CA2265891A1 - Detergent particle - Google Patents

Abstract

The present invention relates to a particle containing cationic compounds with particulate/clay-soil removal/anti-redeposition properties and a carrier material, for use in detergent compositions or components thereof and a process for making the particle.

Description

W0 98/134515101520253035CA 02265891 1999-03-15PCTIUS97/16706Detergent particleTechnical FieldThe present invention relates to a particle containing cationic compounds withparticulate/ clay-soil removal/anti-redeposition properties and a carrier material. foruse in detergent compositions or components thereof and a process for making theparticle.Background to the InventionA particularly important property of a detergent composition is its ability to removeparticulate type soils from a variety of fabrics during laundering. Perhaps the mostimportant particulate soils are the clay—type soils. Clay soil particles generallycomprise negatively charged layers of alurninosilicates and positively chargedcations (e.g. calcium) which are positioned between and hold together the negativelycharged layers.In addition to clay soil removal, there is a need to keep the removed soil insuspension during the laundering (or dish washing) cycle. Soil which is removedfrom the fabric and suspended in the wash water can redeposit on the surface of thefabric. This redeposited soil causes a dulling or "greying" effect which is especiallynoticeable on white fabrics. To minimise this problem, anti-redeposition agents canbe included in the detergent composition.For example EP-B-111 965 discloses the use in detergents of cationic compounds,which have both clay-soil removal and anti-redeposition properties.SUBSTITUTE SHEET (RULE 26)W0 98/134530101520253035CA 02265891 1999-03-15PCT/US97/16706ix)US 4,659,802 and US 4,664,848 describe quatemized amines which have clay-soilremoval and anti-redeposition properties and which can be used in combination withanionic surfactants.The prior art teaches that these cationic compounds can be introduced into adetergent composition via an aqueous slurry, whereafter the product is atomised andspray dried.However, it has been found that the incorporation of the above described cationiccompound in granular detergent compositions or components thereof as described inthe prior art may result in problems such as malodour to the final detergent anddiscolouration of the (white) final detergent.The Applicants have now found that these problems can be ameliorated by the use ofa carefully chosen ratio of cationic compound to carrier material, or when a specificcarrier material absorbs or encapsulates the cationic, (partially) quatemizedethoxylated (poly) amines (which have clay-soil removal/anti-redepositionproperties). The present invention therefor provides a particle in which the cationiccompound is absorbed or bound or encapsulated in such a way that the particleformed is water-soluble, flowable and (temperature-) stable, and has an acceptableodour and colour in the final detergent.Another advantage of the carrier materials used herein is that they also havedetergent properties, such as builder capacities.Particles produced according to the preferred process for making the particle arefound to be very effective, having particularly good flowability, stability andsolubility, whilst overcoming malodour and discolouration problems.Detergent compositions or components thereof, containing this particle, are alsoenvisaged herein.All documents cited in the present description are, in relevant part, incorporatedherein by reference.SUBSTITUTE SHEET (RULE 26)101520W0 98/13453CA 02265891 1999-03-15PCT/US97/ 16706Summag of the InventionThe present invention relates to a particle comprising one or more cationiccompounds, which are cationic, (partially) quaternized ethoxylated (poly) aminecompounds with particulatel clay-soil removal / anti-redeposition properties, and acarrier material and optionally other material. Furthermore the present inventionrelates to a process for making this particle and the use thereof in detergentcompositions or components thereof.In more detail, the present invention relates to a particle comprising(a) a water-soluble cationic compound having clay soil removal/anti-redeposition properties, which is selected from the group consistingof:1)2)ethoxylated cationic monoamines having the formula:32IR2-—1T+—-L-—XR2ethoxylated cationic diamines having the formula:SUBSTITUTE SHEET (RULE 26)CA 02265891 l999-03- 15W0 98/ 13453 PCT/US97/ 167064fR3)d $3 ‘(R3)d $3X-—L-/M1--R1—/N+—L—-X or R3—I\[/I1—R1—N+-R or1|~ If L L LX X )|< Jr :1;$3)‘, R31(x—— L--)2—M2—R1—M2—-R2%R2wherein M1 is an N+ or N group; each M2 is an N+ or N group, and at leastone M2 is an N+ group;3) ethoxylated cationic polyamines having the formula:(.R3)dI4__ 1____ 5__’2_.__R [(A )q (R )t L XlpR21 0 4) mixtures thereof;SUBSTITUTE SHEET (RULE 26)CA 02265891 l999-03- 15W0 98/ 13453 PCT/US97/ 167065H H Ti H Hwhere1nA11s—-NC—, ——1foo—, —Nc1‘~I——, -—CI’\I—-, ——0cN—,I IR R R R R RT’ if i’ if i’—O0—, ———oco-, ——-oc——, -—CI'\IC~—or—--O-—,RR is H or C1-C4 alkyl or hydroxyalkyl, R1 is C2-C12 alkylene, hydroxyalkylene,alkenylene, aiylene or alkarylene, or a C2-C3 oxyalkylene moiety having from 2 to5 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),-A2-(CH2)s-, wherein A2 is -0- or -CH2-, r is 1 or 2, s is 1 or 2 and r + s is 3or 4; each R3 is C1-C3 alkyl or hydroxyalkyl, benzyl, the moiety L-X, or two R3 orone R2 and one R3 together form the moiety -(CH2),-A2-(CH2)s-; R4 is a10 substituted C3-C1;)_ alkyl, hydroxyalkyl, alkenyl, aryl or alkaryl group having psubstitution sites; R5 is C1-C12 alkenyl, hydroxyalkylene, alkenylene, arylene oralkarylene, or a C2-C3 oxyalkylene moiety having from 2 to about 20 oxyalkyleneunits provided that no 0-0 or O-N bonds are formed; X is a nonionic group selectedfrom the group consisting of H, C1-C4 alkyl or hydroxyalkyl ester or ether groups,15 and mixtures thereof; L is a hydrophilic chain which contains the polyoxyalkylenemoiety-[(R5O),,,(CH2CH2O),,]-; wherein R6 is C3-C4 alkylene or hydroxyalkylene and mand n are numbers such that the moiety-(CH2CH2O),,- comprises at least about 50% by weight of said polyoxyalkylene2o moiety; d is 1 when M2 is N+ and is 0 when M2 is N; n is at least about 16 for saidcationic monoamines, is at least about 6 for said cationic diamines and is at leastabout 3 for said cationic polyamines; p is fiom 3 to 8; q is l or 0; t is 1 or 0, providedthattis l whenq is l;andSUBSTITUTE SHEET (RULE 26)101520253035WO 98/13453CA 02265891 1999-03-15PCT/US97l 16706(b) a powdered carrier material, wherein the ratio of (a) to (b) is from 1:15to 4:1 by weight.The invention also relates to a particle comprising:(a) a water-soluble cationic compound having clay soil removal/anti-redeposition properties, selected from the compounds mentioned in (a)above;and(b) an aluminosilicate carrier material.Detailed description of the inventionThe particleIn a first aspect of the present invention, the particle of the present inventioncomprises a water-soluble cationic compound and one or more powdered carriermaterials, present in a ratio from 1:15 to 4:1 by weight, more preferably from 1:7 to1:1, most preferably from 1:4 to 1: 1.5 by weight. In a second aspect, the presentinvention provides a particle comprising a water-soluble cationic compound and oneor more aluminosilicate carrier materials.Optionally other detergent ingredients can be present in the particle, preferablyanionic surfactants and/ or polyethylene glycols (as described herein).The particle size of the particles in accord with the present invention shouldpreferably be such that no more of than 15% of the particles are greater than 1.8mmin diameter and no more than 15% of the particles are smaller than 0.25mm indiameter. Preferably the mean particle size is such that 10% to 50% of the particleshas a particle size of from 0.2mm to 0.7mm in diameter.The term mean particle size as defined herein is calculated by sieving a sample of thecomposition into a number of fractions (typically 5 fractions) on a series of sieves,preferably Tyler sieves. The weight fractions thereby obtained are plotted against theSUBSTITUTE SHEET (RULE 26)101520253035W0 98/ 13453CA 02265891 1999-03-15PCT/US97/ 16706aperture size of the sieves. The mean particle size is taken to be the aperture sizethrough which 50% by weight of the sample would pass.Cationic compoundAn essential feature of the present invention is a water-soluble cationic compoundwhich has paiticu1ate/ clay-soil removal/anti-redeposition properties and which isselected from the group consisting of cationic mono- di- and polyamines.In the particle in accord with the present invention the ratio of cationic compound tothe powdered carrier material and preferably to the aluminosilicate carrier material isfrom 1:15 to 4:1 by weight, more preferably from 1:7 to 1:1, most preferably from1:4 to 1: 1.5 by weight.If the particle in accord with the invention is present in a detergent composition. thewater-soluble cationic compound is preferably present in the detergent compositionat a level of from 0.01% to 30%. more preferably from 0.1% to 15% , mostpreferably from 0.2% to 3.0% by weight of the detergent composition.If the cationic compound does not have a desirable colour, particularly when thecompound is not white. the cationic compound can be discoloured beforeincorporation in the particle of the invention by any standard method.Cationic aminesThe water-soluble cationic compounds of the present invention, which are useful ingranular detergent compositions or components thereof, include ethoxylated cationicmonoamines. ethoxylated cationic diamines and ethoxylated cationic polyamines aspreviously defined.In the preceding formulae for the cationic amines, R1 can be branched(e.g.SUBSTITUTE SHEET (RULE 26)10152025CA 02265891 1999-03-15WO 98/13453 PCT/US97/167068‘F3—CH2—C}3H"'“ ,—"CH2‘—CH"“);C3cyclic (e.g. ——-<:>—— ),or most preferably linear(e. g. ** CHZCHZ —— , ‘— CHZCHZCHZ ”—)alkylene, hydroxyalkylene, alkenylene, alkarylene or oxyalkylene. R1 is preferablyC2-C6 alkylene for the ethoxylated cationic diamines. Each R2 is preferably methylor the moiety -L-X; each R3 is preferably C1-C4 alkyl or hydroxyalkyl, and mostpreferably methyl.The positive charge of the N+ groups is offset by the appropriate number of counteranions. Suitable counter anions include Cl-, Br-, S03-2, P04-2, MeOSO3- and thelike. Particularly preferred counter anions are Cl- and Br-.X can be a non-ionic group selected from hydrogen (H), C1-C4 alkyl orhydroxyalkyl ester or ether groups, or mixtures thereof. Preferred esters or ethers arethe acetate ester and methyl ether, respectively. The particularly preferred nonionicgroups are H and the methyl ether.In the preceding formulae, hydrophilic chain L usually consists entirely of thepolyoxyalkylene moiety -[(R6O),,,(CH2CH2_O,,)-]. The moieties -(R6O)m- and -(CH2CH2O)n- of the polyoxyalkylene moiety can be mixed together or preferably formblocks of -(R5O),,,- and -(CI-l2CH2O),,- moieties. R6 is preferably C31-I5 (propylene); mSUBSTITUTE SHEET (RULE 25)10152025WO 98113453CA 02265891 1999-03-15PCT/U S97/ 16706is preferably from 0 to about 5 and is most preferably 0, i.e. the polyoxyalkylene moietyconsists entirely of the moiety -(CH2CH2O),,-. The moiety -(CH2CH2O),,- preferablycomprises at least about 85% by weight of the polyoxyalkylene moiety and mostpreferably 100% by weight (m is 0). VIn the preceding formulas, M1 and each M2 are preferably an N+ group for thecationic diamines and polyamines.Preferred ethoxylated cationic monoamines and diamines have the formula:‘W3 ‘EH3XJr0cH2cH2>,. v‘r*—cH2~—cH2-<~cH2>a b1f*—cH2cH20%ax(CH2CH207fiX (CH2CH203HXwherein X and n are defined as before, a is from 0 to 20, preferably from O to 4 (e.g.ethylene, propylene, hexamethylene) b is 1 or 0. For preferred cationic monoamines(b=0), n is preferably at least about 16, with a typical range of from about 20 toabout 35. For preferred cationic diamines (b=l), n is at least about 12 with a typicalrange of from about 12 to about 42.In the preceding formula for the ethoxylated cationic polyarnines, R4 (linear,branched, or cyclic) is preferably a substituted C3-C5 alkyl, hydroxyalkyl or arylgroup; A1 is preferably0HHn is preferably at least about 12, with a typical range of from about 12 to about 42; pis preferably from 3 to 6. When R4 is a substituted aryl or alkaryl group, q ispreferably 1 and R5 is preferably C2-C3 alkylene. When R4 is a substituted alkyl,SUBSTITUTE SHEET (RULE 25)CA 02265891 l999-03- 15W0 98,13,453 PCT/US97/16706hydroxyalkyl, or alkenyl group, and when q is 0, R5 is preferably a C2-C3oxyalkylene moiety; when q is 1, R5 is preferably C2-C3 alkylene.These ethoxylated cationic polyamines can be derived from polyamino amides such5 as:if[Clrj-(-C3H6-j-NH2IM’ ‘fHO ;- N —c H NH CN(C H —)—NHlH‘<36“r2°'\\? H36 219 3-CN—(~C3H6—rNH2HThese ethoxylated cationic polyamines can also be derived from10 polyaminopropyleneoxide derivatives such as:wherein each c is a number from 2 to about 20.15Carrier materialAnother essential component of the particle of the present invention is one or morepowdered carrier materials.SUBSTITUTE SHEET (RULE 26)1015202530W0 98/13453CA 02265891 1999-03-15PCT/U S97! 1670611In the particle in accord with the first aspect of the present invention the ratio ofcationic compound to the powdered carrier material and preferably to thealuminosilicate carrier material is from 1:15 to 2:1 by weight, more preferably from1:7 to 1:1, most preferably from 1:4 to 1: 1.5 by weight.The carrier material will preferably be a white, free-flowing material with a lowwater content, preferably less than 25%, more preferably less than 15%, mostpreferably less than 10% by weight of the carrier material.The carrier material preferably has a porous or crystalline structure, providing thus acarrier material with a high surface area for a better interaction with the water-solublecationic compound (and optionally other detergent ingredients).Preferred carrier materials are certain inorganic and organic powders or salts. morepreferably certain water-soluble and partially or largely water insoluble buildermaterials.Suitable organic powders include alkyl or alkylene sulphates, borates or phosphates,preferably alkyl sulphates.Preferred inorganic powdered carrier materials include carbonates. bicarbonates,silicates, sulphates and phosphates.Suitable water-soluble builder materials include the water soluble monomericpolycarboxylates, or their acid forms.A highly preferred carrier material is citrate or citric acid.Other highly preferred examples of carrier materials which are largely waterinsoluble builder materials and which are essential in the second aspect of theinvention, include the aluminosilicates, preferably sodium aluminosilicates. Zeolitesare highly preferred.SUBSTITUTE SHEET (RULE 25)101520253035W0 98l13453CA 02265891 1999-03-15PCT/U S97/ 1670612Suitable aluminosilicate zeolites have the unit cell formula NaZ[(AlO2)Z(SiO2)y].xH2O wherein z and y are at least 6; the molar ratio of z to y is from 1.0 to 0.5 and xis at least 5, preferably such that no more than 25%, more preferably no more than10%, most preferably no more than 5% structure bound water is present, by weightof the aluminosilicate zeolite.The aluminosilicate zeolites can be naturally occurring materials, but are preferablysynthetically derived. Synthetic crystalline aluminosilicate ion exchange materials foruse herein are available under the designations Zeolite A, Zeolite B, Zeolite P,Zeolite X, Zeolite HS and mixtures thereof.Another preferred aluminosilicate zeolite carrier material is zeolite MAPbuilder.Zeolite MAP is described in EP 38407OA (Unilever). It is defined as an alkalimetal alumino-silicate of the zeolite P type having a silicon to aluminium rationot greater than 1.33, preferably within the range from 0.9 to 1.33 and morepreferably within the range of from 0.9 to 1.2.Of particular interest is zeolite MAP having a silicon to aluminium ratio notgreater than 1.15 and, more particularly, not greater than 1.07.In a preferred aspect the alumino silicates. especially zeolite MAP, have aparticle size, expressed as a d50 value of from 1.0 to 10.0 micrometres, morepreferably from 2.0 to 7.0 micrometres, most preferably from 2.5 to 5.0micrometres.The d50 value indicates that 50% by weight of the particles have a diametersmaller than that figure. The particle size may, in particular be determined byconventional analytical techniques such as microscopic determination using ascanning electron microscope or by means of a laser granulometer. Othermethods of establishing d50 values are disclosed in EP 38407OA.The carrier material comprised in the particle of the present invention can comprise asingle carrier material. Preferred carrier materials are mentioned above. AluminoSUBSTITUTE SHEET (RULE 26)5101520253035WO 98/13453CA 02265891 1999-03-15PCT/US97/1670613silicate materials are particularly preferred. Preferably one of the preferred carriermaterials forms at least 50%, more preferably more than 70%, most preferably morethan 80% by weight of the carrier material in the particle.Process for making of a particleThe particle can be made by mixing or spray drying of the carrier material andcationic compound, and optionally other ingredients.In a preferred aspect, the cationic compound is purified before formation of theparticle. A particularly preferred purification step can be the removal from thecationic compound of volatile compounds which can cause a malodour, by use of asteam stripping process, whereafter the cationic compound can be incorporated in aparticle in accord with the present invention. An example is disclosed in EP 1 ll965A.Preferably, the particle of the present invention is made via an agglomerationprocess.This preferred agglomeration process comprises the following steps:(a) heating of the water—solub1e cationic compound to obtain a meltedcompound;(b) agglomerating the melted compound of (a) with the carrier material toa agglomerate particle;(c) cooling the agglomerate particle of (b).Suitable agglomeration techniques used for step (B) are described in more detail inthe Applicants co-pending European Application EP-A-643130. In a highly preferredagglomeration process the melted compound of the present invention is intimatelymixed with the powdered carrier material in a high shear mixer. such as a Loedige®CB unit. The agglomerate particles may be finished in further mixing units, such as aLoedige® KM, or a fluidised bed.SUBSTITUTE SHEET (RULE 26)W0 98ll34531015202530CA 02265891 1999-03-15PCT/US97/1670614In step (c) the agglomerate particles are preferably cooled in a fluidised bed cooler bypassing cool air.Additionally, more than one carrier materials can be added in step (b).Optional detergent ingredients can also be added in step (b). However, preferablyoptional detergent ingredients are added to the melted compound before step (b).Optionally, in step (c) the agglomerate particle is dried before cooled, preferably byuse of a fluid bed dryer by passing hot air.Another technique for obtaining the particle of the present invention is by use ofspray drying techniques. Suitable techniques for spraying the melted compound ontopowdered carrier material(s) are described in the Applicants co-pending PatentApplication WO940576l, published on 17th March 1994.Optional ingredients in the particleOptional ingredients can be comprised in the particle of the present invention, whichcan be selected from the additional detergent components described hereinafter.When comprised in the particle they are preferably present at a level of from 0.05%to 30%, more preferably from 0.5% to 20%, most preferably from 1.0% to 15% byweight of the particle.Preferred optional detergent ingredients present in the particle of the presentinvention are anionic surfactants, preferably alkyl sulphates. alkyl benzenesulphonates or alkyl sulphates condensed with ethylene oxide and polyethyleneglycols, preferably with a molecular weight of from 5000 to 10000.Another preferred ingredient in the particles of the present invention is a cationicpolymers, which has clay-soil removal/ anti-redeposition properties, as described inthe next paragraph.SUBSTITUTE SHEET (RULE 26)1015202530W0 98/ 13453CA 02265891 1999-03-15PCT/US97/1670615Detergent compositions or components thereofThe particle of the present invention can be incorporated in detergent compositions(or be combined with components thereof).If the particle in accord with the invention is present in a detergent compositionthereof, this will be done in such a manner that the water-soluble cationic compoundis preferably present in the detergent composition at a level of from 0.01% to 30%,more preferably from 0.1% to 15% , most preferably from 0.2% to 3.0% by weight ofthe detergent composition.The precise nature of the additional detergent ingredients (some of which can also becomprised in the particle of the present invention as optional ingredient) of thesedetergent compositions or components thereof, and levels of incorporation thereofwill depend on the physical form of the composition or component thereof, and theprecise nature of the washing operation for which it is to be used.The detergent compositions or components thereof preferably contain one or moreadditional detergent components selected from (additional) surfactants, (additional)builders, sequestrants, bleach, bleach precursors, bleach catalysts, organic polymericcompounds. additional enzymes, suds suppressors, lime soap dispersants, additionalsoil suspension and anti-redeposition agents soil releasing agents, perfumes andcorrosion inhibitors.(Additional ) SurfactantThe detergent compositions or components thereof preferably contain an (additional)surfactant selected from anionic, nonionic, cationic, ampholytic, amphoteric andzwitterionic surfactants and mixtures thereof.A typical listing of anionic, nonionic, ampholytic, and zwitterionic classes, andspecies of these surfactants, is given in U.S.P. 3,929,678 issued to Laughlin andHeuring on December 30, 1975. Further examples are given in "Surface ActiveAgents and Detergents" (Vol. I and II by Schwartz, Perry and Berch). A list ofSUBSTITUTE SHEET (RULE 26)101520253035W0 98Il3453CA 02265891 1999-03-15PCT/U S97! 1670616suitable cationic surfactants is given in U.S.P. 4,259,217 issued to Murphy on March31, 1981.Where present, ampholytic, amphoteric and zwitteronic surfactants are generallyused in combination with one or more anionic and/or nonionic surfactants.Anionic surfactantThe detergent compositions or components thereof preferably comprise an additionalanionic surfactant. Essentially any anionic surfactants useful for detersive purposescan be comprised in the detergent composition. These can include salts (including,for example, sodium, potassium, ammonium, and substituted ammonium salts suchas mono-, di- and triethanolamine salts) of the anionic sulfate, sulfonate, carboxylateand sarcosinate surfactants. Anionic sulfate surfactants are preferred.Other anionic surfactants include the isethionates such as the acyl isethionates, N-acyl taurates, fatty acid amides of methyl tauride, alkyl succinates andsulfosuccinates, monoesters of sulfosuccinate (especially saturated and unsaturatedC12-CC 6-C1 4 diesters), N-acyl sarcosinates. Resin acids and hydrogenated resin acids are18 monoesters) diesters of sulfosuccinate (especially saturated and unsaturatedalso suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenatedresin acids present in or derived from tallow oil.Anionic sulfate surfactantAnionic sulfate surfactants suitable for use herein include the linear and branchedprimary and secondary alkyl sulfates, alkyl ethoxysulfates, fatty oleoyl glycerolsulfates, alkyl phenol ethylene oxide ether sulfates, the C5-C17 acyl-N-(C1-C4 alkyl)and -N-(C1-C2 hydroxyalkyl) glucamine sulfates, and sulfates ofalkylpolysaccharides such as the sulfates of alkylpolyglucoside (the nonionicnonsulfated compounds being described herein).Alkyl sulfate surfactants are preferably selected from the linear and branched primaryC10-C13 alkyl sulfates, more preferably the C11-C15 branched chain alkyl sulfatesand the C12-C14 linear chain alkyl sulfates.SUBSTITUTE SHEET (RULE 26)101520253035WO 98/13453CA 02265891 1999-03-15PCT/US97/ 1670617Alkyl ethoxysulfate surfactants are preferably selected from the group consisting ofthe C10-C13 alkyl sulfates which have been ethoxylated with from 0.5 to 20 molesof ethylene oxide per molecule. More preferably, the alkyl ethoxysulfate surfactant isa C11-C13, most preferably C1 1-C15 alkyl sulfate which has been ethoxylated withfrom 0.5 to 7, preferably from 1 to 5, moles of ethylene oxide per molecule.A particularly preferred aspect of the invention employs mixtures of the preferredalkyl sulfate and alkyl ethoxysulfate surfactants. Such mixtures have been disclosedin PCT Patent Application No. W0 93/ 1 8124.Anionic sulfonate surfactantAnionic sulfonate surfactants suitable for use herein include the salts of C 5-C20linear alkylbenzene sulfonates. alkyl ester sulfonates, C6-C22 primary or secondaryalkane sulfonates, C5-C24 olefin sulfonates, sulfonated polycarboxylic acids. alkylglycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfonates. andany mixtures thereof.Anionic carboxvlate surfactantSuitable anionic carboxylate surfactants include the alkyl ethoxy carboxylates. thealkyl polyethoxy polycarboxylate surfactants and the soaps (‘alkyl carboxyls‘).especially certain secondary soaps as described herein.Suitable alkyl ethoxy carboxylates include those with the formula RO(CH;)_CHg0)xCH2C00‘M+ wherein R is a C6 to C13 alkyl group, x ranges from O to 10, and theethoxylate distribution is such that, on a weight basis, the amount of material where xis 0 is less than 20 % and M is a cation. Suitable alkyl polyethoxy polycarboxylatesurfactants include those having the formula R0-(CHR1-CHR2-O)-R3 wherein R isa C6 to C18 alkyl group, x is from 1 to 25, R1 and R2 are selected from the groupconsisting of hydrogen, methyl acid radical, succinic acid radical, hydroxysuccinicacid radical, and mixtures thereof, and R3 is selected from the group consisting ofhydrogen, substituted or unsubstituted hydrocarbon having between 1 and 8 carbonatoms, and mixtures thereof.SUBSTITUTE SHEET (RULE 26)101520253035WO 98113453CA 02265891 1999-03-15PCT/US97/ 1670618Suitable soap surfactants include the secondary soap surfactants which contain acarboxyl unit connected to a secondary carbon. Preferred secondary soap surfactantsfor use herein are water-soluble members selected from the group consisting of thewater-soluble salts of 2-methyl-1-undecanoic acid, 2—ethyl-l—decanoic acid, 2-propyl-l-nonanoic acid, 2-butyl-l-octanoic acid and 2—pentyl—1—heptanoic acid. Certainsoaps may also be included as suds suppressors.Alkali metal sarcosinate surfactant Other suitable anionic surfactants are the alkali metal sarcosinates of formula R-CON(R1) CH2 COOM, wherein R is a C5-C17 linear or branched alkyl or alkenyl group,R1 is a C1—C4 alkyl group and M is an alkali metal ion. Preferred examples are themyristyl and oleoyl methyl sarcosinates in the form of their sodium salts.Alkoxylated nonionic surfactantEssentially any alkoxylated nonionic surfactants are suitable herein. The ethoxylatedand propoxylated nonionic surfactants are preferred.Preferred alkoxylated surfactants can be selected from the classes of the nonioniccondensates of alkyl phenols, nonionic ethoxylated alcohols, nonionicethoxylated/propoxylated fatty alcohols, nonionic ethoxylate/propoxylatecondensates with propylene glycol, and the nonionic ethoxylate condensationproducts with propylene oxide/ethylene diamine adducts.Nonionic alkoxylated alcohol surfactantThe condensation products of aliphatic alcohols with from 1 to 25 moles of alkyleneoxide, particularly ethylene oxide and/or propylene oxide, are suitable for use herein.The alkyl chain of the aliphatic alcohol can either be straight or branched, primary orsecondary, and generally contains from 6 to 22 carbon atoms. Particularly preferredare the condensation products of alcohols having an alkyl group containing from 8 to20 carbon atoms with from 2 to 10 moles of ethylene oxide per mole of alcohol.SUBSTITUTE SHEET (RULE 26)1015202530W0 98/ 13453CA 02265891 1999-03-15PCT/US97l1670619Nonionic polvhvdroxv fatty acid amide surfactantPolyhydroxy fatty acid amides suitable for use herein are those having the structuralformula RZCONRIZ wherein : R1 is H, C1-C4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl, ethoxy, propoxy, or a mixture thereof, preferable C1-C4 alkyl, morepreferably C1 or C2 alkyl, most preferably C1 alkyl (i.e., methyl); and R2 is a C5-C 31 hydrocarbyl, preferably straight-chain C5-C19 alkyl or alkenyl, more preferablystraight-chain C9-C17 alkyl or alkenyl, most preferably straight-chain C11-C17 alkylor alkenyl, or mixture thereof; and Z is a polyhydroxyhydrocarbyl having a linearhydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or analkoxylated derivative (preferably ethoxylated or propoxylated) thereof. Z preferablywill be derived from a reducing sugar in a reductive amination reaction; morepreferably Z is a glycityl.Nonionic fattv acid amide surfactantSuitable fatty acid amide surfactants include those having the formula: R6CON(R7)2wherein R6 is an alkyl group containing from 7 to 21, preferably from 9 to 17 carbonatoms and each R7 is selected from the group consisting of hydrogen, C1-C4 alkyl,C 1-C4 hydroxyalkyl, and -(C2H4O)xH, where x is in the range of from 1 to 3.Nonionic alkylpolysaccharide surfactantSuitable alkylpolysaccharides for use herein are disclosed in U.S. Patent 4,565,647,Llenado, issued January 21, 1986, having a hydrophobic group containing from 6 to30 carbon atoms and a polysaccharide, e.g., a polyglycoside, hydrophilic groupcontaining from 1.3 to 10 saccharide units.Preferred alkylpolyglycosides have the formulaR2O(CnH2n0)t(g1YC05Y1)xwherein R2 is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl,hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups contain from 10SUBSTITUTE SHEET (RULE 26)101520253035W0 98/ 13453CA 02265891 1999-03-15PCTIU S97I 1670620to 18 carbon atoms; n is 2 or 3; t is from 0 to 10, and x is from 1.3 to 8. The glycosylis preferably derived from glucose.Amphoteric surfactantSuitable amphoteric surfactants for use herein include the amine oxide surfactantsand 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 mixtures thereof, containing from 8 to26 carbon atoms; R4 is an alkylene or hydroxyalkylene group containing from 2 to 3carbon atoms, or mixtures thereof; x is from 0 to 5, preferably from 0 to 3; and eachR5 is an alkyl or hydroxyalkyl group containing from 1 to 3, or a polyethylene oxidegroup containing from 1 to 3 ethylene oxide groups. Preferred are C10-C13 alkyldimethylamine oxide, and C10_1 3 acylamido alkyl dimethylamine oxide.A suitable example of an alkyl aphodicarboxylic acid is Miranol(TM) C2M Cone.manufactured by Miranol, lnc., Dayton, NJ.Zwitterionic surfactantZwitterionic surfactants can also be incorporated into the detergent compositions orcomponents. These surfactants can be broadly described as derivatives of secondaryand tertiary amines, derivatives of heterocyclic secondary and tertiary amines, orderivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfoniumcompounds. Betaine and sultaine surfactants are exemplary zwitterionic surfactantsfor use herein.Suitable betaines are those compounds having the formula R(R')2N+R2COO‘wherein R is a C6-C1}; hydrocarbyl group, each R1 is typically C1-C3 alkyl, and R2is a C1-C5 hydrocarbyl group. Preferred betaines are C124 3 dimethyl-ammoniohexanoate and the C1 0-1 3 acylamidopropane (or ethane) dimethyl (or diethyl)betaines. Complex betaine surfactants are also suitable for use herein.SUBSTITUTE SHEET (RULE 26)W0 98/134531015202530CA 02265891 1999-03-15PCT /US97/1670621Cationic surfactantsSuitable cationic surfactants to be used in the detergent compositions or componentsthereof, herein include the quaternary ammonium surfactants selected from monoC6-C16, preferably C6-C10 N-alkyl or alkenyl ammonium surfactants wherein theremaining N positions are substituted by methyl, hydroxyethyl or hydroxypropylgroups.Another suitable group of cationic surfactants which can be used in thedetergent compositions or components thereof, for use herein are cationic estersurfactants.The cationic ester surfactant is a, preferably water dispersible, compound havingsurfactant properties comprising at least one ester (i.e. -COO-) linkage and at leastone cationically charged group.Suitable cationic ester surfactants, including choline ester surfactants, have forexample been disclosed in US Patents Nos. 4228042, 4239660 and 4260529.In one preferred aspect the ester linkage and cationically charged group are separatedfrom each other in the surfactant molecule by a spacer group consisting of a chaincomprising at least three atoms (i.e. of three atoms chain length), preferably fromthree to eight atoms, more preferably from three to five atoms, most preferably threeatoms. The atoms forming the spacer group chain are selected from the groupconsisting of carbon, nitrogen and oxygen atoms and any mixtures thereof, with theproviso that any nitrogen or oxygen atom in said chain connects only with carbonatoms in the chain. Thus spacer groups 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-CH} linkages are included. In a preferred aspect thespacer group chain comprises only carbon atoms, most preferably the chain is ahydrocarbyl chain.SUBSTITUTE SHEET (RULE 26)10152025WO 98/13453CA 02265891 1999-03-15PCT/US97/1670622Cationic polymersThe detergent composition or components thereof can comprise additional polymericcationic ethoxylated amine compounds with particulatel clay-soil removal/ anti-redeposition, selected from the group consisting of water-soluble cationic polymers.These polymers comprise a polymer backbone, at least 2M groups and at least on L-X group, wherein M is a cationic group attached to or integral with the backbone; Xis a nonionic group selected from the group consisting of H, C1 -C4 alkyl orhydroxyalkyl ester or ether groups, and mixtures thereof; and L is a hydrophilic chainconnecting groups M and X or connecting X to the polymer backbone.The polymeric cationic ethoxylated amine compounds can be present in detergentcompositions at a level of from 0.01% to 30%, more preferably from 0.1% to 15%,most preferably from 0.2% to 3% by weight of the detergent composition.As used herein, the term "polymer backbone" refers to the polymeric moiety to whichgroups M and L-X are attached to or integral with. Included within this term areoligomer backbones (2 to 4 units), and true polymer backbones (5 or more units).As used herein, the term "attached to " means that the group is pendent from thepolymer backbone, examples of which are represented by the following generalstructures A and B:IM J.MA )|()l(A BAs used herein, the term "integral with" means that the group forms part of thepolymer backbone, examples of which are represented by the following generalstructures C and D:SUBSTITUTE SHEET (RULE 26)CA 02265891 l999-03- 15wo 93/13453 PCT/US97/1670623CAny polymer backbone can be used as long as the cationic polymer formed is water-5 soluble and has clay soil removal/anti-redeposition properties. Suitable polymerbackbones can be derived from the polyurethanes, the polyesters, the polyethers, thepolyamides, the polyimides and the like, the polyacrylates, the polyacrylamides, thepolyvinylethers, the polyethylenes, the polypropylenes and like polyalkylenes, thepolystyrenes and like polyalkarylenes, the polyalkyleneamines, the10 polyalkyleneimines, the polyvinylamines, the polyalylamines, the polydiallylamines,the polyvinylpyridines, the polyarninotriazoles, polyvinyl alcohol, theaminopolyureylenes, and mixtures thereof.M can be any compatible cationic group which comprises an N*’ (quarternary),15 positively charged center. The quanernary positively charged center can berepresented by the following general structures E and F:20 Particularly preferred M groups are those containing a quatternary center representedby general structure E. The cationic group is preferably positioned close to orintegral with the polymer backbone.SUBSTITUTE SHEET (RULE 26)WO 98/134531015202530CA 02265891 1999-03-15PCTlUS97l 1670624The positive charge of the N+ centres is offset by the appropriate number of counteranions. Suitable counter anions include Cl‘, Br“, S032’, S042‘, PO42‘, MeOSO3'and the like. Particularly preferred counter anions are Cl’ and Br‘.X can be a nonionic group selected from hydrogen (H), C1-C4 alkyl or hydroxyalkylester or ether groups, and mixtures thereof. The preferred ester or ether groups arethe acetate ester and methyl ether, respectively; The particularly preferred nonionicgroups are H and the methyl ether.The cationic polymers suitable for use in granular detergent compositions in accordwith the present inventions normally have a ratio of cationic groups M to nonionicgroups X of from about 1:1 to about 1:2. However, for example, by appropriatecopolymerization of cationic, nonionic (i.e. containing the group L-X), and mixedcationic/nonionic monomers, the ratio of cationic groups M to nonionic groups X canbe varied. The ratio of groups M to groups X can usually range from about 2:1 toabout 1:10. In preferred cationic polymers, the ratio is from about 1:1 to about 1:5.The polymers formed from such copolymerization are typically random, i.e. thecationic, nonionic and mixed cationic/nonionic monomers copolymerize in anonrepeating sequence.The units which contain groups M and groups L-X can comprise 100% of thecationic polymers of the present invention. However, inclusion of other units(preferably nonionic) in the polymers is also permissible. Examples of other unitsinclude acrylamides, vinyl ethers and those containing unquaternized tertiary aminegroups (M1) containing an N centre. These other units can comprise from 0% toabout 90% of the polymer (from about 10% to 100% of the polymer being unitscontaining M and L-X groups, including M1-L-X groups). Normally, these otherunits comprise from 0% to about 50% of the polymer (from about 50% to 100% ofthe polymer being units containing M and L-X groups).The number of groups M and L-X each usually ranges from about 2 to about 200.Typically the number of groups M and L-X are each from about 3 to about 100.Preferably, the ntunber of groups M and L-X are each from about 3 to about 40.SUBSTITUTE SHEET (RULE 26)WO 98/1345310152025CA 02265891 1999-03-15PCT/U S97/ 1670625Other than moieties for connecting groups M and X, or for attachment to thepolymer backbone, hydrophilic chain L usually consists entirely of thepolyoxyalkylene moiety -[(R’O),,,(CH2CH2O),,]-. The moieties -(R'O),,,- and -(CH2CH2O),,- of the polyoxyalkylene moiety can be mixed together, or preferablyform blocks of -(R'O),,,- and -(CH2CH2O),,- moieties. R’ is preferably C3H5(propylene); m is preferably from O to about 5, and most preferably 0; i.e. thepolyoxyalkylene moiety consists entirely of the moiety -(CHQCI-120),,-. The moiety-(CH2CH2O)n- preferably comprises at least about 85% by weight of thepolyoxyalkylene moiety, and most preferably 100% by weight (In is 0). For themoiety -(CH2CH2O),,-, n is usually from about 3 to about 100. Preferably n, is fromabout 12 to about 42.A plurality (2 or more) of moieties -L-X can also be hooked together and attached togroup M or to the polymer backbone, examples of which are represented by thefollowing general structures G and H:MJTTTLT71 f*”"*II4 ,i r f 5X IX X XG HStructures such as G and H can be formed, for example, by reacting glycidol withgroup M or with the polymer backbone, and ethoxylating the subsequently formedhydroxy groups.Representative classes of cationic polymers of the present invention are as follows:A. Polyurethane, Polyester, Polyether, Polyamide or like Polymers.SUBSTITUTE SHEET (RULE 26)CA 02265891 l999-03- 15W0 98,13453 PCT/US97/1670626One class of suitable cationic polymers are derived from polyurethanes, polyesters,polyethers, polyamides and the like. These polymers comprise units selected fromthose having formulas I, II and III:R4ImLmLmm—fi~W—fiX<R5>rt<C3H60>m<CH2CH20>n1-xgR62>kmLmLmm—fi~#—fi Hy137 111%LRL%m_fi_?_QI<R5>r t<CeH60>m<CH2CH20>rXMmmflmo o 0 oH H 11 H H*TGfi—OPfi*K%fi—%—fln—€*,R RSUBSTITUTE SHEET (RULE 25)101520WO 98/13453CA 02265891 1999-03-15PCT/U S97! 1670627X is 0 or 1; R is H or C1-C4 alkyl or hydroxyalkyl; R1 is C2-C12 alkylene,hydroxyalkylene, alkenylene, cycloalkylene, aryiene or alkarylene, or a C2-C3oxyalkylene moiety having from 2 to abut 20 oxyalkylene units provided that no 0-0or O-N bonds are formed with A1; when x is 1, R2 is -R5- except when A1 is‘H’__._C___’or is -(OR8)y- or -OR5- provided that no 0-0 or N-O bonds are formed with A1, andR3 is -R5- except when A1 is‘H’______C_Z.,or is -(R30)-y or -R5O- provided that no O~O or O-N bonds are formed with A1;when x is 0, R2 isIO O O““‘I’fi3"5“’“T’?.’°“5”“tE”«“‘5”"°’"°ffT“‘5”’R0 R0 OR ORand R3 is -R5-; R4 is C1-C4 alkyl or hydroxyalkyl, or the moiety -(R5);r[(C3H5O),,,(CH2CH2O),,]-X; R5 is C1-C12 alkylene, hydroxyalkylene, alkenylene,axylene, or alkarylene; each R6 is C1_C4 alkyl or hydroxyalkyl, or the moiety -(CH2),-A2-(CH2)s-, wherein A2 is -0- or -CH2-; R7 is H or R4; R8 is C2-C3alkylene or hydroxyalkylene; X is H,W._._.__ SUBSTITUTE SHEET (RULE 26)10152025W0 98/13453CA 02265891 1999-03-15PCTlUS97l1670628-R9 or a mixture thereof, wherein R9 is C1-C4 alkyl or hydoxyalkyl; k is O or 1; mand n are numbers such that the moiety -(CH2CH2O),,- comprises at least about 85%by weight of the moiety -[(C3H6O)m(CH2CH2O),,]-; m is from 0 to about 5; n is atleast about 3; r is 1 or 2, s is 1 or 2, and r + sis 3 or 4; y is from 2 to about 20; thenumber of u, v and w are such that there are at least 2 N+ centers and at least 2 Xgroups.In the above formulas, A1 is preferably‘M’ ifIi .R RA2 is preferably -0-; x is preferably 1; and R is preferably H. R1 can be linear (e.g.-CH2-CH2-CH2-,~—-CH2——CH——) orbranched (e.g. ~--- CH2@alkylene, hydroxyalkylene, alkenylene, eycloalkylene, alkarylene or oxyalkylene;when R1 is a C2-C3 oxyalkylene moiety, the number of oxyalkylene units ispreferably from about 2 to about 12; R1 is preferably C2-C6 alkylcne or phenylene,and most preferably C2-C5 alkylene (e. g. ethylene, propylene, hexamethylene). R2is preferably -0115- or -(0118),-; R3 is preferably -R5O- or -(OR8)y-; R4 and R6are preferably methyl. Like R], R5 can be linear or branched, and is preferably C2-C3 alkylene; R7 is preferably H or C1-C3 alkyl; R3 is preferably ethylene; R9 ispreferably methyl; X is preferably H or methyl; k is preferably 0; m is preferably 0,r and s are each preferably 2; y is preferably from 2 to about 12. SUBSTITUTE SHEET (RULE 25)10CA 02265891 1999-03-15W0 98/13453 PCT/US97/1670629In the above formulas. n is preferably at least about 6 when the number of N+ centersand X groups is 2 or 3; n is most preferably at least about 12, with a typical range ofabout 12 to about 42 for all ranges of u + v + w. For homopolymers (v and w are 0),u is preferably from about 3 to about 20. For random compolymers (u is at least 1 orpreferably 0), v and w are each preferably from about 3 to about 40.B. Polyacrylate, Polyacrylamide, Polyvinylether orLike PolymersAnother class of suitable cationic polymers are derived from polyacrylates,polyacrylamides, polyvinylethers and the like. These polymers comprise unitsselected from those having formulas IV, V and VI.SUBSTITUTE SHEET (RULE 26)CA 02265891 l999-03- 15W0 98,11,453 PCT/US97/16706301L1‘g_E/(A >,(R2)j(R3)2 —N+ —— (R2)k- [(C3H6O)m(CH2CH2O)n] — xIV1"113? M;‘Z /(A1)-i(R >k“”f(C3”60>m(CH2CH20>n1"X (R2)j\N*—<R“>3V VIIf’ ‘H’ ‘I’ ‘H’ ‘n’whereinA1 is—o—,~—1IIc—~,—1TIco—,—~i:§Jc—-—,——cN——,R R R RI .E’ ‘n’ if ‘n’ T’—-ocN—— ———oc——,—oco—,——-co—,or --I|\ICI’\I-;iR R RR is H or C1-C4 alkyl or hydroxyalkyl; R1 is substituted C2-C12 alkylene,hydroxyalkylene, alkenylene, arylene or alkarylene, or C2-C3 oxyalkylene; each R25 is C1-C12 alkylene, hydroxyalkylene, alkenylene, arylene or alkarylene; each R3 isC1-C4 alkyl or hydroxyalkyl, the moiety -(R2)k-[(C3H5O)m(CH2CH2O),,]-X, ortogether form the moiety -(CH2),-A2-(CH2)_,-, wherein A2 is -0- or -CH2-; each R4is C1-C4 alkyl or hydroxyalkyl, or two R4 together form the moiety -(CH2),.-A2-(CI-I2)s-; X is H,10SUBSTITUTE SHEET (RULE 26)CA 02265891 l999-03- 15WO 98/13453 PCT/US97/1670631if-— CR5,-R5 or mixture thereof, wherein R5 is C1-C4 alkyl or hydroxalkyl; j is 1 or O; k is 1or 0; m and n are numbers such that the moiety -(CH2CH20),,- comprises at least5 about 85% by weight of the moiety -[(C3H5O),,,(CH2CH2O),,]-; m is from O toabout 5; n is at least about 3; r is 1 or 2, s is 1 or 2 and r + s is 3 or 4; the number ofu, v and w are such that there are at least 2N+ centres and at least 2 X groups.In the above formulas, A1 is preferably1 0Q 0——£N“‘,““‘£JIO‘—— or “—O‘—';1'1A2 is preferably -0-; R is preferably H. R1 can be linear(e.g. —“ CH2 —*- CH“ CH2 —* , *'- CH2CH*') orQCH3branched (e.g. -* CH2 "" "— , *— CH2(’3H—-,CH3is @—— CH2C“—,*"CH2C}I—‘)(‘H215SUBSTITUTE SHEET (RULE 26)W0 98/134531015CA 02265891 1999-03-15PCT/US97/1670632substituted alkylene, hydroxyalkylene, alkenylene, alkarylene or oxyalkylene; R1 ispreferably substituted C2-C5 alkylene or substituted C2-C3 oxyalkylene, and mostpreferablyCH3Each R2 is preferably C2-C3 alkylene, each R3 and R4 are preferably methyl; R5 ispreferably methyl; X is preferably H or methyl; j is preferably 1; k is preferably O;In is preferably 0; r and s are each preferably 2.In the above formulas, n, u, v and w can be varied according to the n, u, v and w forthe polyurethane and like polymers.C. Polyalkyleneamine, Polyalkyleneimine or like polymers.Another class of suitable cationic polymers are derived from polyalkyleneamines,polyalkyleneimines and the like. These polymers comprise units selected from thosehaving formulas VII and VIII and IX.SUBSTITUTE SHEET (RULE 25)CA 02265891 l999-03- 15WO 98/13453 PCT/US97/1670633f“2’d(R1 ._ MII Xi“2’d(R1 - M’j yl(R3)k—~ [(C3H6O)m(CH2CH2O)n) — XfR2"‘(R1 -M‘’ Z?1(R3)k —— [(C3H6O)m(CH2CH2O)n] —— xwherein R1 is C2-C12 alkylene, hydroxyalkylene, alkenylene, cycloalkylene, aryleneor alkarylene, or a C2-C3 oxyalkylene moiety having from 2 to about 20 oxyalkylene5 units provided that no O-N bonds are formed; each R2 is C1-C4 alkyl orhydroxyalkyl, or the moiety -(R3)k-[(C3H5O),,,(CH;;_CH2O),,]-X; R3 is C1-C12alkylene, hydroxyalkylene, alkenylene, arylene or alkaxyleneg M’ is an N+ or Ncentre; X is H,__ ’C'jR4,10 O-R4 or mixture thereof, wherein R4 is C1-C4 alkyl or hydroxyalkyl; d is 1 when M’is N+ and is 0 when M’ is N; e is 2 when M’ is N+ and is 1 when M‘ is N; k is 1 orSUBSTITUTE SHEET (RULE 26)10152025WO 98/13453CA 02265891 l999-03- 15PCT/U S97] 16706340; m and n are numbers such that the moiety -(CH2CH2O)n- comprises at leastabout 85% by weight of the moiety -[(C3H6O)m(CH2CH2O),,]-; m is from 0 toabout 5; n is at least about 3; the number of x, y and 2 are such that there are at least2M’ groups, at least 2N+ centres and at least 2 X groups.In the above formulas, R1 can be varied like R1 of the polyurethene and likepolymers; each R2 is preferably methyl or the moiety -(R3)k-[(C3H6O)m(CH2CH2O)n]-X; R3 is preferably C2-C3 alkylene; R4 is preferablymethyl; X is preferably H; k is preferably 0; m is preferably 0.In the above formulas, n is preferably at least about 6 when the number of M’ and Xgroups is 2 or 3; n is most preferably at least about 12, with a typical range of fromabout 12 to about 42 for all ranges of x + y + 2. Typically, x + y + 2 is from 2 toabout 40 and preferably 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 to 11 X groups. Forlong chain length polymers, x + y + z is at least 10, with a preferred range of from 10to about 42. For the short and long chain length polymers, the M‘ groups aretypically a mixture of from about 50 to 100% N+ centres and from 0 to about 50% NCCIIITCS .Preferred cationic polymers within this class are derived from the C2-C3polyalkyleneamines (x + y + z is from 2 to 9) and polyalkyleneimines (x + y + z is atleast 10, preferably from 10 to about 42). Particularly preferred cationicpolyalkyleneamines and polyalkyleneimines are the cationic polyethyleneamines(PEA's) and polyethyleneimines (PEl's). These preferred cationic polymers compriseunits having the general formula:SUBSTITUTE SHEET (RULE 25)101520CA 02265891 1999-03-15II[(CH2CH20 '1n” X12wo 93/13453 PCTIUS97/1670635um,— -—icH2——cH2¥1x~—l(R2)d (R2)d~—-tcH2CH2M1y— —~tCH2cI*2I~’41z<5{2cH2o>,.—x t<cH2cH2o>,r—><i2wherein R2 (preferably methyl), M’, X, d, x, y, z and n are defined as before; a is 1or 0.Prior to ethoxylation, the PEAs used in preparing cationic polymers of the presentinvention have the following general formula:[H2N]a“‘ —”lCH2CH21“I]x“‘ ‘—[CH2CH21|‘Uy““‘ ““[CH2CH2NH2]zHwherein x + y + z is from 2 to 9, and a is 0 or 1 (molecular weight of from about 100to about 400). Each hydrogen atom attached to each nitrogen atom represents anactive site for subsequent ethoxylation. For preferred PEAS, x + y + z is from about3 to about 7 (molecular weight is from about 140 to about 310). These PEA‘s can beobtained by reactions involving ammonia and ethylene dichloride, followed byfractional distillation. The common PEA's obtained are triethylenetetramine (TETA)and tetraethylenepentamine (TEPA). Above the pentamines, i.e., the hexamines,heptamines, octamines and possibly nonamines, the cogenerically derived mixturedoes not appear to separate by distillation and can include other materials such ascyclic amines and particularly piperazines. There can also be present cyclic amineswith side chains in which nitrogen atoms appear. See US Pat. No. 2,792,372 toDickson, issues May 14, 195 7, which describes the preparation of PEAS.The minimum degree of ethoxylation required for preferred clay soil removal/anti-redeposition performance can vary depending upon the number of units in the PEA.SUBSTITUTE SHEET (RULE 25)10152025W0 98/ 13453CA 02265891 l999-03- 15PCT/US97/ 1670636Where y + z is 2 or 3, n is preferably at least about 6. Where y + 2 is from 4 to 9,suitable benefits are achieved when n is at least about 3. For preferred cationicPEAS, n is at least about 12, with a typical range of about 12 to about 42.The PEIs used in preparing the polymers of the present invention have a molecularweight of at least about 440 prior to ethoxylation, which represents at least about 10units. Preferred PEIs used in preparing these polymers have a molecular weight offrom about 600 to about 1800. The polymer backbone of these PEIs can berepresented by the general formula:Hwherein the sum of x, y, and 2 represents a number of sufficient magnitude to yield apolymer having the molecular weights previously specified. Although linearpolymer backbones are possible, branch chains can also occur. The relativeproportions of primary, secondary and tertiary amine groups present in the polymercan vary, depending on the manner of preparation. The distribution of amine groupsis typically as follows:aw cH2cH2+NH2 30%~— cH2cH2~NH-~~ 40%T’ “_ N ‘T’ 30%Each hydrogen atom attached to each nitrogen atom of the PEI represents an activesite for subsequent ethoxylation. These PEIs can be prepared, for example, bypolymerizing ethyleneimine in the presence of a catalyst such as carbon dioxide,sodium bisulfite, sulfuric acid, hydrogen peroxide, hydrochloric acid, acetic acid, etc.Specific methods for preparing PEIs are disclosed in US Pat. No. 2,182,306 to UlrichSUBSTITUTE SHEET (RULE 26)101520W0 98ll3453CA 02265891 1999-03-15PCT/US97/ 1670637et al., issued Dec. 5, 1939; US Pat No. 3,033,746 to Mayle et al., 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, issued Sept. 17, 1957; and US Pat. No. 2,533,696 to Wilson,issued May 21, 1951 (all herein incorporated by reference).As defined in the preceding formulas, n is at least about 3 for the cationic PEIs.However, it should be noted that the minimum degree of ethoxylation required forsuitable clay soil removal/anti-redeposition performance can increase as themolecular weight of the PEI increases, especially much beyond about 1800. Also,the degree of ethoxylation for preferred polymers increases as the molecular weightof the PEI increases. For PEIs having a molecular weight of at least about 600, n ispreferably at least about 12, with a typical range of from about 12 to about 42. ForPEIs having a molecular weight of at least 1800, n is preferably at least about 24,with a typical range of from about 24 to about 42.D. Diallylamine PolymersAnother class of suitable cationic polymers are those derived from the diallylamines.These polymers comprise units selected from those having formulas X and XI:CA 02265891 l999-03- 15WO 98/13453 PCT/US97/1670638- (CH2)y\ (Q1I2)x \/.,\ u\R1 / (R3)k~- [(C3H6O)m(CH2CH2O)n] — Xr — (CH2)y 1 /(CH2 -~--——' (CH2)x -—<R3>2wherein R1 is C1-C4 alkyl or hydroxyalkyl, or the moiety -(R2)k-[(C3H6O)m(CH2CH2O),,]-X; R2 is C1-C12 alkylene, hydroxyalkylene, alkylene,5 ’ arylene or alkaiylene; each R3 is C1-C4 alkyl or hydroxyalkyl. or together form themoiety -(CH2),~A-(CH2)S-, wherein A is -0- or -CH2—; X is H,; CR4’010 -R4 or mixture thereof, wherein R4 is C1-C4 alkyl or hydroxyalkyl; k is 1 or 0; mand n are numbers such that the moiety -(CH2CH2O),,- comprises at least about 85%by weight of the moiety -[(C3H6O)m(CH2CH2O),,]-; m is from 0 to about 5; n is atleastabout3; ris1or2,sis1or2,andr+sis3 or4; xis1or0; yis1whenxisOand 0 when x is 1; the number of u and v are such that there are at least 2N+ centres15 and at least 2 X groups.SUBSTITUTE SHEET (RULE 26)101520253035WO 98/13453CA 02265891 1999-03-15PCT/U S97! 1670639In the above formulas, A is preferably -0-; R1 is preferably methyl; each R2 ispreferably C2-C3 alkylene; each R3 is preferably methyl; R4 is preferably methyl;X is preferably H; k is preferably 0; m is preferably 0; r and s are each preferably 2.In the above formulas, n is preferably at least about 6 when the number of N+ centresand X groups are each 2 or 3, n is preferably at least 12, with a typical range of fromabout 12 to about 42 for all range of u + v. Typically, v is 0, and u is from 2 to about40. and preferably from 2 to about 20.(Additional) Water-soluble builder compoundThe detergent compositions or components thereof preferably contain a water-solublebuilder compound, typically present in detergent compositions at a level of from 1%to 80% by weight, preferably from 10% to 70% by weight, most preferably from20% to 60% by weight of the composition.Suitable water-soluble builder compounds include the water soluble monomericpolycarboxylates. or their acid forms, homo or copolymeric polycarboxylic acids ortheir salts in which the polycarboxylic 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.The carboxylate or polycarboxylate builder can be momomeric or oligomeric in typealthough monomeric polycarboxylates are generally preferred for reasons of cost andperformance.Suitable carboxylates containing one carboxy group include the water soluble salts oflactic acid, glycolic acid and ether derivatives thereof. Polycarboxylates containingtwo carboxy groups include the water-soluble salts of succinic acid, malonic acid,(ethylenedioxy) diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acidand fumaric acid, as well as the ether carboxylates and the sulfinyl carboxylates.Polycarboxylates containing three carboxy groups include, in particular, water-soluble citrates, aconitrates and citraconates as well as succinate derivatives such asthe carboxymethyloxysuccinates described in British Patent No. 1,3 79,241,lactoxysuccinates described in British Patent No. 1,389,732, and aminosuccinatesSUBSTITUTE SHEET (RULE 26)1015202530CA 02265891 1999-03-15W0 98/13453 PCT/US97/1670640described in Netherlands Application 7205873, and the oxypolycarboxylate materialssuch as 2—oxa-1,1,3-propane tricarboxylates described in British Patent No.1,387,447.Polycarboxylates containing four carboxy groups include oxydisuccinates disclosedin British Patent No. 1,261,829, l,1,2,2-ethane tetracarboxylates, 1,l,3,3—propanetetracarboxylates and l,1,2,3-propane tetracarboxylates. Polycarboxylates containingsulfo substituents include the sulfosuccinate derivatives disclosed in British PatentNos. 1,398,421 and 1,398,422 and in U.S. Patent No. 3,936,448, and the sulfonatedpyrolysed citrates described in British Patent No. 1,439,000. Preferredpolycarboxylates are hydroxycarboxylates containing up to three carboxy groups permolecule, more particularly citrates.The parent acids of the monomeric or oligomeric polycarboxylate chelating agents ormixtures thereof with their salts, e.g. citric acid or citrate/citric acid mixtures are alsocontemplated as useful builder components.Borate builders, as well as builders containing borate-forrning materials that canproduce borate under detergent storage or wash conditions are useful water-solublebuilders herein.Suitable examples of water-soluble phosphate builders are the alkali metaltripolyphosphates, sodium, potassium and ammonium pyrophosphate, sodium andpotassium and ammonium pyrophosphate, sodium and potassium otthophosphate,sodium polymeta/phosphate in which the degree of polymerization ranges from about6 to 21, and salts of phytic acid.Partially soluble or insoluble builder compoundThe detergent compositions or components thereof, of the present invention maycontain a partially soluble or insoluble builder compound, typically present indetergent compositions at a level of from 1% to 80% by weight, preferably from 10%to 70% by weight, most preferably from 20% to 60% weight of the composition.SUBSTITUTE SHEET (RULE 26)101520253035W0 98/131153CA 02265891 1999-03-15PCT/US97/ 1670641Preferred largely insoluble builder compounds are aluminosilicate ionexchange materials, preferably zeolite A and zeolite MAP, as described above.Heavy metal ion sequestrantThe detergent compositions or components thereof preferably contain as an optionalcomponent a heavy metal ion sequestrant. By heavy metal ion sequestrant it is meantherein components which act to sequester (chelate) heavy metal ions. Thesecomponents may also have calcium and magnesium chelation capacity, butpreferentially they show selectivity to binding heavy metal ions such as iron,manganese and copper.Heavy metal ion sequestrants are generally present at a level of from 0.005% to 20%,preferably from 0.1% to l0%, more preferably from 0.25% to 7.5% and mostpreferably from 0.5% to 5% by weight of the compositions.Suitable heavy metal ion sequestrants for use herein include organic phosphonates.such as the amino alkylene poly (alkylene phosphonates), alkali metal ethane 1-hydroxy disphosphonates and nitrilo trimethylene phosphonates.Preferred among the above species are diethylene triamine penta (methylenephosphonate), ethylene diamine tri (methylene phosphonate) hexarnethylene diaminetetra (methylene phosphonate) and hydroxy—ethylene 1,1 diphosphonate.Other suitable heavy metal ion sequestrant for use herein include nitrilotriacetic acidand polyaminocarboxylic acids such as ethylenediaminotetracetic acid,ethylenetriamine pentacetic acid, ethylenediamine disuccinic acid, ethylenediaminediglutaric acid, 2-hydroxypropylenediamine disuccinic acid or any salts thereof.Especially preferred is ethylenediamine-N,N'-disuccinic acid (EDDS) or the alkalimetal, alkaline earth metal, ammonium, or substituted ammonium salts thereof, ormixtures thereof.Other suitable heavy metal ion sequestrants for use herein are iminodiacetic acidderivatives such as 2-hydroxyethyl diacetic acid or glyceryl imino diacetic acid,described in EP-A-317,542 and EP-A-399,133. The iminodiacetic acid-N-2-SUBSTITUTE SHEET (RULE 26)1015202530WO 98/13453CA 02265891 1999-03-15PCTIU S97/ 1670642hydroxypropyl sulfonic acid and aspartic acid N-carboxymethyl N-2—hydroxypropyl~3-sulfonic acid sequestrants described in EP-A-516,102 are also suitable herein. TheB-alanine-N,N'-diacetic acid, aspartic acid-N,N‘-diacetic acid, aspartic acid-N-monoacetic acid and iminodisuccinic acid sequestrants described in EP-A-509,382are also suitable.EP-A-476,257 describes suitable amino based sequestrants. EP-A-510,331 describessuitable sequestrants derived from collagen, keratin or casein. EP-A-528,859describes a suitable alkyl iminodiacetic acid sequestrant. Dipicolinic acid and 2-phosphon0butane-1,2,4-tricarboxylic acid are also suitable. Glycinamide-N,N'—disuccinic acid (GADS), ethylenediamine-N-N’-diglutaric acid (EDDG) and 2-hydroxypropylenediamine-N—N'-disuccinic acid (HPDDS) are also suitable.Organic peroxyacid bleaching systemA preferred feature of detergent compositions or component thereof is an organicperoxyacid bleaching system. In one preferred execution the bleaching systemcontains a hydrogen peroxide source and an organic peroxyacid bleach precursorcompound. The production of the organic peroxyacid occurs by an in situ reaction ofthe precursor with a source of hydrogen peroxide. Preferred sources of hydrogenperoxide include inorganic perhydrate bleaches. In an alternative preferred executiona preformed organic peroxyacid is incorporated directly into the composition.Compositions containing mixtures of a hydrogen peroxide source and organicperoxyacid precursor in combination with a preformed organic peroxyacid are alsoenvisaged.Inorganic perhydrate bleachesInorganic perhydrate salts are a preferred source of hydrogen peroxide. These saltsare normally incorporated in the form of the alkali metal, preferably sodium salt at alevel of from 1% to 40% by weight, more preferably from 2% to 30% by weight andmost preferably from 5% to 25% by weight of the compositions.SUBSTITUTE SHEET (RULE 26)WO 98/134531015202530CA 02265891 1999-03-15PCT/US97/1670643Examples of inorganic perhydrate salts include perborate, percarbonate,perphosphate, persulfate and persilicate salts. The inorganic perhydrate salts arenormally the alkali metal salts. The inorganic perhydrate salt may be included as thecrystalline solid without additional protection. For certain perhydrate salts however,the preferred executions of such granular compositions utilize a coated form of thematerial which provides better storage stability for the perhydrate salt in the granularproduct. Suitable coatings comprise inorganic salts such as alkali metal silicate,carbonate or borate salts or mixtures thereof, or organic materials such as waxes, oils,or fatty soaps.Sodium perborate is a preferred perhydrate salt and can be in the form of themonohydrate of nominal formula NaBO2H2O2 or the tetrahydrateNaBO2H2O2.3H2O.Alkali metal percarbonates, particularly sodium percarbonate are preferredperhydrates herein. Sodium percarbonate is an addition compound having a formulacorresponding to 2Na2CO3.3I-I202, and is available commercially as a crystallinesolid.Potassium peroxymonopersulfate is another inorganic perhydrate salt of use in thedetergent compositions herein.Peroxyacid bleach precursorPeroxyacid bleach precursors are compounds which react with hydrogen peroxide ina perhydrolysis reaction to produce a peroxyacid. Generally peroxyacid bleachprecursors may be represented asOHX—C—Lwhere L is a leaving group and X is essentially any functionality, such that onperhydroloysis the structure of the peroxyacid produced isSUBSTITUTE SHEET (RULE 26)CA 02265891 l999-03- 15WO 98/13453 PCT/US97/16706441?X~C-OOHPeroxyacid bleach precursor compounds are preferably incorporated at a level offrom 0.5% to 20% by weight, more preferably from 1% to 15% by weight, most5 preferably from 1.5% to 10% by weight of the detergent compositions.Suitable peroxyacid bleach precursor compounds typically contain one or more N- orO-acyl groups, which precursors can be selected from a wide range of classes.Suitable classes include anhydrides, esters, imides, lactams and acylated derivatives10 of imidazoles and oximes. Examples of useful materials within these classes aredisclosed in GB-A-1586789. Suitable esters are disclosed in GB-A-83 698 8, 864798,1147871, 2143231 and EP-A-0170386.Leaving groups15The leaving group, hereinafter L group, must be sufficiently reactive for theperhydrolysis reaction to occur within the optimum time frame (e.g., a wash cycle).However, if L is too reactive, this activator will be difficult to stabilize for use in ableaching composition.20Preferred L groups are selected from the group consisting of:L0@, and -o@/RSY—1|~I——c——R‘, --N N , -—N-C—(|3H-—R4,YSUBSTITUTE SHEET (RULE 26)CA 02265891 l999-03- 15wo 9s/13453 PCT/US97/1670645‘F3 T-0-CH=C—CH=CH2 -O—CH=C-CH=CH2O OH Y ||0 CH2-C )—c\II x \ 4 _N NR4—O—C—R‘ -N\C/NR , \C/ .' n U0 O‘F3 i? T—o—c=CHR4 ,and —lTl--fi-—CH—-R4R3 O10152025and mixtures thereof, wherein R1 is an alkyl, aryl, or alkaryl group containing from 1to 14 carbon atoms, R3 is an alkyl chain containing from 1 to 8 carbon atoms, R4 isH or R3, R5 is an alkenyl chain containing from 1 to 8 carbon atoms and Y is H or asolubilizing group. 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 ammmonium groupsThe preferred solubilizing groups are -SO3_M+, -CO2-M+, —SO4'M+, -Nj(R3)4X-and O<--N(R3)3 and most preferably -SO3'M+ and -CO2—M+ wherein R’) is an alkylchain containing from 1 to 4 carbon atoms, M is a cation which provides solubility tothe bleach activator and X is an anion which provides solubility to the bleachactivator. Preferably, M is an alkali metal, ammonium or substituted ammoniumcation, with sodium and potassium being most preferred, and X is a halide,hydroxide, methylsulfate or acetate anion.Alkyl percarboxvlic acid bleach precursorsAlkyl percarboxylic acid bleach precursors form percarboxylic acids onperhydrolysis. Preferred precursors of this type provide peracetic acid onperhydrolysis.SUBSTITUTE SHEET (RULE 26)1015202530CA 02265891 1999-03-15W0 98,13453 PCT/U S97/ 1670646Preferred alkyl percarboxylic precursor compounds of the imide type include the N-,N,N1N1 tetra acetylated alkylene diarnines wherein the alkylene group containsfrom l to 6 carbon atoms, particularly those compounds in which the alkylene groupcontains 1, 2 and 6 carbon atoms. Tetraacetyl ethylene diarnine (TAED) isparticularly preferred.Other preferred alkyl percarboxylic acid precursors include sodium 3,5,5-tri-methylhexanoyloxybenzene sulfonate (iso-NOBS), sodium nonanoyloxybenzene sulfonate(NOBS), sodium acetoxybenzene sulfonate (ABS) and pentaacetyl glucose.Amide substituted alkyl peroxyacid precursorsAmide substituted alkyl peroxyacid precursor compounds are suitable herein,including those of the following general formulae:R1——N——c-—R2—-—c-—L! H I H HR5 0 or R5 O OR1-——c—-N——R2-——c———LH0wherein R1 is an alkyl group with from 1 to 14 carbon atoms, R2 is an alkylenegroup containing from 1 to 14 carbon atoms, and R5 is H or an alkyl groupcontaining 1 to 10 carbon atoms and L can be essentially any leaving group. Amidesubstituted bleach activator compounds of this type are described in EP-A-O1 703 86.Perbenzoic acid precursorPerbenzoic acid precursor compounds provide perbenzoic acid on perhydrolysis.Suitable O-acylated perbenzoic acid precursor compounds include the substituted andunsubstituted benzoyl oxybenzene sulfonates, and the benzoylation products ofsorbitol, glucose, and all saccharides with benzoylating agents, and those of the imidetype including N-benzoyl succinimide, tetrabenzoyl ethylene diarnine and the N-benzoyl substituted ureas. Suitable imidazole type perbenzoic acid precursors includeN-benzoyl imidazole and N-benzoyl benzimidazole. Other useful N-acyl group-containing perbenzoic acid precursors include N-benzoyl pytrolidone, dibenzoyltaurine and benzoyl pyroglutamic acid.suasrrrure sneer (RULE 26)1015202530W0 98ll3453CA 02265891 1999-03-15PCTIUS97/1670647Cationic peroxyacid precursorsCationic peroxyacid precursor compounds produce cationic peroxyacids onperhydrolysis.Typically, cationic peroxyacid precursors are formed by substituting the peroxyacidpart of a suitable peroxyacid precursor compound with a positively chargedfunctional group, such as an ammonium or alkyl ammmonium group, preferably anethyl or methyl ammonium group. Cationic peroxyacid precursors are typicallypresent in the solid detergent compositions as a salt with a suitable anion, such as ahalide ion.The peroxyacid precursor compound to be so cationically substituted may be aperbenzoic acid, or substituted derivative thereof, precursor compound as describedhereinbefore. Alternatively, the peroxyacid precursor compound may be an alkylpercarboxylic acid precursor compound or an amide substituted alkyl peroxyacidprecursor as described hereinafterCationic peroxyacid precursors are described in U.S. Patents 4,904,406; 4,751.0l5;4,988,451; 4,397,757; 5,269,962; 5,127,852; 5,093,022; 5,106,528; U.K. 1,382,594;EP 475,512, 458,396 and 284,292; and in JP 87-318,332.Examples of preferred cationic peroxyacid precursors are described in UK PatentApplication No. 9407944.9 and US Patent Application Nos. 08/298903, 08/298650,08/298904 and 08/298906.Suitable cationic peroxyacid precursors include any of the ammonium or alkylammonium substituted alkyl or benzoyl oxybenzene sulfonates, N-acylatedcaprolactams, and monobenzoyltetraacetyl glucose benzoyl peroxides. Preferredcationic peroxyacid precursors of the N-acylated caprolactam class include thetrialkyl ammonium methylene benzoyl caprolactams and the trialkyl ammoniummethylene alkyl caprolactams.SUBSTITUTE SHEET (RULE 26)10152025WO 98/13453CA 02265891 1999-03-15PCT/U S97/ 1670648Benzoxazin organic peroxyacid precursorsAlso suitable are precursor compounds of the benzoxazin-type, as disclosed forexample in EP-A-332,294 and EP-A-482,807, particularly those having the formula:\?N//C-R1wherein R1 is H, alkyl, alkaryl, aryl, or arylalkyl.Preformed organic peroxyacidThe organic peroxyacid bleaching system may contain, in addition to, or as analternative to, an organic peroxyacid bleach precursor compound, a preformedorganic peroxyacid , typically at a level of from 1% to 15% by weight, morepreferably from 1% to 10% by weight of the composition.A preferred class of organic peroxyacid compounds are the amide substitutedcompounds of the following general formulae:R1—c—N—R-°-c—~—ooHo K25 0 orR1~N—c—R2—c_;»~ooHR5 o 5wherein R1 is an alkyl, aryl or alkaryl group with from 1 to 14 carbon atoms, R2 isan alkylene, arylene, and alkarylene group containing from 1 to 14 carbon atoms, andR5 is H or an alkyl, aryl, or alkaryl group containing 1 to 10 carbon atoms. Amidesubstituted organic peroxyacid compounds of this type are described in EP-A-0170386.SUBSTITUTE SHEET (RULE 26)1015202530W0 98/13453CA 02265891 1999-03-15PCT /US97I 1670649Other organic peroxyacids include diacyl and tetraacylperoxides, especiallydiperoxydodecanedioc acid, diperoxytetradecanedioc acid anddiperoxyhexadecanedioc acid. Mono— and diperazelaic acid, mono- anddiperbrassylic acid and N-phthaloylaminoperoxicaproic acid are also suitable herein.En_zymeAnother preferred ingredient useful in the detergent compositions or componentsthereof is one or more additional enzymes.Preferred additional enzymatic materials include the commercially availablecellulases, endolases, cutinases, amylases, lipases, neutral and alkaline proteases,esterases, pectinases, lactases and peroxidases conventionally incorporated intodetergent compositions. Suitable enzymes are discussed in US Patents 3,519,570 and3,533,139.Preferred commercially available protease enzymes include those sold under thetradenames Alcalase, Savinase, Primase, Durazym, and Esperase by Novo IndustriesA/S (Denmark), those sold under the tradename Maxatase, Maxacal and Maxapemby Gist-Brocades, those sold by Genencor International, and those sold under thetradename Opticlean and Optimase by Solvay Enzymes. Protease enzyme may beincorporated into the compositions in accordance with the invention at a level offrom 0.0001% to 4% active enzyme by weight of the composition.Preferred amylases include, for example, or-amylases obtained from a special strainof B licheniformis, described in more detail in GB-1,269,839 (Novo). Preferredcommercially available amylases include for example, those sold under thetradename Rapidase by Gist-Brocades, and those sold under the tradenameTermamyl and BAN by Novo Industries A/S. Amylase enzyme may be incorporatedinto the composition in accordance with the invention at a level of from 0.0001% to2% active enzyme by weight of the composition.SUBSTITUTE SHEET (RULE 26)WO 98/13453101520253035CA 02265891 1999-03-15PCTIUS97l1670650(Additional) Organic polvmeric compoundOrganic polymeric compounds are preferred additional components of the detergentcompositions or components thereof and are preferably present as components of anyparticulate components where they may act such as to bind the particulate componenttogether. By organic polymeric compound it is meant herein essentially anypolymeric organic compound commonly used as dispersants, and anti-redepositionand soil suspension agents in detergent compositions, including any of the highmolecular weight organic polymeric compounds described as clay flocculating agentsherein, not being an quaternised ethoxylated (poly) amine clay-soi1removal/ anti-redeposition agent in accord with the invention.Organic polymeric compound is typically incorporated in the detergent compositionsof the invention at a level of from 0.1% to 30%, preferably from 0.5% to 15%, mostpreferably from 1% to 10% by weight of the compositions.Examples of organic polymeric compounds include the water soluble organic homo-or co-polymeric polycarboxylic acids or their salts in which the polycarboxylic acidcomprises at least two carboxyl radicals separated from each other by not more thantwo carbon atoms. Polymers of the latter type are disclosed in GB-A-1,596,756.Examples of such salts are polyacrylates of MWt 1000-5000 and their copolymerswith maleic anhydride, such copolymers having a molecular weight of from 2000 to100.000, especially 40,000 to 80,000.The polyarnino compounds are useful herein including those derived from asparticacid such as those disclosed in EP-A-305282, EP-A-305283 and EP-A-351629.Terpolymers containing monomer units selected from maleic acid, acrylic acid,polyaspartic acid and vinyl alcohol, particularly those having an average molecularweight of from 5,000 to 10,000, are also suitable herein.Other organic polymeric compounds suitable for incorporation in the detergentcompositions herein include cellulose derivatives such as methylcellulose,carboxymethylcellulose, hydroxypropylmethylcellulose and hydroxyethylcellulose.SUBSTITUTE SHEET (RULE 26)101520253035WO 98/13453CA 02265891 1999-03-15PCT/US97/1670651Further useful organic polymeric compounds are (additional) the polyethyleneglycols, particularly those of molecular weight 1000-10000, more particularly 2000to 8000 and most preferably about 4000.Suds suppressing systemThe detergent compositions, when formulated for use in machine washingcompositions, preferably comprise a suds suppressing system present at a level offrom 0.01% to 15%, preferably from 0.05% to 10%, most preferably from 0.1% to5% by weight of the composition.Suitable suds suppressing systems for use herein may comprise essentially anyknown antifoam compound, including, for example silicone antifoam compoundsand 2-alkyl alcanol antifoam compounds.By antifoam compound it is meant herein any compound or mixtures of compoundswhich act such as to depress the foaming or sudsing produced by a solution of adetergent composition, particularly in the presence of agitation of that solution.Particularly preferred antifoam compounds for use herein are silicone antifoamcompounds defined herein as any antifoam compound including a siliconecomponent. Such silicone antifoam compounds also typically contain a silicacomponent. The term "silicone" as used herein, and in general throughout theindustry, encompasses a variety of relatively high molecular weight polymerscontaining siloxane units and hydrocarbyl group of various types. Preferred siliconeantifoam compounds are the siloxanes, particularly the polydimethylsiloxanes havingtrimethylsilyl end blocking units.Other suitable antifoam compounds include the monocarboxylic fatty acids andsoluble salts thereof. These materials are described in US Patent 2,954,347, issuedSeptember 27, 1960 to Wayne St. John. The monocarboxylic fatty acids, and saltsthereof, for use as suds suppressor typically have hydrocarbyl chains of 10 to 24carbon atoms, preferably 12 to 18 carbon atoms. Suitable salts include the alkalimetal salts such as sodium, potassium, and lithium salts, and ammonium andalkanolammonium salts.SUBSTITUTE SHEET (RULE 25)W0 98/125453101520253035CA 02265891 1999-03-15PCT/US97l 1670652Other suitable antifoam compounds include, for example, high molecular weightfatty esters (e.g. fatty acid triglycerides), fatty acid esters of monovalent alcohols,aliphatic C13-C40 ketones (e.g. stearone) N-alkylated amino triazines such as tri- tohexa-alkylmelamines or di- to tetra alkyldiamine chlortriazines formed as products ofcyanuric chloride with two or three moles of a primary or secondary aminecontaining 1 to 24 carbon atoms, propylene oxide, bis stearic acid amide andmonostearyl di-alkali metal (e. g. sodium, potassium, lithium) phosphates andphosphate esters.A preferred suds suppressing system comprises(8)(b)(C)antifoam compound, preferably silicone antifoam compound, most preferablya silicone antifoam compound comprising in combination(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% to 25% byweight of the silicone/silica antifoam compound;wherein said silica/silicone antifoam compound is incorporated at a level offrom 5% to 50%, preferably 10% to 40% by weight;a dispersant compound, most preferably comprising a silicone glycol rakecopolymer with a polyoxyalkylene content of 72-78% and an ethylene oxideto propylene oxide ratio of from l:0.9 to 1:l.l, at a level of from 0.5% to10%, preferably 1% to 10% by weight; a particularly preferred silicone glycolrake copolymer of this type is DCO544, commercially available from DOWCorning under the tradename DCO544;an inert carrier fluid compound. most preferably comprising a C16-C18ethoxylated alcohol with a degree of ethoxylation of from 5 to 50, preferably8 to 15, at a level of from 5% to 80%, preferably 10% to 70%, by weight;SUBSTITUTE SHEET (RULE 26)1015202530W0 98/13453CA 02265891 1999-03-15PCT/U S9 7/ 1670653A highly preferred particulate suds suppressing system is described in EP-A-0210731and comprises a silicone antifoam compound and an organic carrier material having amelting point in the range 50°C to 85°C, wherein the organic carrier materialcomprises a monoester of glycerol and a fatty acid having a carbon chain containingfrom 12 to 20 carbon atoms. EP—A-0210721 discloses other preferred particulatesuds suppressing systems wherein the organic carrier material is a fatty acid oralcohol having a carbon chain containing from 12 to 20 carbon atoms, or a mixturethereof, with a melting point of from 45°C to 80°C.Polymeric dye transfer inhibiting agentsThe detergent compositions herein may also comprise from 0.01% to 10 %,preferably from 0.05% to 0.5% by weight of polymeric dye transfer inhibiting agents.The polymeric dye transfer inhibiting agents are preferably selected from polyarnineN-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole,polyvinylpyrrolidonepolymers or combinations thereof, whereby these polymers canbe cross-linked polymers.a1 Polyamine N-oxide polymersPolyamine N-oxide polymers suitable for use herein contain units having thefollowing structure formula 2(I)JU—?—-—'Uwherein P is a polymerisable unit, andO O OH H HA is NC, CO, C, -O-, -S-, -N-; x is O or1;suasrrrure SHEET (RULE 26)10152025W0 98l13453CA 02265891 1999-03-15PCT/US97/ 1670654R are aliphatic, ethoxylated aliphatics, aromatic, heterocyclic or alicyclic groups orany combination thereof whereto the nitrogen of the N-O group can be attached orwherein the nitrogen of the N-O group is part of these groups.The N-O group can be represented by the following generalSHUCHKCS2OA_ 0(R1) x -N-<R2>y ‘(R3); or T:N-(R1)xwherein R1, R2, and R3 are aliphatic groups, aromatic, heterocyclic or alicyclicgroups or combinations thereof, x or/and y or/and z is 0 or 1 and wherein the nitrogenof the N-O group can be attached or wherein the nitrogen of the N-O group formspart of these groups. The N-O group can be part of the polymerisable unit (P) or canbe attached to the polymeric backbone or a combination of both.Suitable polyamine N-oxides wherein the N-O group forms part of the polymerisableunit comprise polyamine N-oxides wherein R is selected from aliphatic, aromatic,alicyclic or heterocyclic groups. One class of said polyamine N-oxides comprises thegroup of polyamine N-oxides wherein the nitrogen of the N-O group forms part ofthe R-group. Preferred polyamine N-oxides are those wherein R is a heterocyclicgroup such as pynidine, pyrrole, imidazole, pyrrolidine, piperidine, quinoline,acridine and derivatives thereof.Other suitable polyamine N-oxides are the polyamine oxides whereto the N-O groupis attached to the polymerisable unit. A preferred class of these polyamine N-oxidescomprises the polyamine N-oxides having the general formula (I) wherein R is anaromatic,heterocyc1ic or alicyclic groups wherein the nitrogen of the N-O functionalgroup is part of said R group. Examples of these classes are polyamine oxidesSUBSTITUTE SHEET (RULE 26)W0 98/ 134531015202530CA 02265891 1999-03-15PCT/US97/1670655wherein R is a heterocyclic compound such as pyrridine, pyrrole, imidazole andderivatives thereof.The polyamine N-oxides can be obtained in almost any degree of polymerisation.The degree of polymerisation is not critical provided the material has the desiredwater-solubility and dye-suspending power. Typically, the average molecular weightis within the range of 500 to 1000,000.b) Copolymers of N-vinylpyrrolidone and N—vinylimidazoleSuitable herein are coploymers of N—vinylimidazole and N—vinylpyrrolidone havingan average molecular weight range of from 5,000 to 50,000. The preferredcopolymers have a molar ratio of N—vinylimidazole to N-vinylpyrrolidone from 1 to0.2.c) PolyvinylpyrrolidoneThe detergent compositions herein may also utilize polyvinylpyrrolidone ("PVP")having an average molecular weight of from 2,500 to 400,000. Suitablepolyvinylpyrrolidones are commercially available from ISP Corporation, New York,NY and Montreal, Canada under the product names PVP K-15 (viscosity molecularweight of 10,000), PVP K-30 (average molecular weight of 40,000), PVP K-60(average molecular weight of 160,000), and PVP K-90 (average molecular weight of360,000). PVP K-15 is also available from ISP Corporation. Other suitablepolyvinylpyrrolidones which are commercially available from BASF Cooperationinclude Sokalan HP 165 and Sokalan HP 12.d) PolyvinyloxazolidoneThe detergent compositions herein may also utilize polyvinyloxazolidones aspolymeric dye transfer inhibiting agents. Said polyvinyloxazolidones have anaverage molecular weight of from 2,500 to 400,000.SUBSTITUTE SHEET (RULE 26)W0 98/ 134531015202530CA 02265891 1999-03-15PCT/U S97! 1670656e) PolvvinylimidazoleThe detergent compositions herein may also utilize polyvinylimidazole as polymericdye transfer inhibiting agent. Said polyvinylimidazoles preferably have an averagemolecular weight of from 2,500 to 400,000.Optical brightenerThe detergent compositions herein also optionally contain from about 0.005% to 5%by weight of certain types of hydrophilic optical brighteners.Hydrophilic optical brighteners useful herein include those having the structuralformula:R1 R2N ‘E ‘E HN G n c= N>—N H H N‘-<R2 SO3M SO3M R,wherein 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 is a salt-forrning cation such as sodium orpotassium.When in the above formula, R1 is anilino, R2 is N-2-bis-hydroxyethyl and M is acation such as sodium, the brightener is 4,4’,-bis{(4-anilino-6-(N—2-bis-hydroxyethyl)-s-triazine-2-yl)amino]-2,2’-stilbenedisulfonic acid and disodium salt.This particular brightener species is commercially marketed under the tradenameTinopal-UNPA-GX by Ciba-Geigy Corporation. Tinopal-UNPA-GX is the preferredhydrophilic optical brightener useful in the detergent compositions herein.When in the above formula, R1 is anilino, R2 is N-2-hydroxyethyl-N-2-methylaminoand M is a cation such as sodium, the brightener is 4,4'-bis[(4-anilino-6-(N-2-hydroxyethyl—N-methylamino)-s-triazine—2-yl)amino]2,2'-stilbenedisulfonic acidSUBSTITUTE SHEET (RULE 26)W0 98/ 13453101520253035CA 02265891 1999-03-15PCT/U S97! 1670657disodium salt. This particular brightener species is commercially marketed under thetradename Tinopal SBM-GX by Ciba-Geigy Corporation.When in the above formula, R1 is anilino, R2 is morphilino and M is a cation such assodium, the brightener is 4,4’-bis[(4-anilino-6-morphilino-s-triazine-2-yl)amino]2,2‘-stilbenedisulfonic acid, sodium salt. This particular brightener species iscommercially marketed under the tradename Tinopal AMS-GX by Ciba GeigyCorporation.Polvmeric Soil Release AgentKnown polymeric soil release agents, hereinafter "SRA", can optionally be employedin the present detergent compositions. If utilized, SRA's will generally comprisefrom 0.01% to 10.0%, typically from 0.1% to 5%, preferably from 0.2% to 3.0% byweight, of the compositions.Preferred SRA's typically have hydrophilic segments to hydrophilize the surface ofhydrophobic fibers such as polyester and nylon, and hydrophobic segments to depositupon hydrophobic fibers and remain adhered thereto through completion of washingand rinsing cycles, thereby serving as an anchor for the hydrophilic segments. Thiscan enable stains occurring subsequent to treatment with the SRA to be more easilycleaned in later washing procedures.Preferred SRA's include oligomeric terephthalate esters, typically prepared byprocesses involving at least one transesterification/oligomerization, often with ametal catalyst such as a titanium(IV) alkoxide. Such esters may be made usingadditional monomers capable of being incorporated into the ester structure throughone, two, three, four or more positions, without, of course, forming a denselycrosslinked overall structure.Suitable SRA's include a sulfonated product of a substantially linear ester oligomercomprised of an oligomeric ester backbone of terephthaloyl and oxyalkyleneoxyrepeat units and allyl-derived sulfonated terminal moieties covalently attached to thebackbone, for example as described in U.S. 4,968,451, November 6, 1990 to U.Scheibel and E.P. Gosselink. Such ester oligomers can be prepared by: (a)SUBSTITUTE SHEET (RULE 26)W0 98Il3453101520253035CA 02265891 1999-03-15PCT/US97l 1670658ethoxylating allyl alcohol; (b) reacting the product of (a) with dimethyl terephthalate("DMT") and ("PG") in atransesterification/oligomerization procedure; and (c) reacting the product of (b) with1 ,2-propylene glycol two-stagesodium metabisulfite in water. Other SRA's include the nonionic end—capped 1,2-propylene/polyoxyethylene terephthalate polyesters of U.S. 4,711,730, December 8,1987 to Gosselink et al., fortransesterification/oligomerization of poly(ethy1eneglyco1) methyl ether, DMT, PGand poly(ethyleneglycol) ("PEG"). Other examples of SRA's include: the partly- andfully- anionic-end-capped oligomeric esters of U.S. 4,721,580, January 26, 1988 toGosselink, such as oligomers from ethylene glycol ("EG"), PG, DMT and Na-3,6-dioxa-8-hydroxyoctanesulfonate; the nonionic-capped block polyester oligomericcompounds of U.S. 4,702,857, October 27, 1987 to Gosselink, for example producedfrom DMT, methyl (Me)-capped PEG and EG and/or PG, or a combination of DMT,EG and/or PG, Me-capped PEG and Na-dimethyl-5—sulfoisophthalate; and theanionic, especially sulfoaroyl, end-capped terephthalate esters of U.S. 4,877,896,October 31, 1989 to Maldonado, Gosselink et al., the latter being typical of SRA'suseful in both laundry and fabric conditioning products, an example being an esterexample those produced bycomposition made from m-sulfobenzoic acid monosodium salt, PG and DMT,optionally but preferably further comprising added PEG, e.g., PEG 3400.SRA's also include: simple copolymeric blocks of ethylene terephthalate orpropylene terephthalate with polyethylene oxide or polypropylene oxideterephthalate, see U.S. 3,959,230 to Hays, May 25, 1976 and U.S. 3,893,929 toBasadur, July 8, 1975; cellulosic derivatives such as the hydroxyether cellulosicpolymers available as METHOCEL from Dow; the C1-C4 alkyl celluloses and C4hydroxyalkyl celluloses, see U.S. 4,000,093, December 28, 1976 to Nicol, et al.; andthe methyl cellulose ethers having an average degree of substitution (methyl) peranhydroglucose unit from about 1.6 to about 2.3 and a solution viscosity of fromabout 80 to about 120 centipoise measured at 20°C as a 2% aqueous solution. Suchmaterials are available as METOLOSE SMIOO and METOLOSE SM200, which arethe trade names of methyl cellulose ethers manufactured by Shin-etsu Kagaku KogyoKK.Additional classes of SRA's include: (I) nonionic terephthalates using diisocyanatecoupling agents to link polymeric ester structures, see U.S. 4,201,824, Violland et al.SUBSTITUTE SHEET (RULE 26)W0 98/ 134531015202530CA 02265891 1999-03-15PCT/US97/1670659and U.S. 4,240,918 Lagasse et al.; and (II) SRA's with carboxylate terminal groupsmade by adding trimellitic anhydride to known SRA's to convert terminal hydroxylgroups to trimellitate esters. With the proper selection of catalyst, the trimelliticanhydride forms linkages to the terminals of the polymer through an ester of theisolated carboxylic acid of trimellitic anhydride rather than by opening of theanhydride linkage. Either nonionic or anionic SRA's may be used as startingmaterials 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) anionic terephthalate-based SRA's of the urethane-linked variety, see U.S. 4,201,824. Violland et al.;Form of the compositionsThe particle of the present invention can be introduced in the detergent componentvia a variety of methods, including dry-mixing and agglomerating of the variouscompounds comprised in the detergent component.The detergent compositions or components thereof can have a variety of physicalforms including granular. tablet, flake, pastille and bar forms. The compositions areparticularly the so-called concentrated granular detergent compositions adapted to beadded to a washing machine by means of a dispensing device placed in the machinedrum with the soiled fabric load.The bulk density of granular detergent compositions in accordance with the presentinvention typically have a bulk density of at least 600 g/litre, more preferably from650 g/litre to 1200 g/litre. Bulk density is measured by means of a simple funnel andcup device consisting of a conical funnel moulded rigidly on a base and providedwith a flap valve at its lower extremity to allow the contents of the funnel to beemptied into an axially aligned cylindrical cup disposed below the funnel. The funnelis 130 mm high and has internal diameters of 130 mm and 40 mm at its respectiveupper and lower extremities. It is mounted so that the lower extremity is 140 mmabove the upper surface of the base. The cup has an overall height of 90 m. aninternal height of 87 mm and an internal diameter of 84 mm. Its nominal volume is500 ml.SUBSTITUTE SHEET (RULE 25)W0 98l134531015CA 02265891 1999-03-15PCTIUS97/1670660To carry out a measurement, the funnel is filled with powder by hand pouring, theflap valve is opened and powder allowed to overfill the cup. The filled cup isremoved from the frame and excess powder removed from the cup by passing astraight edged implement eg; a knife, across its upper edge. The filled cup is thenweighed and the value 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 compacting process, suchas tabletting, briquetting or extrusion, preferably tabletting. Preferably tablets for usein dish washing processes, are manufactured using a standard rotary tabletting pressusing compression forces of from 5 to 13 KN/cmz, more preferably from 5 tol IKN/cmz so that the compacted solid has a minimum hardness of l76N to 275N,preferably from 195N to 245N, measured by 21 C100 hardness test as supplied by 1.Holland instruments. This process may be used to prepare homogeneous or layeredtablets of any size or shape. Preferably tablets are symmetrical to ensure the uniformdissolution of the tablet in the wash solution.SUBSTITUTE SHEET (RULE 26)W0 98/13453101520253035CA 02265891 1999-03-15PCT/U S97/ 1670661Abbreviations used in ExamplesIn the detergent compositions, the abbreviated component identifications have thefollowing meanings:LASTASCxyASC46SASCxyEzSCxyEzQASSoapCFAATFAATPKFASTPPTSPPZeolite AZeolite A (dry)Zeolite MAPNaSKS-6Citric acidBorateCarbonateBicarbonateSodium linear C12 alkyl benzene sulfonateSodium tallow alkyl sulfateSodium C1X — C1y alkyl sulfateSodium C14 - C16 secondary (2,3) alkyl sulfateSodium C1x-C1y alkyl sulfate condensed with 2 moles ofethylene oxideC1x-C1y predominantly linear primary alcohol condensedwith an average of 2 moles of ethylene oxideR2.N+(CH3)2(C2H4OH) with R2 = C12 - C14Sodium linear alkyl carboxylate derived from an 80/20mixture of tallow and coconut oilsC12-C14 (coco) alkyl N-methyl glucamideC16-C13 alkyl N-methyl glucamideC12_C14 topped whole cut fatty acidsAnhydrous sodium tripolyphosphateTetrasodium pyrophosphateHydrated Sodium Aluminosilicate of formulaNa12(A102SiO2)12.27H2O having a primary particle sizein the range from 0.1 to 10 micrometersZeolite A with a moisture content of lee than 10% byweightHydrated sodium aluminosilicate zeolite MAPhaving asilicon to aluminium ratio of 1.07Crystalline layered silicate of formula 5- Na2Si2O5Anhydrous citric acidSodium borateAnydrous sodium carbonate with a particle size between200nm and 900umAnhydrous sodium bicarbonate with a particle sizedistribution between 4O01.tm and l2OO11mSUBSTITUTE SHEET (RULE 26)W0 98/ 13453101520253035SilicateSodium sulfateCitrateMA/AAAACMCCellulose etherProteaseAlcalaseCellulaseAmylaseLipaseEndolasePB4PBIPercarbonateNOBSTAEDMn catalystCA 02265891 1999-03-15PCT/US97/ 1670662Amorphous Sodium Silicate (SiO2:Na2O = 2.0:1)Anhydrous sodium sulfateTri-sodium citrate dihydrate of activity 86.4% with aparticle size distribution between 425 um and 850umCopolymer of 1:4 maleic/acrylic acid, average molecularweight about 70,000Sodium polyacrylate polymer of average molecular weight4,500Sodium carboxymethyl celluloseMethyl cellulose ether with a degree of polymerization of650 available from Shin Etsu ChemicalsProteolytic enzyme of activity 4KNPU/ g sold by NOVOIndustries A/ S under the tradename SavinaseProteolytic enzyme of activity 3AU/g sold by NOVOIndustries A/SCellulytic enzyme of activity 1000 CEVU/g sold byNOVO Industries A/S under the tradename CarezymeAmylolytic enzyme of activity 120KNU/g sold by NOVOIndustries A/ S under the tradename Termamyl 120TLipolytic enzyme of activity IOOKLU/g sold by NOVOIndustries Al S under the tradename LipolaseEndoglucanase enzyme of activity 3000 CEVU/g sold byNOVO Industries A/SSodium perborate tetrahydrate of nominal formulaNaBO2.3H2O.H2O2Anhudrous sodium perborate bleach of nominal formulaNaBO2.H2O2Sodium percarbonate of nominal formula2Na2CO3.3H2O2Nonanoyloxybenzene sulfonate in the form of the sodiumsaltTetraacetylethylenediamineMnIV2(m-O)3(l ,4,7-trimethyl-1,4,7-triazacyclononane)2(PF6)2, as described in U.S. Pat. Nos.5,246,621 and 5,244,594.SUBSTITUTE SHEET (RULE 26)W0 98Il3453101520253035DTPADTPMPPhotoactivatedBrightener lBrightener 2HEDPEDDSQEAIQEA2QEA3PEGXPEOTEPAEPVPPVNOPVPVISRP 1SRP2Silicone antifoamWaxCA 02265891 1999-03-15PCT/US97ll670663Diethylene triamine pentaacetic acidDiethylene triamine penta (methylene phosphonate),marketed by Monsanto under the Tradename Dequest2060Sulfonated Zinc Phthlocyanine encapsulated in bleachdextrin soluble polymerDisodium 4,4'—bis(2-sulphostyry)biphenylDisodium 4,4‘—bis(4-ani1ino-6-morpholino-1.3.5-triazin-2-yl)amino) stilbene-2:2‘-disulfonate1 ,1 -hydroxyethane diphosphonic acidEthylenediamine-N, N‘-disuccinic acidbis((C2H50)(C2H40)n) (CH3) 'N+'C6H12'N+'(CH3)bis((C2H5O)-(C2H4O)n), wherein n=from 20 to 30bis((C2H5O)-(C2H4O)n) (CH3) N+ R1, wherein R1 isC4-C12 alkyl group and n=from 20 to 30tri{(bis((C2H5O)-(C3H4O)n)(CH3)-N+)-(CONC3H5)}-C3H6O, wherein n=from 20 to 26Polyethylene glycol. with a molecular weight of xPolyethylene oxide, with a molecular weight of 50,000Tetraethylenepentaamine ethoxylatePolyvinylpyrolidone polymerPolyvinylpyridine N-oxideCopolymer of polyvinylpyrolidone and vinylimidazoleSulfobenzoyl and capped esters with oxyethylene oxy andterephtaloyl backboneDiethoxylated poly (1, 2 propylene terephtalate) shortblock polymerPolydimethylsiloxane foam controller with siloxane-oxyalkylene copolymer as dispersing agent with a ratio ofsaid foam controller to said dispersing agent of 10:1 to10021Paraffin waxIn the following examples all levels are quoted as % by weight of the composition:SUBSTITUTE SHEET (RULE 26)CA 02265891 l999-03- 15W0 98/13453 PCT/US97/ 1670664Example 1The following detergent formulations of particular utility under European machine5 wash conditions were prepared.A B C DBlown 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 0.6Brightener 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 -AgglomerateQEA 1 0.8 1.0 1.4 0.5QEA 2 - - - 0.5Zeolite A (dry) 2.5 2.5 3.0 2.0Dry 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 18.5SUBSTITUTE SHEET (RULE 26)CA 02265891 l999-03- 15WO 98/13453 PCT/US97/1670665TAED 3.0 2.0 - 2.0EDDS - 2.0 2.4 -Protease 1.0 1.0 1.0 1.0Lipase 0.4 0.5 0.4 0.2Amylase 0.2 0.2 0.2 0.4Photoactivated - - - 0. 1 5bleachTotal 100.0 100.0 100.0 lO0.0SUBSTITUTE SHEET (RULE 26)CA 02265891 l999-03- 15WO 98/13453 PCT/US97/1670666Example 2The following granular detergent formulations were prepared.E F G H I JBlown 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 - - -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 6.0PEG 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 onC25E9 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 2.0QEA 1 0.9 0.9 - - 0.5 1.1QEA 2 - - 0.8 1.0 - -QEA 3 - - 0.4 - - -Zeolite A (dry) 4.5 7.5 7.5 2.0 7.5 7.5HEDP - 1.0 - - 2.0 —Carbonate - 4.0 4.0 - 4.0 4.0PEG 6000 - - - 0.5 0.5 -SUBSTITUTE SHEET (RULE 26)CA 02265891 1999-03-15W0 98/13453 PCT/US97/1670667PEG 8000 - 0.5 0.5 - ~ 0.5Misc (water etc) - 2.0 2.0 — 2.0 2.0Dry additivesTEAD 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 — - 0.6Cumene sulfonic — 2.0 2.0 - 2.0 2.0acidLipase 0.4 0.4 0.4 0.06 0.05 0.2Cellulase 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 - - -SRP1 - 0.5 0.5 - - -Silicone amifoam — 0.2 0.2 - 0.2 0.2Total 100.0 100.0 100.0 100.0 100.0 100.0SUBSTITUTE SHEET (RULE 26)CA 02265891 l999-03- 15W0 98/ 13453 PCT/US97/1670668Example 3The following granular detergent formulations were prepared.5K L MBlown 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 0.2Carbonate 8.0 16.0 20.0DTPMP - 0.4 0.4Spray On - 1.0 5.0C45E7 1.0 1.0 1.0AgglomerateQEA 1 0.6 2.0 1.0Zeolite A (dry) 2.0 4.0 2.2Dry additivesHEDP 1.0 - -PVPVI/PVNO 0.5 0.5 0.5Protease 1 .0 1.0 1 .0Lipase 0.4 0.1 0.2Amylase 0.1 0.1 0.1Cellulase 0.1 0.1 0.1TEAD - 6.1 4.5PB1 11.0 5.0 6.0Sodium Sulfate - 6.0 -Balance (Moisture and Misc.)SUBSTITUTE SHEET (RULE 26)CA 022565891 l999-03- 15WO 98/1345369Example 4The following granular detergent compositions.PCT/US97/16706N 0Blown powderZeolite A 20.0 -STPP - 20.0LAS 7.0 6.0C68AS 6.0 2.0Silicate 3.0 8.0MA/AA 5.0 2.0CMC 3.0 0.6QEA 3 0.1 -Brightener 1 - 0.2DTPMP 0.1 0.4Spray onC45E7 6.5 5.0Silicone antifoam 0.3 0.3Perfume 0.2 0.2Dry additivesCitric Acid - 2.0Carbonate 10.0 9.0PB1 1.5 2.0PB4 - 13.0TAED 7.0 2.0Photoactivated bleach 15 ppm 15 ppmProtease 10.5 1 .0Lipase 0.1 0.08Amylase 0.3 0.4Cellulase 0.4 0.1Sulfate 8.0 20.0AgglomerateQEA 1 0.9 0.6SUBSTITUTE SHEET (RULE 26)CA02265891 1999-03-15PCT/US97/16706W0 98Il345370Zeolite A (dry) 2.0 1.4LAS 1.0 1.5Balance (Moisture and misc.)Density (g/litre) 700 700SUBSTITUTE SHEET (RULE 26)CA 02265891 l999-03- 15W0 98/13453 PCTIUS97/16706Example 5The following detergent compositions were prepared.P Q R SBlown PowderZeolite MAP — - - 20.0Zeolite A 15.0 15.0 17.0 -Sodium Sulfate 0.0 5.0 0.0 -LAS 3.0 3.0 5.0 5.0QAS — 1.5 0.5 -DTPMP 0.4 0.2 0.0 -CMC 0.4 0.4 0.4 1.0MA/AA 4.0 2.0 2.0 1.0AgglomeratesLAS 5.0 5.0 1.0 6.0TAS 2.0 2.0 0.4 2.0Silicate 3.0 3.0 0.5 2.5QEA 1 1.0 2.5 1.0 1.0Zeolite A (dry) 8.0 8.0 5.0 5.0Carbonate 8.0 8.0 10.0 -PEG 8000 - 2.0 1.0 0.2Spray OnPerfume 0.3 0.3 0.4 0.4C25E5 2.0 2.0 6.0 5.0C25E3 2.0 - - 1.5Dry additivesCitric Acid - 2.0 2.0 2.0Citrate 3.0 3.5 2.0 1.5Bicarbonate - 3.0 - -Carbonate 8.0 15.0 14.0 10.0Percarbonate — 7.0 10.0 20.0TAED 6.0 2.0 4.0 4.0PB1 14.0 7 .0 - -EDDS - 2.0 0.5 -SUBSTITUTE SHEET (RULE 26)CA 02265891 l999-03- 15SUBSTITUTE SHEET (RULE 26)W0 98I13453 PCT/US97/ 1670672Polyethylene oxide ofMW 5,000,000 - - 0.2 -Bentonite clay - 8.0 - -Protease 1.0 1.0 1.3 0.8Lipase 0.4 0.1 0.5 0.3Amylase 0.6 0.6 0.6 0.2Cellulase 0.6 0.6 0.3 -Silicone antifoam 5.0 3.0 1.0 0.7Dry additivesSodium sulfate 0.0 3.0 0.3 -Balance (Moisture and Misc.) 100.0 100.0 100.0 100Density (g/litre) 850 850 850 850

Claims (18)

Claims

1. A particle comprising (a) 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 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) and mixtures thereof;

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 substitution C3-C12 alkyl, 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 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 -[(R60)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; and (b) a powdered carrier material, wherein the ratio of (a) to (b) is from 1:15 to 4:1 by weight.

2. A particle comprising:

(a) 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 or wherein M1 is an N+ or N group; each M2 is an N+ or N group, and at least one M2is an N+ group;

3) ethoxylated cationic polyamines having the formula:

4) and mixtures thereof;

wherein A1 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 for ned; 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 -[(R6O)m(CH2CH2O)n]-; wherein R6 is C3-C4 alkylene or hydroxyalkylene and m and n are nurnbers 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 monomamines, 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; and (b) an aluminosilicate carrier material.

3. A particle according to Claim 1 or 2 wherein said cationic compound comprises an ethoxylated cationic monoamine, wherein one R2 is methyl, two R2 groups are the moiety L-X, m is 0 and n is at least about 20.

4. A particle according to any of Claims 1 to 3 wherein said cationic compound comprises an ethoxylated cationic diamine wherein R1 is a C2-C6 alkylene.

5. A particle according to Claim 4 wherein R1 in said ethoxylated cationic diamine is hexamethylene.

6. A particle according to any of Claims 1 to 5 wherein said cationic compound comprises an ethoxylated cationic polyamine wherein R4 is a substituted C3-C6 alkyl, hydroxylakyl or aryl group;
A1 is and p is from 3 to 6.

7. A particle according to any of Claims 4 to 6, wherein each R2 group of the cationic compound is methyl or the moiety -L-X, each R3 group of the cationic compound is methyl and M1 and each M2 are an N+ group.

8. A particle according to any of Claims 4 to 7 wherein m is 0 and n is at least 12.

9. A particle according to any of Claims 4 to 6 wherein m is 0 and n is at least 20.

10. A particle according to any of Claims 1 to 9 wherein said carrier material has a water content of less than 15% by weight of the carrier material.

11. A particle according to any of Claims 1 to 10 wherein said carrier material comprises a sodium aluminosilicate zeolite.

12. A particle according to any of Claims 1 to 11 wherein the ratio of water-soluble cationic compound to carrier material is from 1:7 to 1:1.

13. A particle according to any of Claims 1 to 11 wherein an anionic surfactant is present.

14. A particle according to Claim 13 wherein said anionic anionic is selected from the group consisting of alkyl sulphates, alkyl benzene sulphonates and alkyl sulphates condensed with ethylene oxide.

15. A particle according to any of Claims 1 to 14 wherein a polyethylene glycol is present.

16. The use of a particle according to any of Claims 1 to 15 in a granular detergent composition, wherein said cationic compound is present in an amount of from 0.01% to 30% by weight of said detergent composition.

17. The use of a particle according to any of Claims 1 to 16 in granular detergent composition, wherein the cationic compound is present in an amount of from 0.2% to 3% by weight of said detergent composition.

18. An agglomeration process for making a particle according to any of Claims 1 to 17 which comprises the steps:

(a) heating of the water-soluble cationic compound to obtain a melted compound;

(b) agglomerating the melted compound of (a) with the carrier material to an agglomerate particle;

(c) cooling the agglomerate particle of (b).