mean particle size is such that from 10% to50% of the particles has a particle size of from 0.2mm to 0.7mm indiameter.CA 02265899 l999-03- 16W0 98/ 13449 PCT/US97l1707767The term mean particle size as defined herein is calculated by sieving asample of the composition into a number of fractions (typically 5fractions) on a series of sieves, preferably Tyler sieves. The weightfractions thereby obtained are plotted against the aperture size of thesieves. The mean particle size is taken to be the aperture size throughwhich 50% by weight of the sample would pass.The bulk density of granular detergent compositions in accordancewith the present invention typically have a bulk density of at least 600g/litre, more preferably from 650 g/litre to 1200 g/litre. Bulk densityis measured by means of a simple funnel and cup device consisting of aconical funnel moulded rigidly on a base and provided with a flapvalve at its lower extremity to allow the contents of the funnel to beemptied into an axially aligned cylindrical cup disposed below thefunnel. The funnel is 130 mm high and has internal diameters of 130mm and 40 mm at its respective upper and lower extremities. It ismounted so that the lower extremity is 140 mm above the uppersurface of the base. The cup has an overall height of 90 m, aninternal height of 87 mm and a.n internal diameter of 84 mm. Itsnominal volume is 500 ml.To carry out a measurement, the funnel is filled with powder by handpouring, the flap valve is opened and powder allowed to overfill thecup. The filled cup is removed from the frame and excess powderremoved from the cup by passing a straight edged implement eg; aknife, across its upper edge. The filled cup is then weighed and thevalue obtained for the weight of powder doubled to provide a bulkdensity in g/litre. Replicate measurements are made as required.Compacted solids may be manufactured using any suitable compactingprocess, such as tabletting, briquetting or extrusion, preferablytabletting. Preferably tablets for use in dish washing processes, aremanufactured using a standard rotary tabletting press usingcompression forces of from 5 to 13 KN/cm2, more preferably’ from 5to 11KN/cm2 so that the compacted solid has a minimum hardness of176N to 275N, preferably from 195N to 245N, measured by a C100hardness test as supplied by 1. Holland instruments. This process mayCA 02265899 l999-03- 16W0 98/ 13449 PCT/US97/1707768be used to prepare homogeneous or layered tablets of any size orshape. Preferably tablets are symmetrical to ensure the uniformdissolution of the tablet in the wash solution.Laundry washing methodMachine laundry methods herein typically comprise treating soiledlaundry with an aqueous wash solution in a washing machine havingdissolved or dispensed therein an effective amount of a machinelaundry detergent composition in accord with the invention. By aneffective amount of the detergent composition it is meant from 10g to300g of product dissolved or dispersed in a wash solution of volumefrom 5 to 65 litres, as are typical product dosages and wash solutionvolumes commonly employed in conventional machine laundrymethods.In a preferred use aspect a dispensing device is employed in thewashing method. The dispensing device is charged with the detergentproduct, and is used to introduce the product directly into the drum ofthe washing machine before the commencement of the wash cycle. Itsvolume capacity should be such as to be able to contain sufficientdetergent product as would normally be used in the washing method.The dispensing device containing the detergent product is placed insidethe drum before the commencement of the wash, before,simultaneously with or after the washing machine has been loaded withlaundry. At the commencement of the wash cycle of the washingmachine water is introduced into the drum and the drum periodicallyrotates. The design of the dispensing device should be such that itpermits containment of the dry detergent product but then allowsrelease of this product during the wash cycle in response to its agitationas the drum rotates and also as a result of its contact with the washwater.To allow for release of the detergent product during the wash thedevice may possess a number of openings through which the productmay pass. Alternatively, the device may be made of a material whichCA 02265899 l999-03- 16W0 98/ 13449 PCT/US97I1707769is permeable to liquid but impermeable to the solid product, which willallow release of dissolved product. Preferably, the detergent productwill be rapidly released at the start of the wash cycle thereby providingtransient localised high concentrations of product in the drum of thewashing machine at this stage of the wash cycle.Preferred dispensing devices are reusable and are designed in such away that container integrity is maintained in both the dry state andduring the wash cycle. Especially preferred dispensing devices for usewith the composition of the invention have been described in thefollowing patents; GB—B-2, 157, 717, GB—B-2, 157, 718, EP-A-0201376, EP-A-0288345 and EP-A-0288346. An article by J .Blandpublished in Manufacturing Chemist, November 1989, pages 41-46also describes especially preferred dispensing devices for use withgranular laundry products which are of a type commonly know as the"granulette". Another preferred dispensing device for use with thecompositions of this invention is disclosed in PCT Patent ApplicationNo. WO94/ 11562.Especially preferred dispensing devices are disclosed in EuropeanPatent Application Publication Nos. 0343069 & 0343070. The latterApplication discloses a device comprising a flexible sheath in the formof a bag extending from a support ring defining an orifice, the orificebeing adapted to admit to the bag sufficient product for one washingcycle in a washing process. A portion of the washing medium flowsthrough the orifice into the bag, dissolves the product, and the solutionthen passes outwardly through the orifice into the washing medium.The support ring is provided with a masking arrangemnt to preventegress of wetted, undissolved, product, this arrangement typicallycomprising radially extending walls extending from a central boss in aspoked wheel configuration, or a similar structure in which the wallshave a helical form.Alternatively, the dispensing device may be a flexible container, suchas a bag or pouch. The bag may be of fibrous construction coated witha water impermeable protective material so as to retain the contents,such as is disclosed in European published Patent Application No.CA 02265899 l999-03- 16WO 98/13449 PCT/U S97l17077700018678. Alternatively it may be formed of a water—insolublesynthetic polymeric material provided with an edge seal or closuredesigned to rupture in aqueous media as disclosed in Europeanpublished Patent Application Nos. 0011500, 0011501, 0011502, and0011968. A convenient form of water frangible closure comprises awater soluble adhesive disposed along and sealing one edge of a pouchformed of a water impermeable polymeric film such as polyethylene orpolypropylene.Machine dishwashing methodAny suitable methods for machine dishwashing or cleaning soiledtableware, particularly soiled silverware are envisaged.A preferred machine dishwashing method comprises treating soiledarticles selected from crockery, glassware, hollowware, silverware andcutlery and mixtures thereof, with an aqueous liquid having dissolvedor dispensed therein an effective amount of a machine dishwashingcomposition in accord with the invention. By an effective amount ofthe machine dishwashing composition it is meant from 8g to_p60g ofproduct dissolved or dispersed in a wash solution of volume from 3 to10 litres, as are typical product dosages and wash solution volumescommonly employed in conventional machine dishwashing methods.Packaging for the compositionsCommercially marketed executions of the bleaching compositions canbe packaged in any suitable container including those constructed frompaper, cardboard, plastic materials and any suitable laminates. Apreferred packaging execution is described in European ApplicationNo. 94921505.7.Abbreviations used in ExamplesIn the detergent compositions, the abbreviated componentidentifications have the following meanings:LAS : Sodium linear C12 alkyl benzene sulfonateW0 98/ 13449TASCxyASC46SASsulfateCxyEzSCxyEzalcoholethyleneQASC14SoapanCFAATFAATPKFASTPPTSPPZeolite AZeolite MAPNaSKS-6Citric acidBorateCarbonatesizeBicarbonateSilicate2.0: 1)Sodium sulfateCA 02265899 l999-03- 16PCT/US97/1707771Sodium tallow alkyl sulfateSodium C1x - C1y alkyl sulfateSodium C14 - C15 secondary (2,3) alkylSodium C1x—C1y alkyl sulfate condensed withmoles of ethylene oxideC1,;-C1y predominantly linear primarycondensed with an average of z moles ofoxideR2.N+(CH3)2(C2H4OH) with R2 = C12 -Sodium linear alkyl carboxylate derived from80/20 mixture of tallow and coconut oilsC12-C14 (coco) alkyl N-methyl glucamideC 16-C13 alkyl N-methyl glucamideC12_C14 topped whole cut fatty acidsAnhydrous sodium tripolyphosphateTetrasodium pyrophosphateHydrated Sodium Aluminosilicate of formulaNa12(A1O2SiO2)12.27I-I20 having a primaryparticle size in the range from 0.1 to 10micrometersHydrated sodium aluminosilicate zeolite MAPhaving a silicon to aluminium ratio of 1.07Crystalline layered silicate of formula 5-Na2Si2O5Anhydrous citric acidSodium borateAnydrous sodium carbonate with a particlebetween 200p.m and 900p.mAnhydrous sodium bicarbonate with a particlesize distribution between 400nm and 1200umAmorphous Sodium Silicate (SiO_7_:Na20 =Anhydrous sodium sulfateW0 98/123449Citrate425p.mMA/AAaverageAACMCZCellulose etherEtsuProteasebyAlcalaseCellulasesoldtradenameAmylasesold bytradenameLipasetradenameEndolaseCEVU/ gPB4formulaPB 1nominalPercarbonateNAC-OBSinNACA02265899 l999-03- 16PCT/US97/1 707772Tri-sodium citrate dihydrate of activity 86.4%with a particle size distribution betweenand 850p.mCopolymer of 1:4 maleic/acrylic acid,molecular weight about 70,000Sodium polyacrylate polymer of averagemolecular weight 4,500Sodium carboxymethyl celluloseMethyl cellulose ether with a degree ofpolymerization of 650 available from ShinChemicalsProteolytic enzyme of activity 4KNPU/g soldNOVO Industries A/S under the tradenameSavinaseProteolytic enzyme of activity 3AU/ g sold byNOVO Industries A/SCellulytic enzyme of activity 1000 CEVU/ gby NOVO Industries A/S under theCarezymeAmylolytic enzyme of activity 120KN U/ gNOVO Industries A/S under theTermamyl 120TLipolytic enzyme of activity 100KLU/ g soldby NOVO Industries A/S under theLipolaseEndoglucanase enzyme of activity 3000sold by NOVO Industries A/SSodium perborate tetrahydrate of nominalNaBO2.3H2O.H2O2Anhudrous sodium perborate bleach offormula NaBO2.H202Sodium percarbonate of nominal formula2Na2CO3.3H202(Nonanamido caproyl) oxybenzene sulfonatethe form of the sodium salt.6 nonylamino — 6 0x0 - capronic acid.WO 98/13449NOBStheTAEDMn catalystU.S.DTPADTPMPunder thePhotoactivatedin bleachBrightener 1Brightener 21.3.5-HEDPEDDSQEAlC5H12-N + —wherein n=fromQEA2R1, whereinn=from 20 to 30QEA3N +)-n=fromPEGXof xPEOofTEPAEPVPPVNOPVPVI02265899 l999-03- 16PCT/US97ll 707773Nonanoyloxybenzene sulfonate in the form ofsodium saltTetraacetylethylenediamineMnIV2(m—O)3(1,4,7-trimethyl-1,4,7—triazacyclononane)2(PF5)2, as described inPat. Nos. 5,246,621 and 5,244,594.Diethylene triamine pentaacetic acidDiethylene triamine penta (methylenephosphonate), marketed by MonsantoTradename Dequest 2060Sulfonated Zinc Phthlocyanine encapsulateddextrin soluble polymerDisodium 4,4'-bis(2-sulphostyry)biphenylDisodium 4,4'—bis(4—anilino-6—morpholino-triazin~2—yl)amino) stilbene-2:2‘—disulfonate1, 1—hydroxyethane diphosphonic acidEthylenediamine-N, N'—disuccinic acidbi-S((C2H50)(C2H4O)n) (CH3) —N+-(CH3) bis((C2H5O)-(C2H40)n).20 to 30bis((C2H50)-(C2H40)n) (CH3) N+R1 is C4-C1; alkyl group andtri{(bis((C2H50)—(C2H40)n)(CH3)—(CONC3H6)}-C3H50, wherein20 to 26Polyethylene glycol, with a molecular weightPolyethylene oxide, with a molecular weight50,000Tetraethylenepentaamine ethoxylatePolyvinylpyrolidone polymerPolyvinylpyridine N-oxideCopolymer of polyvinylpyrolidone andvinylimidazoleCA 02265899 l999-03- 16W0 98/13449 PCT/US97l1707774SRP 1 : Sulfobenzoyl and capped esters withoxyethylene oxy and terephtaloyl backboneSRP 2 : Diethoxylated poly (1, 2 propyleneterephtalate) short block polymerSilicone antifoam : Polydimethylsiloxane foam controller withsiloxane-oxyalkylene copolymer as dispersingagent with a ratio of said foam controller tosaid dispersing agent of 10:1 to 100:1Wax : Paraffin waxIn the following examples all levels are quoted as % by weight of thecomposition:Example 1The following high density granular laundry detergent compositions Ato F of particular utility under European machine wash conditions wereprepared in accord with the invention:A B C D E FLAS 8.0 8.0 8.0 8.0 8.0 8.0C25E3 3.4 3.4 3.4 3.4 3.4 3.4C46AS 1.0 2.0 2.5 — 3.0 4.0C68AS 3.0 2.0 5.0 7.0 1.0 0.5QAS — — 1 0.8 - - 0.8Zeolite A 18.1 18.1 16.1 18.1 18.1 18.1Zeolite MAP — 4.0 3.5 - — —Carbonate 13.0 13.0 13.0 27.0 27.0 27.0Silicate 1.4 1.4 1.4 3.0 3.0 3.0CA 02265899 l999-03- 16W0 98/ 13449 PCT/US97/ 1707775Sodium Sulfate 26.1 26.1 26.1 26.1 26.1 26.1MA/AA 0.3 0.3 0.3 0.3 0.3 0.3CMC 0.2 0.2 0.2 0.2 0.2 0.2PB4 9.0 9.0 9.0 9.0 9.0 9.0NAC OBS 2.5 1.5. 3.0 4.0 3.2 2.2Mn Catalyst - 0.03 0.07 — - —DTPMP 0.25 0.25 0.25 0.25 0.25 0.25HEDP 0.3 0.3 0.2 0.2 0.3 0.3EDDS - - 0.4 0.2 — -QEA 1 1.0 0.8 0.7 1.2 — 0.5QEA 2 - — — - 1.0 0.5Protease 0.26 0.26 0.26 0.26 0.26 0.26Amylase 0.1 0.1 0.4 0.3 0.1 0.1Photoactivated ’ 15 15 15 15 15 15bleach (PPT11) ppm PPTT1 PPU1 PP!“ Ppm PpmBrightener 1 0.09 0.09 0.09 0.09 0.09 0.09Perfume 0.3 0.3 0.3 0.3 0.3 0.3Silicone antifoam 0.5 0.5 0.5 0.5 0.5 0.5Misc/minors to100%Density in g/litre 850 850 850 850 850 850CA 02265899 l999-03- 16WO 98113449 PCTIUS97l1707776Example 2The following granular laundry detergent compositions G to I ofparticular utility under European machine wash conditions wereprepared in accord with the invention: ’G H ILAS 5.25 5.61 4.76TAS 1.25 1.86 1.57C45AS — 2.24 3.89C25E3S ~ 0.76 1.18C45E7 3.25 — 5.0C25E3 - 5.5 -QAS 0.8 2.0 p 2.0STPP 19.7 - -Zeolite A - 19.5 19.5Zeolite MAP 2.0 - -NaSKS—6/citric acid (79:21) - 10.6 10.6Carbonate 6.1 21.4 21.4Bicarbonate - 2.0 2.0Silicate 6.8 — -Sodium Sulfate 39.8 — 14.3MA/AA 0.8 1.6 1.6CMC 0.2 . 0.4 0.4CA 02265899 l999-03- 16W0 98/13449 PCT/US97/1707777PB4 5.0 12.7 7.1TAED 0.5 0.2 -NAC OBS 1.0 1.3 3.0DTPMP 0.25 0.2 0.2HEDP - 0.3 0.3QEA 1 0.9 1.2 —QEA 2 - — 1.0Protease 0.26 0.85 0.85Lipase 0.15 0.15 0.15Cellulase 0.28 0.28 0.28Amylase 0.4 0.1 0.1PVP 0.9 1.3 0.8Photoactivated bleach (ppm) 15 ppm 27 ppm 27 ppmBrightener 1 0.08 0.19 0.19Brightener 2 — 0.04 0.04Perfume 0.3 0.3 0.3Silicone antifoam 0.5 2.4 2.4Minors/misc to 100%CA 02265899 l999-03- 16wo 98/13449 PCT/US97/1707778Example 3The following detergent formulations of particular utility underEuropean machine wash conditions were prepared in accord with theinvention.J K L MBlown powderLAS 6.0 5.0 11.0 6.0TAS 2.0 — — 2.0Zeolite A - 27.0 — 20.0STPP 24.0 — 24.0 —Sulfate 9.0 6.0 13.0 -MA/AA 2.0 4.0 6.0 4.0Silicate 7.0 3.0 3.0 3.0CMC 1.0 1.0 0.5 0.6QEA 1 0.8 1.0 1.4 0.5QEA 2 - — — 0.5Brightener 0.2 0.2 0.2 0.2Silicone antifoam 1.0 1.0 1.0 0.3DTPMP 0.4 0.4 0.2 0.4Spray onC45E7 - — - 5.0C45E2 2.5 2.5 2.0 -C45E3 2.6 2.5 2.0 —Perfume 0.3 0.3 0.3 0.2Silicone antifoam 0.3 0.3 0.3 -Dry additivesSulfate 3.0 3.0 5.0 10.0Carbonate 6.0 13.0 15.0 14.0PB1 — - - 1.5PB4 18.0 18.0 10.0 18.5NAC OBS 3.0 4.2 1.0 2.0EDDS — 2.0 2.4 —Protease 1.0 1.0 1.0 1.0_ Lipase 0.4 0.4 0.4 0.2CA02265899 1999-03-16wo 98/13449 PCT/US97/1707779Amylase 0.2 0.2 0.2 0.4Photoactivated bleach — — - 0.15Total 100.0 100.0 100.0 100.0CA 02265899 l999-03- 16W0 93/13449 PCT/US97/1707780Example 4The following granular detergent formulations were prepared in accordwith the invention. Formulation N is particularly suitable for usageunder Japanese machine wash conditions. Formulations O to S areparticularly suitable for use under US machine wash conditions.N O P Q R SBlown powderLAS 22.0 5.0 4.0 9.0 8.0 7.0C45AS 7.0 7.0 6.0 — — —C46AS — 4.0 3 .0 - — -C45E35 - 3.0 2.0 8.0 5.0 4.0Zeolite A 6.0 16.0 14.0 19.0 16.0 14.0MA/AA 6.0 3.0 3.0 - -—a -AA - 3.0 3.0 2.0 3.0 3.0Sodium Sulfate 7.0 18.3 11.3 24.0 19.3 19.3Silicate 5.0 1.0 1.0 2.0 1.0 1.0Carbonate 28.3 9.0 7.0 25.7 8.0 6.0QEA 1 0.9 0.9 — — 0.5 1.1QEA 2 — — 0.8 1.0 — _QEA 3 — - 0.4 — — —PEG 4000 0.5 1.5 1.5 1.0 1.5 1.0Sodium oleate 2.0 - — - — —DTPA 0.4 — 0.5 — - 0.5Brightener 0.2 0.3 0.3 0.3 0.3 0.3Spray on gC25E9 1.0 — - - - —C45E7 - 2.0 2.0 0.5 2.0 2.0Perfume 1.0 0.3 0.3 1.0 0.3 0.3AgglomeratesC45AS — 5.0 5.0 - 5.0 5.0LAS — 2.0 2.0 — 2.0 2.0Zeolite A — 7.5 7.5 - 7.5 7.5HEDP — 1.0 - - 2.0 —Carbonate — 4.0 4.0 - 4.0 4.0CA 02265899 l999-03- 16wo 9s/13449 PCTIUS97/1707781PEG 4000 - 0.5 0.5 — 0.5 0.5Misc (water etc) — 2.0 2.0 - 2.0 2.0Dry additivesNAC OBS 1.0 2.0 3.0 1.0 3.0 2.0PB4 — 1.0 4.0 - 5.0 0.5PB1 6.0 - - — — —Percarbonate — 5.0 12.5 — - -Carbonate - 5.3 1.8 — 4.0 4.0NOBS 4.5 — 6.0 - — 0.6Cumeme ~sulfonic acid - 2.0 2.0 - 2.0 2.0Lipase 0.4 0.4 0.4 - 0.4 0.4Cellulase 0.1 0.2 0.2 — 0.2 0.2Amylase 0.1 0.3 0.3 - — -Protease 1.0 0.5 0.5 0.5 0.5 0.5PVPVI — 0.5 0.5 — — -PVP 0.5 0.5 0.5 - - —PVNO — 0.5 0.5 — — —SRPI - 0.5 0.5 - — —Silicone antifoam — 0.2 0.2 - 0.2 0.2Total _ 100.0 100.0 100.0 100.0 100.0 100.0CA 02265899 l999-03- 16W0 98/ 13449 PCT/US97ll 707782Example 5The following granular detergent formulations were prepared in accordwith the invention. Formulations W and X are of particular utilityunder US machine wash conditions. Y is of particular utility underJapanese machine wash conditionsT U VBlown PowderZeolite A 30.0 22.0 6.0Sodium Sulfate 19.0 5.0 7.0MA/AA 3.0 3.0 6.0LAS 14.0 12.0 22.0C45AS 8.0 7.0 7.0Silicate - 1 .0 5 .0Soap - - 2.0Brightener 1 0.2 0.2 0.2QEA 1 0.6 2.0 1.0Carbonate 8.0 16.0 20.0DTPMP - 0.4 0.4Spray On — 1.0 5.0C45E7 1.0 1.0 1.0Dry additivesHEDP 1.0 - —PVPVI/PVNO 0.5 0.5 0.5Protease 1 .0 1 .0 1.0Lipase 0.4 0.4 0.4Amylase 0.1 0.1 0.1Cellulase 0. 1 0.1 0.1NAC OBS - 6.1 4.5PB1 1 1.0 5 .0 6.0Sodium Sulfate — 6.0 -NACA 5.0 1.0 0.8Balance (Moisture and Misc)CA 02265899 l999-03- 16WO 98/13449 PCT/US97/17077Example 6The following granular detergent compositions of particular utilityunder European wash conditions were prepared in accord with theinvention. 1W XBlown powderZeolite A 20.0 —STPP - 20.0LAS 6.0 6.0C68AS 2.0 2.0Silicate 3.0 8.0MA/AA 4.0 2.0CMC 0.6 0.6QEA 1 0.9 0.6QEA 3 0.1 —Brightener 1 0.2 0.2DTPMP 0.4 0.4Spray on ‘C45E7 5.0 5.0Silicone antifoam 0.3 0.3Perfume 0.2 0.2Dry additivesCarbonate 14.0 9.0NAC OBS 6.0 2.0NACA — 4.0PB4 18.5 13.0TAED 2.0Photoactivated bleach 15 ppm 15 ppmProtease 1 .0 1 .0Lipase 0.2 0.2Amylase 0.4 0.4Cellulase 0. 1 0. 1Sulfate 10.0 20.0Balance (Moisture and Misc.)W0 98/ 13449CA 02265899 l999-03- 1684PCT/US97/17077Density (g/ litre)700700CA 02265899 l999-03- 16WO 98/13449 PCT/US97/1707785Example 7The following detergent compositions, according to the presentinvention were prepared:Y Z AABlown PowderZeolite A 15.0 15.0 15.0Sodium Sulfate 0.0 5.0 0.0LAS 3.0 3.0 3.0QAS — 1.5 1.5DTPMP 0.4 0.2 0.4CMC 0.4 0.4 0.4MA/AA 4.0 2.0 2.0AgglomeratesLAS 5.0 5.0 5.0TAS 2.0 2.0 1.0Silicate 3.0 3.0 4.0QEA 1 1.0 2.5 0.6Mn Catalyst 0.03 — -Zeolite A 8.0 8.0 8.0Carbonate 8.0 8.0 4.0Spray OnPerfume 0.3 0.3 0.3C45E7 2.0 2.0 2.0C25E3 2.0 - -Dry additivesCitrate 5.0 - 2.0Bicarbonate - 3.0 -Carbonate 8.0 15.0 10.0NAC OBS 6.0 2.0 4.0TAED - 2.0 -PB1 14.0 7.0 10.0NACA — 1.0 1.0Polyethylene oxide of MW 5,(IX),(XI) — — 0.2Bentonite clay - - 10.0EDDS — 2.0 —CA 022658991999-03-16wo 98/13449 PCT/US97/1707786Protease 1 .0 1 .0 1.0Lipase 0.4 0.4 0.4Amylase 0.6 0.6 0.6Cellulase 0.6 0.6 0.6Silicone antifoam 5.0 5.0 5.0Dry additivesSodium sulfate 0.0 3.0 0.0Balance (Moisture and Misc.) 100.0 100.0 100.0Density (g/litre) 850 850 850CA 02265899 l999-03- 16W0 93/13449 PCT/US97/1707787Example 8The following detergent formulations, according to the presentinvention were prepared:BB CC DD EELAS 20.0 14.0 24.0 22.0QAS 0.7 1.0 — 0.7TFAA — 1.0 - -C25E5/C45E7 - 2.0 - 0.5C45E3S — 2.5 - —STPP 30.0 18.0 30.0 22.0Silicate 9.0 5.0 10.0 8.0Carbonate 13.0 7.5 - 5.0Bicarbonate — 7.5 — -DTPMP 0.7 1.0 — —QEA 1 0.4 1.2 0.5 2.0QEA 2 0.4 - — —SRP 1 0.3 0.2 - 0.1MA/AA 2.0 1.5 2.0 1.0CMC 0.8 0.4 0.4 0.2Protease 0.8 1.0 0.5 0.5Amylase ‘ 0.8 0.4 - 0.25Lipase 0.2 0.1 0.2 0.1Cellulase 0.15 0.05 — -Photoactivated 70ppm 45ppm — 10ppmbleach (ppm)Brightener 1 0.2 0.2 0.08 0.2Percarbonate 6.0 5.0 9.0 15.0PB1 - 2.0 — —NAC OBS 4.2 5.0 2.0 1.0HEDP - - 2.3 -TEAD 2.0 1.0 - -Balance(Moisture andMiscellaneous)

Claims (23)

What is claimed is:

1. A granular detergent composition or component thereof comprising (a) a hydrophobic organic peroxyacid bleaching system, capable of providing a hydrophobic organic peroxyacid compound; and (b) a water-soluble cationic compound having clay soil removal/anti-redeposition properties, which is selected from the group consisting of:

1) ethoxylated cationic monoamines having the formula:
2) ethoxylated cationic diamines having the formula:

or wherein M1 is an N+ or N group; each M2 is an N+ or N group, and at least one M2 is an N+ group;

3) ethoxylated cationic polyamines having the formula:

4) mixtures thereof;
where A 1 is , , , , , , , , , - or - , R is H or C1-C4 alkyl or hydroxyalkyl, R1 is C2-C12 alkylene, hydroxyalkylene, alkenylene, arylene or alkarylene, or a C2-C3 oxyalkylene moiety having from 2 to about 20 oxyalkylene units provided that no O-N bonds are formed; each R2 is C1-C4 alkyl or hydroxyalkyl, the moiety -L-X, or two R2 together form the moiety -(CH2) r -A2-(CH2) s-, wherein A2 is -O- or -CH2-, r is 1 or 2, s is 1 or 2 and r + s is 3 or 4; each R3 is C1-C8 alkyl or hydroxyalkyl, benzyl, the moiety L-X, or two R3 or one R2 and one R3 together form the moiety -(CH2) r -A2-(CH2) s-; R4 is a substituted C3-C12 alkyl, hydroxyalkyl, alkenyl, aryl or alkaryl group having p substitution sites; R5 is C1-C12 alkenyl, hydroxyalkylene, alkenylene, arylene or alkarylene, or a C2-C3 oxyalkylene moiety having from 2 to about 20 oxyalkylene units provided that no O-O or O-N bonds are formed; X is a nonionic group selected from the group consisting of H, C1-C4 alkyl or hydroxyalkyl ester or ether groups, and mixtures thereof; L is a hydrophilic chain which contains the polyoxyalkylene moiety -[(R 6 O) m (CH2CH2O) n]-; wherein R6 is C3-C4 alkylene or hydroxyalkylene and m and n are numbers such that the moiety -(CH2CH2O) n- comprises at least about 50% by weight of said polyoxyalkylene moiety; d is 1 when M2 is N+ and is 0 when M2 is N; n is at least about 16 for said cationic monoamines, is at least about 6 for said cationic diamines and is at least about 3 for said cationic polyamines; p is from 3 to 8; q is 1 or 0; t is 1 or 0, provided that t is 1 when q is 1.

2. A granular detergent composition according to Claim 1 wherein said cationic compound is present at a level of from 0.01% to 30%
by weight of the detergent composition.

3. A granular detergent composition according to Claim 1 or 2 wherein the cationic compound is present at a level of from 0.2 % to 3 %
by weight of the detergent composition.

4. A granular detergent composition or component thereof according to any of Claims 1 to 3 wherein said cationic compound is an ethoxylated cationic monoamine and is characterized in that one R2 is methyl, two R2 are the moiety L-X, m is 0 and n is at least about 20.

5. A granular detergent composition or component thereof according to any of Claims 1 to 3 wherein said cationic compound is an ethoxylated cationic diamine and is characterized in that R1 is a C2- C6 alkylene.

6. A granular detergent composition or component thereof according to Claim 5 wherein said ethoxylated cationic diamine is characterized in that R1 is hexamethylene.

7. A granular detergent composition or component thereof according to any of Claims 5 to 6, wherein the cationic compounds is characterized in that each R2 is methyl or the moiety -L-X, each R3 is methyl and M1 and each M2 are an N+
group.

8. A granular detergent composition or component thereof according to any of Claims 5 to 7 wherein m is 0 and n is at least 12.

9. A detergent composition or component thereof according to any of Claims 1 to 3 wherein said cationic compound is an ethoxylated cationic polyamine and is characterized in that R4 is a substituted C3-C6 alkyl, hydroxyalkyl or aryl group; A1 is and p is from 3 to 6.

10. A granular detergent composition or component thereof according to any of Claims 5 to 7 wherein m is 0 and n is at least 20.

11. A granular detergent composition or component thereof according to any of Claims 1 to 10 wherein a cationic clay-soil removal/ anti- redeposition polymer is present characterised in that it has a backbone, at least 2M groups and at least one L-X group, wherein M is a cationic group attached to or integral with the backbone and contains an N+ positively charged centre; and L
connects groups M and X or connects group X to the polymer backbone; X is a nonionic group selected from the group consisting of H, C1-C4 alkyl or hydroxyalkyl ester or ether groups, and mixtures thereof; and L is a hydrophilic chain which contains the polyoxyalkylene moiety - [(R60) m (CH2CH20) n]-;

12. A granular detergent composition or component thereof according to Claim 11 wherein said cationic polymer is an ethoxylated cationic polymer which has a backbone, selected from the group consisting of the polyurethanes, the polyesters, the polyethers, the polyimides, the polyalkyleneimines and mixtures thereof.

13. A detergent composition or component thereof according to any of Claims 1 to 12 wherein said hydrophobic organic peroxyacid compound has at least 7 carbon atoms.

14. A detergent composition or component thereof according to any of Claims 1 or 13 wherein said hydrophobic organic peroxyacid bleaching system comprises a hydrogen peroxide source and a hydrophobic organic peroxyacid precursor.

15. A detergent composition according to Claim 14 wherein said hydrophobic organic peroxyacid precursor is present at a level of from 0.2% to 10% by weight of the detergent composition.

16. A detergent composition or component thereof according to either of Claims 14 or 15 wherein the organic peroxyacid precursor compound is an amide substituted alkyl peroxyacid precursor compound selected from the group consisting of and wherein L can be essentially any leaving group, R1 is an aryl or alkaryl group with from 1 to 14 carbon atoms, R2 is an alkylene, arylene, and alkarylene group containing from 1 to 14 carbon atoms, and R5 is H or an alkyl, aryl, or alkaryl group containing 1 to 10 carbon atoms such that R1 and R5 in total not contain more than 18 carbon.

17. A detergent composition or component thereof according to any of Claims 1 or 12 wherein said hydrophobic organic peroxyacid bleaching system comprises a preformed organic peroxyacid.

18. A detergent composition according to Claim 17 wherein said preformed organic peroxyacid is present at a level of from 1% to 10% by weight of the detergent composition.

19. A detergent composition or component thereof according to either of Claims 17 or 18 wherein the preformed organic peroxyacid is selected from the group consisting of:

and wherein R1 is an aryl or alkaryl group with from about 1 to about 14 carbon atoms, R2 is an alkylene, arylene, and alkarylene group containing from about 1 to 14 carbon atoms, and R5 is H or an alkyl, aryl, or alkaryl group containing 1 to 10 carbon atoms such that R1 and R5 not contain more than 18 carbon atoms total.

20. A granular detergent composition according to any of Claims 1 to 19 wherein the composition is formulated in such a manner as to provide a wash pH of from 8.0 to 10.5.

21. A detergent composition according to any of Claims 1 to 20 wherein a heavy metal ion sequestrant is present at a level of from 0.1 % to 10% by weight of the detergent composition.

22. A granular detergent composition or component thereof according to any of Claims 1 to 21 wherein a surfactant is present, selected from the group consisting of anionic, nonionic, cationic, ampholytic, amphoteric and zwitterionic surfactants and mixtures thereof.

23. A method of washing laundry in a domestic washing machine wherein an effective amount of a granular detergent composition according to any of Claims 1 to 22 is introduced into the drum of the washing machine, preferably before the commencement of the wash by use of a dispensing device which permits progressive release of said granular detergent composition into the wash liquor during the wash.