Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
W0 98/13452101520253035CA 02265942 1999-03-llPCT/US97ll670SDetergent Composition or ComponentTechnical FieldThe present invention relates to a detergent composition or component containingcationic compounds with clay-soil/ particulate soil removal/anti-redepositionproperties and one or more carboxylate-containing polyelectrolyte compounds.with builder or dispersant properties, for use in laundry and dish washingprocesses.Background to the InventionA particularly important property of a detergent composition is its ability toremove particulate type soils from a variety of fabrics during laundering. Oneimportant particulate group of soils is the clay-type soils. Clay soil particlesgenerally comprise negatively charged layers of aluminosilicates and positivelycharged cations (e.g. calcium) which are positioned between and hold together thenegatively charged layers.A variety of models can be proposed for compounds which have clay soil removalproperties. One model requires that the compound have two distinct characteristics.The first is the ability of the compound to adsorb onto the negatively chargedlayers of the clay particle; and the ability of the compound. once adsorbed, to pushapart (swell) the negatively charged layers so that the clay particle loses itscohesive force and can be removed in the wash water.SUBSTITUTE SHEET (RULE 26)W0 98/ 13452101520253035CA 02265942 1999-03-llPCTIU S97/ 16705In 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 isespecially noticeable on white fabrics. To minimise this problem, antiâredepositionagents are also often included in detergent compositions.Other detergent compounds traditionally employed in detergents are soildispersants and antiâencrustation agent, such as carboxylate-containingpolyelectrolyte compounds.EP-B-111 965 discloses the use in detergents of cationic compounds, which haveboth clay-soil removal and antiâredeposition properties.US 4,659,802 and US 4,664,848 describe quaternized amines which have clay-soilremoval and antiâredeposition properties and which can be used in combinationwith anionic surfactants.A model proposed for the antiâredeposition action of these compounds is asfollows. Adsorption of the positively charged molecule on the surface of clayparticles in the wash water gives the clay particles the dispersancy properties of themolecule. As more and more of these compounds adsorb onto the suspended claysoil particles, the latter become encased within a hydrophilic layer. As such thehydrophilically encased soil is prevented from redepositing on hydrophobic fabricssuch as polyester, during the laundering or dish washing cycle.It has been found that the known cationic clay-soil removal compounds do notalways remove the clay particles rapidly and efficiently from the fabric surface intothe washing water. This may be due to clay and particulate soils being heldtogether by calcium bridges which may prevent the cationic clay soil removalcompound from pushing apart the negatively charged layers of the clay, therebypreventing the clay particles losing their cohesive force.It has also been found that the antiâredeposition properties of these known cationicclay-soil removal compounds can be diminished under hardâwater conditionsduring the laundry or dishwashing process, i.e when a high level of free calcium(and/ or magnesium) is present in the wash water.SUBSTITUTE SHEET (RULE 26)W0 98/13452101520253035CA 02265942 1999-03-113PCT/US97I16705The Applicants have now found that these problems can be ameliorated byinclusion of speciï¬c amounts of carboxylate-containing polyelectrolyte compounds,which have builder or dispersant properties, in a detergent component or in adetergent composition comprising speciï¬c amounts of cationic, (partially)quaternized ethoxylated (poly) amines which have clayâsoil removal/anti-redeposition properties. An example of such a component is a spray-dried granularparticle. Such detergent components or detergent compositions have now beenfound to deliver a surprisingly better clay/ soil removal and cleaning performancethan that of detergent compositions employing either of the two componentsindividually. It has also been found that speciï¬c ratios of the cationic quaternizedethoxylated (poly) amines to the carboxylateâcontaining polyelectrolyte compoundsare particularly preferred and enable good performance beneï¬ts to be achievedeven when using very low amounts of each component.The cleaning performance beneï¬ts of the detergent compositions containing bothcarboxylateâcontaining polyelectrolyte compounds and cationic, (partially)quaternized ethoxylated (poly) amines are found to depend both on the amount ofcarboxylate-containing polyelectrolyte compound used and its properties (e. g. themolecular weight of the polymeric compound and the monomeric segmentscomprised in the polymeric compound). For example, in built conditions it hasbeen found that co-polymeric polycarboxylic compounds, for example maleic/acrylic co-polymers, have a better (calcium) builder/ dispersant performance thanhomo-polymeric polycarboxylic compounds of a similar molecular weight. Thus,lower levels of certain, preferred polymeric compounds are as effective as higherlevels of others.A further advantage of the present invention is that the clay/ soil removal beneï¬tscan even be observed after the completion of only one wash cycle.All documents cited in the present description are, in relevant part, incorporatedherein by reference.SUBSTITUTE SHEET (RULE 26)CA 02265942 l999-03- ll4W0 98/13452 PCT/US97/ 16705Summary of the invention5 In accordance with the present invention there is provided a solid, preferably agranular detergent composition or component thereof which comprises:(a) a carboxylate-containing polyelectrolyte compound;and10(b) a water-soluble cationic compound having clay soil removal/anti-redepositionproperties, which is selected from the group consisting of:l) ethoxylated cationic monoamines having the formula:15R2R2 ~âN+ ~â L E XR22) ethoxylated cationic diamines having the formula:<R3>d R3 <R3>d R3X#LvM1-âR1~N+~--LâX or R3*~M1âR1âN+e-R or/ /L L L L LX X X X X3(XâLA)2"-*M2~R1"M2-âMR220 R2SUBSTITUTE SHEET (RULE 26)CA 02265942 l999-03- 11âLW0 98/ 13452 H PCT/US97/16705wherein 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>dR4v[<A1>q~(R5>tâ~M2~L- X]pR24) mixtures thereof;0 o o o owhereinA1is~"NCâ-', -% Nco-~â, -- NCN-~, --âcN-4, +-A ocNâ,R R R R R Ro o -o o o---coâ, ---ocoâ~, AcNc--- or ---oâ,lo RR 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 toabout 20 oxyalkylene units provided that no O-N bonds are formed; each R2 isC1-C4 alkyl or hydroxyalkyl, the moiety -L-X, or two R2 together form the15 moiety -(CH2)r-A2-(CH2)s-, wherein A2 is -0- or -CH2-, r is 1 or 2, s is 1 or 2and r + s is 3 or 4; each R3 is C1-C3 alkyl or hydroxyalkyl, benzyl, the moietyL-X, or two R3 or one R2 and one R3 together form the moiety -(CH2),-Al(CH2)s-; R4 is a substituted C3-C1; alkyl, hydroxyalkyl, alkenyl, aryl or alkarylgroup having p substitution sites; R5 is C31-C12 alkenyl, hydroxyalkylene,2o alkenylene, arylene or alkarylene, or a C2-C3 oxyalkylene moiety having from 2 toabout 20 oxyalkylene units provided that no 0-0 or O-N bonds are formed: X is anonionic group selected from the group consisting of H, C1-C4 alkyl orSUBSTITUTE SHEET (RULE 26)WO 98/13452101520253035CA 02265942 1999-03-ll6 PCT/US97/ 16705hydroxyalkyl ester or ether groups, and mixtures thereof; L is a hydrophilic chainwhich contains the polyoxyalkylene moietyâ[(R6O)m(CH7_CH2O),,]-; wherein R6 is C3-C4 alkylene or hydroxyalkylene andIn and n are numbers such that the moiety-(CH2CH2O),,- comprises at least about 50% by weight of said polyoxyalkylenemoiety; d is 1 when M2 is N+ and is 0 when M2 is N; n is at least about 16 forsaid cationic monoamines, is at least about 6 for said cationic diamines and is atleast 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 wherein the ratio of (a) to (b) is from 1:95 to 95:1.A preferred ratio of (a) to (b) is from 1:1 to 126.Furthermore, it has been found that the detergent compositions but particularly thedetergent components and especially the sprayâdried particles comprising thecationic quaternized ethoxylated (poly) amines and the carboxylate-containingpolyelectrolyte compounds in the specific levels and ratios are crisp and freeï¬owing and do not have the tendency to cake, and are capable of absorbing otherdetergent compounds when present, such as for example anionic, cationic andnonionic surfactants. This thus minimises caking of the compositions comprisingthe components or sprayâdried particles.Therefore in accordance with a preferred aspect of the invention is a sprayâdriedparticle or granule comprising compounds (21) and (b) as described above and with(a) and (b) in a referred ratio of from 1:1 to 1.10.Preferred anionic counterions for the cationic waterâsoluble compounds are halidessuch as Clâ and Brâ, or most preferably MeSO4'.SUBSTITUTE SHEET (RULE 26)W0 98/ 13452101520253035CA 02265942 1999-03-ll7 PCT/US97I16705Detailed description of the inventionAn essential feature of the present invention is a water-soluble cationic compoundwhich has particulate soil/ clay-soil removal/anti-redeposition properties and whichis selected from the group consisting of cationic mono-di- and polyamines.The ratio in the composition or component thereof of the cationic compound to thecarboxylate-containing polyelectrolyte compound is from 1:95 to 95:1, morepreferably from 1:25 to 25:1, most preferably from 1:5 to 5:1.Where low amounts of cationic compound and carboxylate-containingpolyelectrolyte are used it may be preferred that the ratio of the carboxylate-containing polyelectrolyte compound to the water-soluble cationic compound in thecomponent is preferably from 1:1 to 1:10, more preferably from 1:1 to 1:4, mostpreferably from 1:1 to 1:2.If present in a detergent composition in accordance with the present invention thewater-soluble cationic compound is preferably present at a level of from 0.01% to30%, more preferably from 0.1% to 15% , most preferably from 0.2% to 3.0% byweight of the detergent composition.In the spray-dried particle it is particularly preferred that the ratio of thecarboxylate-containing polyelectrolyte compound to the water-soluble cationiccompound in the component is from 1:1 to 1210, more preferably from 1:1 to 1:4,most preferably from 1:1 to 1:2.In the spray-dried particle or in a detergent component in accordance with thepresent invention the water-soluble cationic compound is preferably present at alevel of from 0.1% to 30%, more preferably from 0.5% to 15% , even morepreferably from 0.5% to 7%, most preferably from 0.6% to 2% by weight of thespray-dried particle or detergent component.Such a spray-dried particle or such a component preferably is present in a granulardetergent composition at a level of from 5% to 90%, more preferably from 20% to60%, most preferably from 30% to 50% by weight of the composition.SUBSTITUTE SHEET (RULE 25)WO 98/1345210152025CA 02265942 1999-03-ll8 PCT/US97/ 16705Cationic aminesThe waterâsoluble cationic compounds of the present invention useful in thedetergent compositions or components in accord with the present invention includeethoxylated cationic monoamines, ethoxylated cationic diamines and ethoxylatedcationic polyamines as previously defined.In the preceding formulas for the cationic amines, R1 can be branched(e. g.CH3ââ CH2 CH , â« CH2 ~~â CH H );C3cyclic (e.g. ),or most preferably linear(e. g. -2 CHZCH2 â , H» CH2CH2CH2 W )alkylene, hydroxyalkylene, alkenylene, alkarylene or oxyalkylene. R1 ispreferably C2-C6 alkylene for the ethoxylated cationic diamines. Each R2 ispreferably methyl or the moiety âL-X; each R3 is preferably C1-C4 alkyl orhydroxyalkyl, and most preferably methyl.The positive charge of the N+ groups is offset by the appropriate number ofcounter anions. Suitable counter anions include C 1-, Br-. S03-2, P04-2, MeSO4-and the like. Particularly preferred counter anions are Cl~ and Br-, but mostpreferably MeSO4â.SUBSTITUTE SHEET (RULE 26)W0 98/1254521015202530CA 02265942 1999-03-119PCTlUS97Il6705X can be a non-ionic group selected from hydrogen (H), C1-C4 alkyl orhydroxyalkyl ester or ether groups, or mixtures thereof. Preferred esters or ethersare the acetate ester and methyl ether, respectively. The particularly preferrednonionic groups are H and the methyl ether.In the preceding formulas, hydrophilic chain L usually consists entirely of thepolyoxyalkylene moiety -[(R6O)m(CH2CH2..O,,)-]. The moieties -(R6O)mâ and -(CH2CH2O)n- of the polyoxyalkylene moiety can be mixed together or preferablyform blocks of -(R6o),,,â and â(CH2CH2O),,- moieties. R6 is preferably C3116(propylene); m is preferably from 0 to about 5 and is most preferably 0, i.e. thepolyoxyalkylene moiety consists entirely of the moiety -(CH2CH2O),,-. The moiety â(CH2CH2O),,- preferably comprises at least about 85 % by weight of thepolyoxyalkylene moiety and most preferably 100% by weight (In is O).In 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:CH3 CH3xv oCH2CH2)ne ~ N+ CH2â CH2f( he CH2), E N* ~â~- CH2CH2O")ï¬ X(C112Cj12())ï¬)( ((]&2C3T2C)xi)(wherein X and n are deï¬ned as before, a is from 0 to 20, preferably from 0 to 4(e.g. ethylene, propylene, hexamethylene), b is l or 0. For preferred cationicmonoamines (b=O), n is preferably at least about 16, with a typical range of fromabout 20 to about 35. For preferred cationic diamines (b=1), n is at least about12 with a typical range of from about 12 to about 42.In the preceding formula for the ethoxylated cationic polyamines, R4 (linear,branched, or cyclic) is preferably a substituted C3-C6 alkyl, hydroxyalkyl or arylgroup; A1 is preferablySUBSTITUTE SHEET (RULE 25)CA 02265942 l999-03- ll10W0 98l13452 PCTIUS97/167050i#"CN_;Hn is preferably at least about 12, with a typical range of from about 12 to about 42;p is preferably from 3 to 6. When R4 is a substituted aryl or alkaryl group, q is5 preferably 1 and R5 is preferably C2-C3 alkylene. When R4 is a substituted alkyl,hydroxyalkyl, or alkenyl group, and when q is O, 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 such10 3520CN -(-V C3H6 ~)~ NH2HO â OHOWâ-â* âCN~-6* C3H6 â~)â NH2 or I /~â CN(C3H6 â)âNH2H C Ti?â HO 3CN -Jr C-3H6 ~f NH2HThese ethoxylated cationic polyamines can also be derived from15 polyaminopropyleneoxide derivatives such as:~(OC3H6)c ~ NH2-~(OC3H6)C ~ NH2SUBSTITUTE SHEET (RULE 25)W0 98/13452101520253035CA 02265942 1999-03-111 IPCT/US97/16705wherein each c is a number from 2 to about 20.Carboxylateâcontaining polyelectrolyte compoundsAn essential component of the invention is one or more carboxylate-containingpolyelectrolyte compounds, which have builder or dispersant properties.Preferably these compounds are homo- or co-polymeric polycarboxylic compoundsand most preferably coâpolymeric polycarboxylic compounds in which the acidmonomer of said polycarboxylic compound comprises at least two carboxyl groupsseparated by not more than two carbon atoms. Salts of these polycarboxyliccompounds are also considered herein. In a preferred aspect the polycarboxyliccompounds of the present invention will comprise at least 12 carboxylate groups.If present in a detergent composition in accord with the present invention thecarboxylate-containing polyelectrolyte compound is preferably present at a level offrom 0.01% to 40%, more preferably from 0.1% to 10% . most preferably from0.2% to 6% by weight of the detergent compositionIf present in a detergent component of the present invention the carboxylate-containing polyelectrolyte compound is preferably present at a level of from 0.05 %to 30%, more preferably from 0.1% to 15%, more preferably from 0.15% to 7%.most preferably from 0.2% to 2.0% or more preferred to 1.2% by weight of thedetergent component.Where the component is a sprayâdried particle, the carboxylate-containingpolyelectrolyte compound is preferably present at a level from 0.2% to 2.0% ormore preferred to 1.2% by weight of the sprayâdried particle.Such a sprayâdried particle or such a component preferably is present in a granulardetergent composition at a level of from 5% to 90%, more preferably from 20% to60% , most preferably from 30% to 50% by weight of the composition.The carboxylate-containing polyelectrolyte materials can be prepared bypolymerising or copolymerizing suitable unsaturated monomers, preferably in theirSUBSTITUTE SHEET (RULE 26)WO 98/13452101520253035CA 02265942 1999-03-ll12 PCT/U S97/ 16705acid form. Unsaturated monomeric acids that can be polymerised to form suitablepolymeric polycarboxylates are selected from acrylic acid, maleic acid (or maleicanhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconicacid and methylenemalonic acid. The presence in these carboxylate~containingpolyelectrolyte compounds herein of monomeric segments, containing nocarboxylate radicals such as vinylmethyl ether, styrene, ethylene, etc. is suitableprovided that such segments do not constitute more than 40% by weight.Carboxylate-containing materials can also optionally include further monomericunits such as nonionic spacing units. For example, suitable nonionic spacing unitsmay include vinyl alcohol or vinyl acetate.Particular preferred carboxylate-containing polyelectrolyte compounds areacrylic/maleicâbased coâpolymers. Such materials include the water-soluble salts ofcopolymers of acrylic acid and maleic acid/ maleic anhydride. The averagemolecular weight of such copolymers in the acid form preferably can range from1,000 to 100,000, more preferably from 2,000 to 75,000 or even more preferred to70,000, but most preferred are the co-polymers with a average molecular weight offrom 2.500 to 20,000 or in another preferred embodiment from 60,000 to 75,000or even 70,000. The ratio of acrylate to maleate segments in such copolymers willgenerally range from 30:1 to 1:30, more preferably from 10:1 to 1:1, mostpreferably from 4:1 to 7:3. Water-soluble salts of such acrylic acid/maleic acidcopolymers can include, for example, the alkali metal, ammonium and substitutedammonium salts. Soluble acrylate/maleate copolymers of this type are knownmaterials which are described in European Patent Application No. 66915,published December 15, 1982, as well as in EP 193,360, published September 3,1986.Other suitable carboxylate-containing polyelectrolyte compounds can be derivedfrom acrylic acid. Such acrylic acidâbased polymers which are useful herein arefor example the water-soluble salts of polymerized acrylic acid. The averagemolecular weight of such homo-polymers in the acid form preferably ranges from1,800 to 100,000, more preferably from 2,000 to 10,000, most preferably from3,000 to 5,000. Water-soluble salts of such acrylic acid polymers or can include,for example, the alkali metal, ammonium and substituted ammonium salts. Solublepolymers of this type are known materials. Use of polyacrylates of this type inSUBSTITUTE SHEET (RULE 26)W0 98/13452101520253035CA 02265942 1999-03-ll13 PCTIUS97/16705detergent compositions has been disclosed, for example, in Diehl, U.S. Patent3,308,067, issued March 7, 1967.Also polyamino-based compounds are useful herein including those derived fromaspartic acid such as those disclosed in EP-Aâ305282, EPâA-305283 and EP~A-351629.A further example of carboxylate-containing polyelectrolyte compounds suitablefor the purpose of the invention include the maleic/acrylic/vinyl alcoholterpolymers. Such materials are also disclosed in EP 193,360, including, forexample, the 45/45/10 terpolymer of acrylic/maleic/vinyl alcohol.Terpolymers containing monomer units selected from maleic acid, acrylic acid andpolyaspartic acid, particularly those having an average molecular weight of from5.000 to 2 0,000, are also suitable herein.Further useful carboxylate-containing polyelectrolyte compounds are thepolyelectrolyte-containing glycols, particularly those of molecular weight 1.000-10,000, more particularly 2,000 to 8,000 and most preferably about 4,000.Other preferred carboxylate-containing polyelectrolyte compounds are those whichtypically have a hydrophilic backbone and at least one hydrophobic side chain.Preferably this type of carboxylate-containing polyelectrolyte compounds have amolecular weight of between 500 and 100,000, more preferred from 1.000 to70,000, especially preferred from 1,500 to 10,000, or in another preferredembodiment from 2,800 to 6,000. Carboxylate-containing polyelectrolytecompounds for use herein may for example be prepared by using conventionalaqueous polymerisation procedures, suitable methods are for example described inGB 89 24477, GB 89 24478 and GB 89 24479.Generally the hydrophilic backbone of the polymer is predominantly linear (themain chain of the backbone constitutes at least 50%, preferably more than 75%,most preferred more than 90% by weight of the backbone), suitable monomerconstituents of the hydrophilic backbone are for example unsaturated C1-C5 acids,ethers, alcohols, aldehydes, ketones or esters. sugar units, alkoxy units. maleicSUBSTITUTE SHEET (RULE 26)WO 98/134521015202530CA 02265942 1999-03-ll14 PCT/US97l 16705anhydride and saturated polyalcohols such as glycerol. Preferably the hydrophobicside groups are composed of alkoxy groups for example butylene oxide and/orpropylene oxide and/or alkyl or alkenyl chains having from 5 to 24 carbon atoms.The hydrophobic groups may be connected to the hydrophilic backbone viarelatively hydrophilic bonds for example a poly ethoxy linkage.Preferred carboxylateâcontaining polyelectrolyte compounds of this type are thepolymers described in W0 91/ 08281.Preferred counterions for the carboxy1ateâcontaining polyelectrolyte compounds arefor example sodium, magnesium or calcium ions.Sprayâdried particleA preferred component according to the invention comprises a spray-dried particlecan be used in a detergent composition. The detergent composition may consistessentially of such particles, but preferably the detergent composition comprisesthe particles and other components, having a different chemical composition.The spray-dried particle of the invention are formed by a process, which includes asprayâdrying step. The spray-drying step produces a spray-dried particle, generallyhaving a free-moisture content below 10% by weight, preferably less than 7%, ormore preferably less than 6%.As used herein, freeâmoisture content is determined by placing 2 grams of asample of base detergent granules in for example a petri dish, placing the sample ina heating chamber up to 160°C for 10 minutes, followed by measurement of theweight loss due to water evaporation.Generally, the particles of the invention are formed in a process whereby a paste orslurry or crutcher mix comprising the cationic compound and the carboxylateâcontaining polyelectrolytes, is formed into particles and dried in a sprayâdryingprocess as known in the art.SUBSTITUTE SHEET (RULE 26)WO 98/13452101520253035CA 02265942 1999-03-ll1 5 PCT/US97/ 16705The process for manufacturing the spray-dried particles comprises preparing anaqueous solution-dispersion, commonly referred to as a paste or slurry or crutchermix, comprising the components of the ï¬nal particle.The cationic compound and the carboxylateâcontaining polyelectrolyte can bemixed together prior to addition to the other ingredients of the crutcher mix, whichwill be comprised in the spray-dried particle. Alternatively, the cationic compoundand the carboxylateâcontaining polyelectrolyte can be mixed with other organiccompounds, which will be comprised in the final spray-dried particle, prior toaddition to the other ingredients of the crutcher mix (which will be comprised inthe ï¬nal spray-dried particle). Alternatively, the cationic compound and thecarboxylate-containing polyelectrolyte can be added to the crutcher or crutcher mixat the same time as the other ingredients, which will be comprised in the ï¬nalspray-dried particle.To save energy and to increase throughput of the drying equipment the crutchermix will usually be of as high a solids content as feasible, e.g., 40% to 80%, withthe balance, e.g. 10% to 60%, being water. More water may be used but thenenergy demands are increased, tower throughput are diminished, products resultingmay be tackier and poorer ï¬owing g and often the desired low density base andï¬nal detergent composition particles will not be obtained. The crutcher mixpreferably has a temperature of from 50°C to 100°C, typically 80°C prior to thedrying step.The crutcher mix is then sprayed at an elevated pressure (usually from 40 to 100bar, preferably 70 to 90 bar, typically at about 80 bar) through one or more spraynozzles into a drying tower, through which drying air, passes to dry the resultingdroplets of crutcher mix to globular the particles. Instead of spray nozzles,equivalent atomisers of other designs may also be used. The preferred spray towerdesign is counter-current, the height of the tower usually being from 5 to 25 metersand the entering hot air, usually the gaseous products of combustion of oil or gas,being at a temperature in the range of from 150° to 400°C and the outlet air usuallyat a temperature in the range of from 50° to 160°C. Concurrent tower designs mayalso be employed wherein similar inlet and outlet air temperatures obtain.SUBSTITUTE SHEET (RULE 26)W0 98/13452101520253035CA 02265942 1999-03-1116PCTIUS97/16705The nozzle size for producing droplets of crutcher mix will be chosen suchparticles of the preferred particle size are formed, preferably of from 0.1 mm to3.0 mm. Preferably, substantially all the particles are within this range whenremoved from the spray tower, but any offâsize particles can be removed byscreening, may be size-reduced to the desired size range or may be recycled in thesame or a subsequent crutcher mix.Preferred additional ingredient of the crutcher mix can be anionic surfactants,cationic softeners or cationic surfactants, nonionic, sulphate and carbonate salts,and hydrotropes.Optionally, after drying is complete and the particles in the desired size range areobtained, additional detergent compounds or components can be added to theparticles, preferably by melting the compound or component and spraying themolten compound or component, which may be in concentrated aqueous solutionbut preferably is free of water, onto the surfaces of the tumbling base particles inan inclined drum, through which the particles progress from an elevation feed endto the discharge end.The particle can be introduced to a detergent composition by any method, knownin the art. Preferably, the particles are dryâadded to the other detergent ingredients.Additional detergent ingredientsThe detergent compositions or components in accordance with the invention mayalso contain additional detergent ingredients. The precise nature of these additionalingredients, and levels of incorporation thereof will depend on the physical form ofthe component, and the precise nature of the washing operation for which it is tobe used.The components or the detergent compositions in accordance with the inventionpreferably contain one or more additional detergent components selected fromsurfactants, additional builders, sequestrants, bleach, bleach precursors, bleachcatalysts, additional organic polymeric compounds, enzymes, suds suppressors,additional lime soap dispersants, additional soil suspension and anti-redepositionagents soil releasing agents, perfumes and corrosion inhibitors.SUBSTITUTE SHEET (RULE 26)W0 98/ 1345210152025CA 02265942 1999-03-111 7PCT/US97/16705Cationic polymersA preferred additional component can be additional polymeric cationic ethoxylatedamine compounds with particulate soil/clay-soil remova1/ antiâredeposition,selected from the group consisting of waterâsoluble cationic polymers. Thesepolymers comprise a polymer backbone, at least 2M groups and at least one L-Xgroup, 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 hydrophilicchain connecting groups M and X or connecting X to the polymer backbone.As used herein, the term "polymer backbone" refers to the polymeric moiety towhich groups M and L-X are attached to or integral with. Included within thisterm are oligomer backbones (2 to 4 units), and true polymer backbones (5 or moreunits).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:M M LL XXA 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 02265942 l999-03- 11WO 98/13452 18 PCT/US97I16705_._._ M .2 ___ M 4m.L LX XC DAny polymer backbone can be used as long as the cationic polymer formed iswaterâsoluble and has clay soil removal/anti-redeposition properties. Suitable5 polymer backbones can be derived from the polyurethanes, the polyesters, thepolyethers, the polyamides, the polyimides and the like, the polyacrylates, thepolyacrylamides, the polyvinylethers, the polyethylenes, the polypropylenes andlike polyalkylenes, the polystyrenes and like polyalkarylenes, thepolyalkyleneamines, the polyalkyleneimines, the polyvinylamines, the10 polyalylamines, the polydiallylamines, the polyvinylpyridines, thepolyaminotriazoles, polyvinyl alcohol, the aminopolyureylenes, and mixturesthereof.M can be any compatible cationic group which comprises an N+ (quarternary),15 positively charged center. The quartemary positively charged center can berepresented by the following general structures E and F:20 Particularly preferred M groups are those containing a quarternary centerrepresented by general structure E. The cationic group is preferably positionedclose to or integral with the polymer backbone.SUBSTITUTE SHEET (RULE 26)W0 98/123452101520253035CA 02265942 1999-03-ll19 PCTIU S97/ 16705The positive charge of the Nâ'â centres is offset by the appropriate number ofcounter anions. Suitable counter anions include Clâ, Brâ, S032â, S042â, PO42â,MeOSO3' and the like. Particularly preferred counter anions are C1â and Brâ.X can be a nonionic group selected from hydrogen (H), C1-C4 alkyl orhydroxyalkyl ester or ether groups, and mixtures thereof. The preferred ester orether groups are the acetate ester and methyl ether, respectively; The particularlypreferred nonionic groups are H and the methyl ether.The cationic polymers suitable for use in granular detergent components 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 Xcan be varied. The ratio of groups M to groups X can usually range from about2:1 to about 1:10. In preferred cationic polymers, the ratio is from about 1:1 toabout 1:5. The polymers formed from such copolymerization are typicallyrandom, i.e. the cationic, nonionic and mixed cationic/nonionic monomerscopolymerize in a non repeating sequence.The units which contain groups M and groups LâX 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 LâX groups, including M1-LâX 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 LâX are each from about 3 to about 100.Preferably, the number of groups M and L-X are each from about 3 to about 40.Other than moieties for connecting groups M and X, or for attachment to thepolymer backbone, hydrophilic chain L usually consists entirely of theSUBSTITUTE SHEET (RULE 26)10152025WO 98/13452CA 02265942 1999-03-1120PCT/U S97/ 16705polyoxyalkylene moiety -[(R'O)m(CH2CH2O),,]-. The moieties -(R'O)m- and -(CH2CH2O),,- of the polyoxyalkylene moiety can be mixed together, or preferablyform blocks of -(R'O)mâ and â(CH2CH2O),,- moieties. Râ is preferably C3H5(propylene); m is preferably from 0 to about 5, and most preferably 0; i.e. thepolyoxyalkylene moiety consists entirely of the moiety â(CH2CH2O),,-. Themoiety â(CH2CH2O)n- preferably comprises at least about 85% by weight of thepolyoxyalkylene moiety, and most preferably 100% by weight (In is 0). For themoiety -(Cl-I2CH2O),,-, n is usually from about 3 to about 100. Preferably n, isfrom about 12 to about 42.A plurality (2 or more) of moieties -LâX can also be hooked together and attachedto group M or to the polymer backbone, examples of which are represented by thefollowing general structures G and H:M ______d,L L J, ,2 1 7X 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.One class of suitable cationic polymers are derived from polyurethanes, polyesters,polyethers, polyarnides and the like. These polymers comprise units selected fromthose having formulas I, II and III:snsslmntsuitl (RM 15)CA 02265942 l999-03- ll21W0 98/ 13452 PCT/US97l16705$mLmLmmâï¬âW~ï¬(R5)kâ"[(C3H6O)n1(CH2CH2O)r1]_Xg<62>kmLmLmmâï¬âWâï¬ Hyï¬ mmLmLm§~ï¬~£âï¬â 5>rt<CaH60>m<cH2cH20>n1-Xmmmï¬s0 0I! H V! H H«Toa~ow¢âmâ¢wnâmâ~&aR RX is 0 or 1; R is H or C1-C4 alkyl or hydroxyalkyl; R1 is C2-C12 alkylenc,hydroxyalkylene, alkenylene, cycloalkylene, arylene or alkarylene, or a C2-C35 oxyalkylene moiety having from 2 to abut 20 oxyalkylene units provided that no 0-O or OâN bonds are formed with A1; when x is 1, R2 is -R5- except when A1 issunsmlni SHEET (N15 2â)101520W0 98/ 13452CA 02265942 1999-03-1122PCT/US97/16705O___C__,or is -(OR3)yâ or -OR5- provided that no 0-0 or NO bonds are formed with A1,and R3 is -R5- except when A1 is0H_._.C._._âor is -(R80)-y or -R5O- provided that no 0-0 or O-N bonds are formed with A1;when x is 0, R2 isâ-â(0R3>yâ,~oR5~,~ï¬oR5~,âoï¬R5â,-âoï¬R5,O O Oâiâif"5ââââ»âiâ°â5ââ"»C»â*ââ5â"â°â â°iiââ5_âi . IR0 R0 OR ORand R3 is -R5-; R4 is C1-C4 alkyl or hydroxyalkyl, or the moiety -(R5)k-[(C3H6O)m(CH2CH2O),«,]-X; R5 is C1-C12 alkylene, hydroxyalkylene,alkenylene, arylene, or alkarylene; each R6 is C1_C4 alkyl or hydroxyalkyl, or themoiety â(CH2),âA2-(CI-I2)s-, wherein A2 is -0- or -CH2-; R7 is H or R4; R8 isC2-C3 alkylene or hydroxyalkylene; X is H,if__ CR9,-R9 or a mixture thereof, wherein R9 is C1-C4 alkyl or hydoxyalkyl; k is O or 1;In and n are numbers such that the moiety -(CH2CH2O),,â comprises at least about85% by weight of the moiety -[(C3H50)m(CH2CH2O),,]-; In is from 0 to about 5;n is at least about 3; r is 1 or 2, s is 1 or 2, and r + s is 3 or 4; y'is from2 toSI|B$|Tl|I|Isl|EEl(|lâ|-515)10152025W0 98/ 13452CA 02265942 1999-03-ll23 PCT/U S97/ 16705about 20; the number of u, v and w are such that there are at least 2 N'*â centersand at least 2 X groups.In the above formulas, A1 is preferablylaâ ânâââNC * or â- CN ââ~ ;R RA2 is preferably -0-; x is preferably 1; and R is preferably H. R1 can be linear(e.g. -CH2-CH2-CH2-,âEH3ââCH2*-CH-)o1'brariched(e.g.â-CH2-"CH-,"*-CI-I2â"CHâ*) alkylene, hydroxyalkylene, alkenylene, cycloalkylene, 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 alkylene orphenylene, and most preferably C2-C6 alkylene (e. g. ethylene, propylene,hexamethylene). R2 is preferably âOR5- or â(OR8)y-; R3 is preferably âR5O- or â(OR8)y-; R4 and R5 are preferably methyl. Like R1, R5 can be linear orbranched, and is preferably C2-C3 alkylene; R7 is preferably H or C1-C3 alkyl;R8 is preferably ethylene; R9 is preferably methyl; X is preferably H or methyl;1: is preferably 0; m is preferably 0, r and s are each preferably 2; y is preferablyfrom 2 to about 12.In the above formulas, n is preferably at least about 6 when the number of N +centers and X groups is 2 or 3; n is most preferably at least about 12, with atypical range of about 12 to about 42 for all ranges of u + v + w. Forhomopolymers (v and w are 0), u is preferably from about 3 to about 20. Forrandom copolymers (u is at least 1 or preferably 0), v and w are each preferablyfrom about 3 to about 40.8|IISlll1llESllEE|'(R|ll.£26)CA 02265942 l999-03- ll24W0 98/13452 PCT/US97/16705B. Polyacrylate, Polyacrylamide, Polyvinylether orLike Polymers5 Another 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.R1+, 3;/(A )j(R2)j(R3)2 âN*â (R2)k-â [(C3H6O)m(CH2CH2O)n] ~ xIV\N+ââ(R4)3V VIT? if âMâ ifwherein A1 isâo-â,âr'~1cââ,~r1~1coâ,ââcrI1cââ,~âcrI1~â~,R R R Rif âHâ âHâ â:1â ânâââoc1|~Iââ ~âocâ,âocoââ,~âcoââ~, r âNcNâ;R R R10 R is H or C1-C4 alkyl or hydroxyalkyl; R1 is substituted C2-C12 alkylene,hydroxyalkylene, alkenylene, arylene or alkarylene, or C2-C3 oxyalkylene; eachR2 is C1-C12 alkylene, hydroxyalkylene, alkenylene, arylene or alkarylene; eachâ$IlB'a"Il'llï¬I SIIEH (RULE Z6)101520W0 98/13452CA 02265942 1999-03-1125PCT/US97/ 16705R3 is C1-C4 alkyl or hydroxyalkyl, the moiety -(R2)k-[(C3H5O),,,(CH2CH2O),,]-X, or together form the moiety -(CH2),-A2â(CH2)s-, wherein A2 is -0- or -CH;;_â;each R4 is C1-C4 alkyl or hydroxyalkyl, or two R4 together form the moiety -(CH2),âA2-(CH2)sâ; x is H,âHââ-âcR5,âR5 or mixture thereof, wherein R5 is C1-C4 alkyl or hydroxalkyl; j is 1 or 0; kis 1 or 0; In and n are numbers such that the moiety â(CH2CH2O),,- comprises atleast about 85% by weight of the moiety â[(C3H5O)m(CH2CH2O),,]-; m is from 0to about 5; n is at least about 3; r is 1 or 2, s is 1 or 2 and r + s is 3 or 4; thenumber of u, v and w are such that there are at least 2N + centres and at least 2 Xgroups.In the above formulas, A1 is preferablyEifâuâCN , COlRor â-*0-â-;A2 is preferably -0-; R is preferably H. R] can be linearCA 02265942 l999-03- 11WO 98/13452 26 PCT/US97ll6705(e.g â CH2â- CHâ CH2-~ , -â CH2CHâ) or$â3branched (e. g. â CH2 -â ('3 -â , -â CH2Câ3H-- ,CH3CH3CH2lsubstituted alkylene, hydroxyalkylene, alkenylene, alkarylene or oxyalkylene; R1is preferably substituted C2-C5 alkylene or substituted C2-C3 oxyalkylene, andmost preferablyas»~âcH2cHâorâcH2ââCâ.Each R2 is preferably C2-C3 alkylene, each R3 and R4 are preferably methyl; R5is preferably methyl; X is preferably H or methyl; j is preferably 1; k is10 preferably 0; m 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 wfor the polyurethane and like polymers.15C. Polyallcyleneamine, Polyalkyleneimine or like polymers.SlllSlTllï¬ESllEH(R|ll.E26)CA 02265942 l999-03- ll27W0 93/13452 PCT/US97/16705Another class of suitable cationic polymers are derived from polyalkyleneamines,polyalkyleneimines and the like. These polymers comprise units selected fromthose having fonnulas VH and VIII and IX.TR2â(R1 *M.I XTR2â(R1 _ M.y (R3)R â~â~ [(C3H6O)m(CH2CH2O)n) â~â X?â2âââ(R1_;M.Z (R3)kââ [(C3H6O)m(CH2CH2O)n] -â Xwherein R1 is C2-C12 alkylene, hydroxyalkylene, alkenylene, cycloalkylene,arylene or alkarylene, or a C2-C3 oxyalkylene moiety having from 2 to about 201o oxyallcylene units provided that no O-N bonds are formed; each R2 is C1-C4 alkylor hydroxyalkyl, or the moiety -(R3)k-[(C3H5O),,,(CH2CH20),,]-X; R3 is C1-C12 alkylene, hydroxyalkylene, alkenylene, arylene or alkarylene; M ' is an N+or N centre; X is H,sunsImntsu£Er(RIILE26)W0 98/ 134521015202530CA 02265942 1999-03-1128PCT/US97ll6705.t__ CR4,6-R4 or mixture thereof, wherein R4 is C1-C4 alkyl or hydroxyalkyl; d is 1 whenMâ is N+ and is 0 when Mâ is N; e is 2 when Mâ is N+ and is 1 when Mâ is N;k is 1 or 0; m and n are numbers such that the moiety -(CH2CH2O),,- comprisesat least about 85% by weight of the moiety -[(C3H6O)m(CH2CH2O),,]â; m isfrom O to about 5; n is at least about 3; the number of x, y and z are such thatthere are at least 2Mâ 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),,]-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 Mâ andX groups is 2 or 3; n is most preferably at least about 12, with a typical range offrom about 12 to about 42 for all ranges of x + y + 2. Typically, x + y + z isfrom 2 to about 40 and preferably from 2 to about 20. For short chain lengthpolymers, x + y + 2 can range from 2 to 9 with from 2 to 9 N+ centres and from2 to 11 X groups. For long chain length polymers, x + y + z is at least 10, witha preferred range of from 10 to about 42. For the short and long chain lengthpolymers, the Mâ groups are typically a mixture of from about 50 to 100% N+centres and from 0 to about 50% N centres.Preferred cationic polymers within this class are derived from the C2-C3polyalkylenearnines (x + y + z is from 2 to 9) and polyalkyleneimines (x + y + zis at least 10, preferably from 10 to about 42). Particularly preferred cationicpolyalkyleneamines and polyalkyleneimines are the cationic polyethyleneamines(PEA's) and polyethyleneirnines (PEI's). These preferred cationic polymerscomprise units having the general formula:SUBSTITUTE SHEET (RULE 26)CA 02265942 l999-03- 11WO 93113452 29 PCT/US97ll6705(R2)d (R2)d[Mir â[CH2âââCH2M1râ101520[(CH2CH20'1nâ X12<R2>d (R2>dââtcH2CH2M1y- â~iCH2CH2M1z(CH2CH20)nâX [(CH2CH20)n"' X12wherein R2 (preferably methyl), Mâ, X, d, x, y, z and n are deï¬ned as before: ais l or 0.Prior to ethoxylation, the PEAS used in preparing cationic polymers of the presentinvention have the following general formula:[H2N]aââ ââ[CH2CH2N]xâ ââ[CH2CH2N]y'ââ i{[CH2CH2NH2]zHwherein x + y + z is from 2 to 9, and a is 0 or 1 (molecular weight of from about100 to about 400). Each hydrogen atom attached to each nitrogen atom representsan active site for subsequent ethoxylation. For preferred PEAS, x + y + z is fromabout 3 to about 7 (molecular weight is from about 140 to about 310). ThesePEA's can be obtained by reactions involving ammonia and ethylene dichloride,followed by fractional distillation. The common PEA's obtained aretriethylenetetramine (TETA) and tetraethylenepentamine (TEPA). Above thepentamines, i.e., the hexamines, heptamines, octamines and possibly nonamines,the cogenerically derived mixture does not appear to separate by distillation andcan include other materials such as cyclic amines and particularly piperazines.There can also be present cyclic amines with side chains in which nitrogen atomsappear. See US Pat. No. 2,792,372 to Dickson, issues May 14, 1957, whichdescribes 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 theSUBSTITUTE SHEET (RULE 26)W0 98/12545210152025CA 02265942 1999-03-1130PCTIUS97/16705PEA. Where y + z is 2 or 3, n is preferably at least about 6. Where y + z isfrom 4 to 9, suitable beneï¬ts are achieved when n is at least about 3. Forpreferred cationic PEAS, n is at least about 12, with a typical range of about 12 toabout 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 about10 units. Preferred PEIs used in preparing these polymers have a molecularweight of from about 600 to about 1800. The polymer backbone of these PEIs canbe represented by the general formula:H}{2PJ_fâ(:I{2(:}I2Tqâi;?' "fâ(:}{2(:}{2TJâiSf' â1%"(:}{2(:}{2TJ}{2]Zwherein the sum of x, y, and 2 represents a number of sufficient magnitude to yielda polymer having the molecular weights previously speciï¬ed. Although linearpolymer backbones are possible, branch chains can also occur. The relativeproportions of primary, secondary and tertiary amine groups present in thepolymer can vary, depending on the manner of preparation. The distribution ofamine groups is typically as follows:'T""A:}i2Cj{2âTâTq}{2 3096â# CHZCH2 â NH-~ 40%~âCH2cH2â~Nâ 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 bisulï¬te, sulfuric acid, hydrogen peroxide, hydrochloric acid, acetic acid,etc. Speciï¬c methods for preparing PE1s are disclosed in US Pat. No. 2,182,306to Ulrich et al., issued Dec. 5, 1939; US Pat No. 3,033,746 to Mayle et al.,SUBSTITUTE SHEET (RULE 26)W0 98/ 13452101520CA 02265942 1999-03-ll3 1 PCTIUS97/16705issued 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 byreference).As deï¬ned 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/antiâredeposition performance can increase as themolecular weight of the PEI increases, especially much beyond about 1800. Also,the degree of ethoxyalation for preferred polymers increases as the molecularweight of the PEI increases. For PEIs having a molecular weight of at least about600, n is preferably at least about 12, with a typical range of from about 12 toabout 42. For PEIS having a molecular weight of at least 1800, n is preferably atleast 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 thediallylamines. These polymers comprise units selected from those having formulasX and XI:SUBSTITUTE SHEET (RULE 26)CA 02265942 l999-03- 11W0 98/13452 32 PCT/US97/16705\_._ *_,// \ uR1 (R2)k~â [(C3H6O)m(CH2CH2O)n ~x(CH2)Y\rt /(CH2 #2\ (R3)2wherein R1 is C1-C4 alkyl or hydroxyalkyl, or the moiety â(R2)kâ[(C3H6O)m(CH2CH2O),,]-X; R2 is C1-C12 alkylene, hydroxyalkylene, alkylene,5 arylene or alkarylene; each R3 is C1-C4 alkyl or hydroxyalkyl, or together formthe moiety -(CH2),»Aâ(CH2)S-, wherein A is -0- or -CH2-; X is H,_, CR4,3?O10 âR4 or mixture thereof, wherein R4 is C1-C4 alkyl or hydroxyalkyl; k is 1 or O;m and n are numbers such that the moiety â(CH2CH2O),,â comprises at least about85% by weight of the moiety -[(C3H6O)m(CH2CH2O),,]-; m is from 0 to about 5;nisatleastabout3; ris1or2, sis 1or2,andr + sis3or4; xis1or0; yis1 when x is O and 0 when x is 1; the number of u and v are such that there are at15 least 2N + centres and at least 2 X groups.SUBSTITUTE SHEET (RULE 26)W0 98/13452101520253035CA 02265942 1999-03-ll33 PCTIUS97/16705In the above formulas, A is preferably -0-; R1 is preferably methyl; each R2 ispreferably C2-C3 alkylene; each R3 is preferably methyl; R4 is preferablymethyl; X is preferably H; k is preferably 0; m is preferably 0; r and s are eachpreferably 2.In the above formulas, n is preferably at least about 6 when the number of N+centres and X groups are each 2 or 3, n is preferably at least 12, with a typicalrange of from about 12 to about 42 for all range of u + v. Typically, v is 0, and uis from 2 to about 40, and preferably from 2 to about 20.Additional surfactantThe detergent compositions or components preferably contain an additionalsurfactant 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 ofsuitable cationic surfactants is given in U.S.P. 4,259,217 issued to Murphy onMarch 31, 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 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,carboxylate and sarcosinate surfactants. Anionic sulfate surfactants are preferred.SUBSTITUTE SHEET (RULE 25)WO 98113452101520253035CA 02265942 1999-03-1134PCT/US97l16705Other 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-C18 monoesters) diesters of sulfosuccinate (especially saturated andunsaturated C6-C14 diesters), N-acyl sarcosinates. Resin acids and hydrogenatedresin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids andhydrogenated resin acids present in or derived from tallow oil.Anionic sulfate surfactantAnionic sulfate surfactants suitable for use herein include the linear and branchedprimary and secondary alkyl sulfates, alkyl ethoxysulfates, fatty oleoyl glycerolsulfates, alkyl phenol ethylene oxide ether sulfates, the C5-C17 acyl-N-(C1-C4alkyl) 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 branchedprimary C10-C13 alkyl sulfates, more preferably the C11-C15 branched chainalkyl sulfates and the C12-C14 linear chain alkyl sulfates.Alkyl ethoxysulfate surfactants are preferably selected from the group consisting ofthe C10-C18 alkyl sulfates which have been ethoxylated with from 0.5 to 20 molesof ethylene oxide per molecule. More preferably, the alkyl ethoxysulfate surfactantis a C11-C13, most preferably C11-C15 alkyl sulfate which has been ethoxylatedwith from 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/ 18124.Anionic sulfonate surfactantAnionic sulfonate surfactants suitable for use herein include the salts of C5-C20linear alkylbenzene sulfonates, alkyl ester sulfonates, C6-C2; primary orsecondary alkane sulfonates, C6-C24 oleï¬n sulfonates, sulfonated polycarboxylicSUBSTITUTE SHEET (RULE 26)W0 98/13452101520253035CA 02265942 1999-03-ll35 PCTIU S971 16705acids, alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerolsulfonates, and any mixtures thereof.Anionic carboxylate 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(CH2CH20)xCH2CO0'Mâ*â wherein R is a C6 to C13 alkyl group, x ranges from O to 10, andthe ethoxylate distribution is such that, on a weight basis, the amount of materialwhere x is 0 is less than 20 % and M is a cation. Suitable alkyl polyethoxypolycarboxylate surfactants include those having the formula ROâ(CHR1âCHR2-O)-R3 wherein R is a C6 to C13 alkyl group, x is from 1 to 25, R1 and R2 areselected from the group consisting of hydrogen, methyl acid radical, succinic acidradical, hydroxysuccinic acid radical, and mixtures thereof, and R3 is selectedfrom the group consisting of hydrogen, substituted or unsubstituted hydrocarbonhaving between 1 and 8 carbon atoms, and mixtures thereof.Suitable soap surfactants include the secondary soap surfactants which contain acarboxyl unit connected to a secondary carbon. Preferred secondary soapsurfactants for use herein are water-soluble members selected from the groupconsisting of the water-soluble salts of 2âmethyl-1-undecanoic acid, 2âethylâl-decanoic acid, 2âpropyl-1ânonanoic acid, 2-butyl-l-octanoic acid and 2-pentylâ1-heptanoic acid. Certain soaps may also be included as suds suppressors.Alkali metal sarcosinate surfactantOther 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 oralkenyl group, R1 is a C1-C4 alkyl group and M is an alkali metal ion. Preferredexamples are the myristyl and oleoyl methyl sarcosinates in the form of theirsodium salts.Alkoxylated nonionic surfactantSUBSTITUTE SHEET (RULE 25)W0 98ll3452101520CA 02265942 1999-03-ll36 PCT/US9'7ll6705Essentially any alkoxylated nonionic surfactants are suitable herein. Theethoxylated and 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 ofalkylene oxide, particularly ethylene oxide and/or propylene oxide, are suitable foruse herein. The alkyl chain of the aliphatic alcohol can either be straight orbranched, primary or secondary, and generally contains from 6 to 22 carbonatoms. Particularly preferred are the condensation products of alcohols having analkyl group containing from 8 to 20 carbon atoms with from 2 to 10 moles ofethylene oxide per mole of alcohol.SUBSTITUTE SHEET (RULE 26)W0 98/13452101520253035CA 02265942 1999-03-ll37 PCTIUS97l16705Nonionic polyhydroxy fatty acid amide surfactantPolyhydroxy fatty acid amides suitable for use herein are those having thestructural formula R2CONR1Z wherein : R1 is H, C1-C4 hydrocarbyl, 2âhydroxyethyl, 2âhydroxy propyl, ethoxy, propoxy, or a mixture thereof, preferable C1-C4alkyl, more preferably C1 or C2 alkyl, most preferably C1 alkyl (i.e., methyl); andR2 is a C5-C31 hydrocarbyl, preferably straightâchain C5-C19 alkyl or alkenyl,more preferably straight-chain C9-C17 alkyl or alkenyl, most preferably straight-chain C11âC17 alkyl or alkenyl, or mixture thereof; and Z is apolyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3hydroxyls directly connected to the chain, or an alkoxylated derivative (preferablyethoxylated or propoxylated) thereof. Z preferably will be derived from a reducingsugar in a reductive amination reaction; more preferably Z is a glycityl.Nonionic fatty acid amide surfactantSuitable fatty acid amide surfactants include those having the formula:R6CON(R7)2 wherein R6 is an alkyl group containing from 7 to 21, preferablyfrom 9 to 17 carbon atoms and each R7 is selected from the group consisting ofhydrogen, C1-C4 alkyl, C1-C4 hydroxyalkyl, and -(C2H4O)xH, where x is in therange of from 1 to 3.Nonionic alglpolysaccharide surfactantSuitable alkylpolysaccharides for use herein are disclosed in U.S. Patent4,565,647, Llenado, issued January 21, 1986, having a hydrophobic groupcontaining from 6 to 30 carbon atoms and a polysaccharide, e.g., a polyglycoside,hydrophilic group containing from 1.3 to 10 saccharide units.Preferred alkylpolyglycosides have the formulaR2O(CnH2nO)t(glycosyl)Xwherein R2 is selected from the group consisting of alkyl, alkylphenyl,hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl groupsSUBSTITUTE SHEET (RULE 26)W0 98/13452101520253035CA 02265942 1999-03-ll3 8 PCTIUS97/16705contain from 10 to 18 carbon atoms; 11 is 2 or 3; t is from O to 10, and x is from1.3 to 8. The glycosyl is 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,acylarnidopropoyl and alkyl phenyl group, or mixtures thereof, containing from 8to 26 carbon atoms; R4 is an allcylene or hydroxyalkylene group containing from 2to 3 carbon atoms, or mixtures thereof; x is from 0 to 5, preferably from 0 to 3;and each R5 is an alkyl or hydroxyalkyl group containing from 1 to 3, or apolyethylene oxide group containing from 1 to 3 ethylene oxide groups. Preferredare C10-C13 alkyl dimethylamine oxide, and C10_1g acylamido alkyldimethylamine oxide.A suitable example of an alkyl aphodicarboxylic acid is Miranol(TM) C2M Conc.manufactured by Miranol, Inc., Dayton, NJ.Zwitterionic surfactantZwitterionic surfactants can also be incorporated into the detergent compositions orcomponents. These surfactants can be broadly described as derivatives ofsecondary and tertiary amines, derivatives of heterocyclic secondary and tertiaryamines, or derivatives of quaternary ammonium, quaternary phosphonium ortertiary sulfonium compounds. Betaine and sultaine surfactants are exemplaryzwitterionic surfactants for use herein.Suitable betaines are those compounds having the formula R(R')2N'*'R2COO'wherein R is a C6-C13 hydrocarbyl group, each R1 is typically C1-C3 alkyl, andR2 is a C1-C5 hydrocarbyl group. Preferred betaines are C12_13 dimethyl-ammonio hexanoate and the C10_1g acylamidopropane (or ethane) dimethyl (ordiethyl) betaines. Complex betaine surfactants are also suitable for use herein.SUBSTITUTE SHEET (RULE 26)WO 98/134521015202530CA 02265942 1999-03-ll39 PCT/US97/16705Cationic surfactantsPreferably, if a cationic surfactant is present, the cationic surfactant is selectedfrom the group consisting of cationic monoâalkoxylated amine surfactants, cationicbis-alkoxylated amine surfactants and mixtures thereof.The cationic surfactant is preferably present at a level of from 0.1% to 20%, morepreferably from 0.4% to 7%, most preferably from 0.5% to 3% by weight of thedetergent composition.Cationic mono-alkox lated amine surfactants The cationic surfactant can be a cationic monoâalkoxylated amine surfactant. whichhas the general formula I:(I)wherein R1 is an alkyl or alkenyl moiety containing from about 6 to about 18carbon atoms, preferably 6 to about 16 carbon atoms, most preferably from about6 to about 14 carbon atoms; R2 and R3 are each independently alkyl groupscontaining from one to about three carbon atoms, preferably methyl, mostpreferably both R2 and R3 are methyl groups; R4 is selected from hydrogen(preferred), methyl and ethyl; Xâ is an anion such as chloride, bromide,methylsulfate, sulfate, or the like, to provide electrical neutrality; A is a alkoxygroup, especially a ethoxy, propoxy or butoxy group; and p is from 0 to about 30,preferably 2 to about 15, most preferably 2 to about 8, with the proviso that if A isethoxy and R4 is hydrogen and p is 1, R1 is not a C12-C14 alkyl group.Preferably the ApR4 group in formula I has p=1 and is a hydroxyalkyl group,having no greater than 6 carbon atoms whereby the ââOH group is separated fromthe quaternary ammonium nitrogen atom by no more than 3 carbon atoms.Particularly preferred ApR4 groups are âCH2CH2OH, âCH2CH2CH2OH, âCH2CH(CH3)OH and âCH(CH3)CH2OH, with â-CHQCHQOH beingSUBSTITUTE SHEET (RULE 26)W0 98/ 134521015202530CA 02265942 1999-03-1140PCT/US97ll6705particularly preferred. Preferred R1 groups have no greater than 10 carbon atoms,or even no greater than 8 or 9 carbon atoms. Preferred R1 groups are linear alkylgroups. Linear R1 groups having from 8 to 11 carbon atoms, or from 8 to 10carbon atoms are preferred. Such a cationic surfactant which is highly preferredhas a formula wherein R1 is a Cg-C10 alkyl group, p is 1, A is ethoxy and R2 andR3 are methyl groups.Another highly preferred cationic monoâa1koxylated amine surfactants for useherein are of the formula1RNCIi3///// \\\\CI{3wherein R1 is C10-C18 hydrocarbyl and mixtures thereof, especially C10-C14/(CH2CH20)2-5H+ X9alkyl, preferably C10 and C12 alkyl, and X is any convenient anion to providecharge balance, preferably chloride or bromide.Cationic bis-alkox lated amine surfactant The cationic surfactant can also be a cationic bis-alkoxylated amine surfactant,which has the general formula II:(11)wherein R1 is an alkyl or alkenyl moiety containing from about 8 to about 18carbon atoms, preferably 10 to about 16 carbon atoms, most preferably from about10 to about 14 carbon atoms; R2 is an alkyl group containing from one to threecarbon atoms, preferably methyl; R3 and R4 can vary independently and areselected from hydrogen (preferred), methyl and ethyl, Xâ is an anion such aschloride, bromide, methylsulfate, sulfate, or the like, sufficient to provideelectrical neutrality. A and Aâ can vary independently and are each selected fromSUBSTITUTE SHEET (RULE 26)W0 98/ 1345210152025CA 02265942 1999-03-114 1PCT/US97l 16705C1-C4 alkoxy, especially ethoxy, (i.e., âCH2CH2O-), Propoxy, butoxy andmixtures thereof; p is from 1 to about 30, preferably 1 to about 4 and q is from 1to about 30, preferably 1 to about 4, and most preferably both p and q are 1.Highly preferred cationic bis-alkoxylated amine surfactants for use herein are ofthe formulaRâ CHZCHZOH\ +/N\\\ VcH3/ CH2CH2OHX9wherein R1 is C10-C13 hydrocarbyl and. mixtures thereof, preferably C10, C12,C14 alkyl and mixtures thereof. X is any convenient anion to provide chargebalance, preferably chloride. With reference to the general cationic bis-alkoxylatedamine structure noted above, since in a preferred compound R1 is derived from(coconut) C12âC14 alkyl fraction fatty acids, R2 is methyl and ApR3 and A'qR4are each monoethoxy.Other cationic bis-alkoxylated amine surfactants useful herein include compoundsof the formula:1R\N+ /(cH3cH20)pHX_18/ \(cH2cH2o)qHwherein R1 is C10-C13 hydrocarbyl, preferably C10-C14 alkyl, independently p is1 to about 3 and q is 1 to about 3, R2 is C1-C3 alkyl, preferably methyl, and X isan anion, especially chloride or bromide.Other compounds of the foregoing type include those wherein the ethoxy(CHQCHQO) units (E0) are replaced by butoxy (Bu) isopropoxy [CH(CH3)CH2O]and [CH2CH(CH3O] units (i-Pr) or n-propoxy units (Pr), or mixtures of E0and/or Pr and/or i-Pr units.SUBSTITUTE SHEET (RULE 26)W0 98/ 13452101520253035CA 02265942 1999-03-1142PCTIUS97/16705Water-soluble builder compoundThe detergent components or compositions can contain additional water-solublebuilder compounds.Suitable water-soluble builder compounds include carboxylate materials, borates,phosphates, and mixtures of any of the foregoing.Borate builders, as well as builders containing borate-forming 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 orthophosphate,sodium polymeta/phosphate in which the degree of polymerization ranges fromabout 6 to 21, and salts of phytic acid.The carboxylate builder suitable for use in the detergent composition orcomponents thereof can be monomeric or oligomeric (containing up to fourcarboxylate groups) in type although monomeric polycarboxylates are generallypreferred for reasons of cost and performance.Suitable, additional carboxylates containing one carboxy group include the watersoluble salts of lactic acid, glycolic acid and ether derivatives thereof. Carboxylatescontaining two carboxy groups include the water-soluble salts of succinic acid,malonic acid, (ethylenedioxy) diacetic acid, maleic acid, diglycolic acid, tartaricacid, tartronic acid and fumaric acid, as well as the ether carboxylates and thesulfmyl carboxylates. Carboxylates containing three carboxy groups include, inparticular, water-soluble citrates, aconitrates and citraconates as well as succinatederivatives such as the carboxymethyloxysuccinates described in British Patent No.1,379,241, lactoxysuccinates described in British Patent No. 1,389,732, andaminosuccinates described in Netherlands Application 7205873, and theoxypolycarboxylate materials such as 2-oxaâ1,l,3âpropane tricarboxylatesdescribed in British Patent No. 1,387,447.SUBSTITUTE SHEET (RULE 26)W0 98/13452101520253035CA 02265942 1999-03-1143PCT/US97ll6705Carboxylates containing four carboxy groups include oxydisuccinates disclosed inBritish Patent No. 1,261,829, 1,1,2,2âethane tetracarboxylates, l,l,3,3-propanetetracarboxylates and l,1,2,3~propane tetracarboxylates. Carboxylates 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 thesulfonated pyrolysed citrates described in British Patent No. 1,439,000. Preferredadditional carboxylates are hydroxycarboxylates containing up to three carboxygroups per molecule, more particularly citrates.The parent acids of the monomeric or dimeric polycarboxylate chelating agents ormixtures thereof with their salts, e. g. citric acid or citrate/citric acid mixtures arealso contemplated as useful builder components.Partially soluble or insoluble builder compoundThe detergent component or compositions may contain a partially soluble orinsoluble builder compound, typically present in detergent compositions at a levelof from 1% to 80% by weight, preferably from 10% to 70% by weight. mostpreferably from 20% to 60% weight of the composition.Examples of largely water insoluble builders include the sodium aluminosilicates.Suitable 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 0.5and x is at least 5, preferably from 7.5 to 276, more preferably from 10 to 264.The aluminosilicate material are in hydrated form and are preferably crystalline,containing from 10% to 28%, more preferably from 18% to 22% water in boundform.The aluminosilicate zeolites can be naturally occurring materials, but are preferablysynthetically derived. Synthetic crystalline aluminosilicate ion exchange materialsare available under the designations Zeolite A, Zeolite B, Zeolite P, Zeolite X,Zeolite HS and mixtures thereof. Zeolite A has the formulaNa 12 [AlO2) 12 (SiO2)12]. xH2OSUBSTITUTE SHEET (RULE 26)W0 98/ 134521015202530CA 02265942 1999-03-ll44 PCT/US97/ 16705wherein x is from 20 to 30, especially 27. Zeolite X has the formula Nag6l(A102)86(Si02)106l. 276 H20-Another preferred aluminosilicate zeolite is zeolite MAP builder.The zeolite MAP can be present at a level of from 1% to 80%, morepreferably from 15% to 40% by weight of the compositions.Zeolite MAP is described in EP 384070A (Unilever). It is defined as analkali metal aluminoâsilicate of the zeolite P type having a silicon toaluminium ratio not greater than 1.33, preferably within the range from 0.9to 1.33 and more preferably 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 zeolite MAP detergent builder has a particle size,expressed as a d50 value of from 1.0 to 10.0 micrometres, more preferablyfrom 2.0 to 7.0 micrometres, most preferably from 2.5 to 5.0 micrometres.The d50 value indicates that 50% by weight of the particles have a diametersmaller than that ï¬gure..The particle size may, in particular be determinedby conventional analytical techniques such as microscopic determinationusing a scanning electron microscope or by means of a laser granulometer.Other methods of establishing d5Q values are disclosed in EP 384070A.Heavy metal ion seguestrantThe detergent components or compositions preferably contain as an optionalcomponent a heavy metal ion sequestrant. By heavy metal ion sequestrant it ismeant herein 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.SUBSTITUTE SHEET (RULE 26)WO 98113452101520253035CA 02265942 1999-03-1145PCT/US97/ 16705Heavy metal ion sequestrants are generally present at a level of from 0.005 % to20%, preferably from 0.1% to 10%, more preferably from 0.25% to 7.5% andmost preferably 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) hexamethylenediamine tetra (methylene phosphonate) and hydroxy-ethylene 1,1 diphosphonate.Other suitable heavy metal ion sequestrant for use herein include nitrilotriaceticacid and 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 'âdisuccinic 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 2âhydroxyethyl diacetic acid or glyceryl imino diacetic acid,described in EPâA-317,542 and EPâA-399,133. The iminodiacetic acid-N -2-hydroxypropyl sulfonic acid and aspartic acid Nâcarboxymethyl N-2-hydroxypropyl-3âsulfonic acid sequestrants described in EP-A-516,102 are alsosuitable herein. The Bâalanine-N,N'-diacetic acid, aspartic acid-N,N'âdiacetic acid,aspartic acidâN-monoacetic acid and iminodisuccinic acid sequestrants described inEP-A-509,382 are also suitable.EP-A-476,257 describes suitable amino based sequestrants. EP-Aâ510,33ldescribes suitable sequestrants derived from collagen, keratin or casein. EP-A-528,859 describes a suitable alkyl irninodiacetic acid sequestrant. Dipicolinic acidand 2-phosphonobutane-l,2,4-tricarboxylic acid are also suitable. GlycinamideâN.N'-disuccinic acid (GADS), ethylenediamine-N-Nâ-diglutaric acid (EDDG) and2-hydroxypropylenediamine-NâN'-disuccinic acid (HPDDS) are also suitable.SUBSTITUTE SHEET (RULE 26)W0 98/ 13452101520253035CA 02265942 1999-03-1146PCT /US97/ 16705Organic peroxyacid bleaching systemA preferred feature of detergent compositions or components 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 reactionof the precursor with a source of hydrogen peroxide. Preferred sources ofhydrogen peroxide include inorganic perhydrate bleaches. In an alternativepreferred execution a preformed organic peroxyacid is incorporated directly intothe composition. Compositions containing mixtures of a hydrogen peroxide sourceand organic peroxyacid precursor in combination with a preformed organicperoxyacid are also envisaged.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 ata level of from 1% to 40% by weight, more preferably from 2% to 30% by weightand most preferably from 5% to 25% by weight of the compositions.Examples 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 asthe crystalline solid without additional protection. For certain perhydrate saltshowever, the preferred executions of such granular compositions utilize a coatedform of the material which provides better storage stability for the perhydrate saltin the granular product. Suitable coatings comprise inorganic salts such as alkalimetal silicate, carbonate or borate salts or mixtures thereof, or organic materialssuch 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 aSUBSTITUTE SHEET (RULE 26)1015202530WO 98/13452CA 02265942 1999-03-1147PCT/US97/ 16705formula corresponding to 2Na2CO3.3H202, and is available commercially as acrystalline solid.Potassium peroxymonopcrsulfate is another inorganic perhydrate salt of use in thedetergent compositions or components thereof.Peroxyacid bleach precursorPeroxyacid bleach precursors are compounds which react with hydrogen peroxidein a perhydrolysis reaction to produce a peroxyacid. Generally peroxyacid bleachprecursors may be represented as0HX-CâLwhere L is a leaving group and X is essentially any functionality, such that onperhydroloysis the structure of the peroxyacid produced isOHXâCâOOHPeroxyacid bleach precursor compounds are preferably incorporated at a level offrom 0.5% to 20% by weight, more preferably from 1% to 15% by weight, mostpreferably from 1.5% to 10% by weight of the detergent compositions.Suitable peroxyacid bleach precursor compounds typically contain one or more N-or O-acyl groups, which precursors can be selected from a wide range of classes.Suitable classes include anhydrides, esters, imides, lactams and acylated derivativesof imidazoles and oximes. Examples of useful materials within these classes aredisclosed in GB-A-1586789. Suitable esters are disclosed in GBâA-836988,864798, 1147871, 2143231 and EPâA-0170386.Leaving groupsThe leaving group, hereinafter L group, must be sufficiently reactive for theperhydrolysis reaction to occur within the optimum time frame (e.g., a washsuIstnuItsntEI(|I|lï¬Â°)CA 02265942 l999-03- ll48wo 98/13452 PCT/US97/16705cycle). However, if L is too reactive, this activator will be difficult to stabilize foruse in a bleaching composition.Preferred L groups are selected from the group consisting of:,,@Y, ,, c,@â5YOâârl~1~ââcâRâ, âN/\\N , âNâgâCI-lâR4,R5 L_._.J R3 4,5 l'33 T-OâCH=C-âCH=CH2 --OâCH=CâCH=CH2 ,o oï¬l) /C H2_ in v)_(n;\NR4-OâCâR" âN\C/NRâ , âN\C/ .3» «"3is S? T-0-C=CHR4 ,and 'â'fIlâï¬-CHâR4R3 0101and mixtures thereof, wherein R is an alkyl, aryl, or alkaryl group containingfrom 1 to 14 carbon atoms, R3 is an alkyl chain containing from 1 to 8 carbonatoms, R4 is H or R3, R5 is an alkenyl chain containing from 1 to 8 carbon atomsand Y is H or a solubilizing group. Any of R1, R3 and R4 may be substituted by15 essentially any functional group including, for example alkyl, hydroxy, alkoxy,halogen, amine, nitrosyl, amide and ammonium or alkyl ammonium groupsThe preferred solubilizing groups are -SO3'M+, âCO2'M+, -SO4'M+,-N+(R3)4X' and O <--N(R3)3 and most preferably -SO3'M+ and -CO2'M+smsnnntsurmmuze)1015202530W0 98/ 13452CA 02265942 1999-03-1149PCT/U S97/ 16705wherein R3 is an alkyl chain containing from 1 to 4 carbon atoms, M is a cationwhich provides solubility to the bleach activator and X is an anion which providessolubility to the bleach activator. Preferably, M is an alkali metal, ammonium orsubstituted ammonium cation, with sodium and potassium being most preferred,and X is a halide, hydroxide, methylsulfate or acetate anion.Al 1 ercarbox lic acid bleach recur orsAlkyl percarboxylic acid bleach precursors form percarboxylic acids onperhydrolysis. Preferred precursors of this type provide peracetic acid onperhydrolysis.Preferred alkyl percarboxylic precursor compounds of the imide type include theN-,N,N1N1 tetra acetylated alkylene diamines wherein the alkylene group containsfrom 1 to 6 carbon atoms, particularly those compounds in which the alkylenegroup contains 1, 2 and 6 carbon atoms. Tetraacetyl ethylene diamine (TAED) isparticularly preferred.Other preferred alkyl percarboxylic acid precursors include sodium 3,5,5-tri-methyl hexanoyloxybenzene sulfonate (iso-NOBS), sodium nonanoyloxybenzenesulfonate (NOBS), sodium acetoxybenzene sulfonate (ABS) and pentaacetylglucose.Amide substituted alkyl peroxyacid precursgrsAmide substituted alkyl peroxyacid precursor compounds are suitable herein,including those of the following general formulae:R1ââNâ-câ~R2âcâLtall!R1-CââNâR2â-CâLH!Ho R5 0 orwherein 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. AmideW0 98/ 13452101520253035CA 02265942 1999-03-ll50 PCT/US97/16705substituted bleach activator compounds of this type are described in EP-A-0170386.Perbenzoic acid precursorPerbenzoic acid precursor compounds provide perbenzoic acid on perhydrolysis.Suitable O-acylated perbenzoic acid precursor compounds include the substitutedand unsubstituted benzoyl oxybenzene sulfonates, and the benzoylation products ofsorbitol, glucose, and all saccharides with benzoylating agents, and those of theimide type including Nâbenzoyl succinimide, tetrabenzoyl ethylene diamine and theNâbenzoyl substituted ureas. Suitable imidazole type perbenzoic acid precursorsinclude Nâbenzoyl imidazole and Nâbenzoyl benzimidazole. Other useful N-acylgroup-containing perbenzoic acid precursors include Nâbenzoyl pyrrolidone.dibenzoyl taurine and benzoyl pyroglutamic acid.Cationic peroxyacid DrecursorsCationic peroxyacid precursor compounds produce cationic peroxyacids onperhydrolysis.Typically, cationic peroxyacid precursors are formed by substituting theperoxyacid part of a suitable peroxyacid precursor compound with a positivelycharged functional group, such as an ammonium or alkyl arnrnmonium group,preferably an ethyl or methyl ammonium group. Cationic peroxyacid precursorsare typically present in the solid detergent compositions as a salt with a suitableanion, such as a halide ion.The peroxyacid precursor compound to be so cationically substituted may be aperbenzoic acid, or substituted derivative thereof, precursor compound asdescribed hereinbefore. Alternatively, the peroxyacid precursor compound may bean alkyl percarboxylic acid precursor compound or an amide substituted alkylperoxyacid precursor as described hereinafterCationic peroxyacid precursors are described in U.S. Patents 4,904,406;4,751,015; 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.SUBSTITUTE SHEET (RULE 26)WO 98/134521015202530CA 02265942 1999-03-115 1PCT/US97/16705Examples of preferred cationic peroxyacid precursors are described in UK PatentApplication No. 9407944.9 and US Patent Application Nos. O8/298903,08/298650, 08/298904 and 08/298906.Suitable cationic peroxyacid precursors include any of the ammonium or alkylammonium substituted alkyl or benzoyl oxybenzene sulfonates, N âacylatedcaprolactams, and monobenzoyltetraacetyl glucose benzoyl peroxides. Preferredcationic peroxyacid precursors of the Nâacylated caprolactam class include thetrialkyl ammonium methylene benzoyl caprolactams and the trialkyl ammoniummethylene alkyl caprolactams.Benzoxazin organic peroxyacid precursorsAlso suitable are precursor compounds of the benzoxazin-type, as disclosed forexample in EPâAâ332,294 and EP-Aâ482,807, particularly those having theformula:*3N//CâR1wherein 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:SUBSTITUTE SHEET (RULE 26)W0 98/ 134521015202530CA 02265942 1999-03-1152PCT/US97ll6705R1v~I}4eNâ~R2~*I}â~OOH0 R5 0 orR1â-Nâ~C*âR2-C*-OOHR5 o 0wherein R1 is an alkyl, aryl or alkaryl group with from 1 to 14 carbon atoms, R2is an alkylene, arylene, and alkarylene group containing from 1 to 14 carbonatoms, and R5 is H or an alkyl, aryl, or alkaryl group containing 1 to 10 carbonatoms. Amide substituted organic peroxyacid compounds of this type aredescribed in EP-A-0170386.Other organic peroxyacids include diacyl and tetraacylperoxides, especiallydiperoxydodecanedioc acid, diperoxytetradecanedioc acid anddiperoxyhexadecanedioc acid. Monoâ and diperazelaic acid, mono- anddiperbrassylic acid and Nâphthaloylaminoperoxicaproic acid are also suitableherein.EnzymeAnother preferred ingredient useful in the detergent compositions or components isone or more additional enzymes.Preferred additional enzymatic materials include the commercially availablecellulases, endolases, cutinases, lipases, amylases, neutral and alkaline proteases,esterases, pectinases, lactases and peroxidases conventionally incorporated intodetergent compositions. Suitable enzymes are discussed in US Patents 3,519,570and 3,533,139.Preferred commercially available protease enzymes include those sold under thetradenames Alcalase, Savinase, Primase, Durazym, and Esperase by NovoIndustries A/S (Denmark), those sold under the tradename Maxatase, Maxacal andMaxapem by GistâBrocades, those sold by Genencor International, and those soldunder the tradename Opticlean and Optimase by Solvay Enzymes. Proteaseenzyme may be incorporated into the compositions in accordance with theSUBSTITUTE SHEET (RULE 26)W0 98/13452101520253035CA 02265942 1999-03-1153PCTIUS97I 16705invention at a level of from 0.0001 % to 4% active enzyme by weight of thecomposition.Preferred amylases include, for example, on-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 tradenameTerrnamyl and BAN by Novo Industries A/S. Amylase enzyme may beincorporated into the composition in accordance with the invention at a level offrom 0.0001% to 2% active enzyme by weight of the composition.Lipolytic enzyme may be present at levels of active lipolytic enzyme of from0.0001% to 2% by weight, preferably 0.001 % to 1% by weight, most preferablyfrom 0.001% to 0.5% by weight of the compositions.The lipase may be fungal or bacterial in origin being obtained, for example, from alipase producing strain of Humicola sp., '_lâ_hermomyces sp. or Pseudomonas sp.including Pseudomonas 1Lseudoalcaligenes or Pseudomas ï¬uorescens. Lipase fromchemically or genetically modiï¬ed mutants of these strains are also useful herein.A preferred lipase is derived from Pseudomonas pseudoalcaligenes, which isdescribed in Granted European Patent, EPâBâ0218272.Another preferred lipase herein is obtained by cloning the gene from Humicolalanuginosa and expressing the gene in Aspergillus o_ry;_a, as host, as described inEuropean Patent Application, EP-A-0258 068, which is commercially availablefrom Novo Industri A/S, Bagsvaerd, Denmark, under the trade name Lipolase.This lipase is also described in U.S. Patent 4,810,414, Huge-Jensen et al, issuedMarch 7, 1989.Suds suppressing systemThe detergent components or compositions when formulated for use in machinewashing compositions, preferably comprise a suds suppressing system present at alevel of from 0.01% to 15%, preferably from 0.05% to 10%. most preferablyfrom 0.1% to 5% by weight of the composition.SUBSTITUTE SHEET (RULE 26)W0 98l13452101520253035CA 02265942 1999-03-ll54 PCT /US97/ 16705Suitable 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. Preferredsilicone antifoam compounds are the siloxanes, particularly thepolydimethylsiloxanes having trimethylsilyl 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.Other suitable antifoam compounds include, for example, high molecular weightfatty esters (e. g. fatty acid triglycerides), fatty acid esters of monovalent alcohols,aliphatic C18-C40 ketones (e. g. stearone) Nâalkylated amino triazines such as tri-to hexa-alkylmelamines or di- to tetra alkyldiamine chlortriazines formed asproducts of cyanuric chloride with two or three moles of a primary or secondaryamine containing 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 comprisesSUBSTITUTE SHEET (RULE 26)W0 98/125452101520253035CA 02265942 1999-03-ll55 PCTlUS97/ 16705(a) antifoam compound, preferably silicone antifoam compound, mostpreferably a 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 of from5% to 50%, preferably 10% to 40% by weight;(b) 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 120.9 to 121.1, at a level of from 0.5% to10%, preferably 1% to 10% by weight; a particularly preferred siliconeglycol rake copolymer of this type is DCO544, commercially availablefrom DOW Corning under the tradename DCO544;(C) an inert carrier ï¬uid compound, most preferably comprising a C16âC13ethoxylated alcohol with a degree of ethoxylation of from 5 to 50,preferably 8 to 15, at a level of from 5% to 80%, preferably 10% to 70%,by weight;A highly preferred particulate suds suppressing system is described in EP-A-0210731 and comprises a silicone antifoam compound and an organic carriermaterial having a melting point in the range 50°C to 85°C, wherein the organiccarrier material comprises a monoester of glycerol and a fatty acid having a carbonchain containing from 12 to 20 carbon atoms. EPâA-0210721 discloses otherpreferred particulate suds suppressing systems wherein the organic carrier materialis a fatty acid or alcohol having a carbon chain containing from 12 to 20 carbonatoms, or a mixture thereof, with a melting point of from 45°C to 80°C.Polymeric dye transfer inhibiting agentsSUBSTITUTE SHEET (RULE 26)W0 98/ 1345210152025CA 02265942 1999-03-ll56 PCT /US97/16705The detergent components or compositions may also comprise from 0.01% to 10%, preferably from 0.05% to 0.5% by weight of polymeric dye transfer inhibitingagents.The polymeric dye transfer inhibiting agents are preferably selected frompolyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinylpyrrolidonepolymers or combinations thereof, wherebythese polymers can be cross-linked polymers..a) Polyamine N-oxide polymersPolyamine N-oxide polymers suitable for use herein contain units having thefollowing structure formula :(I) Axwherein P is a polymerisable unit, andO O OA is NC, CO, C, -O-, -8-, -Nâ; x is O or1;R are aliphatic, ethoxylated aliphatics, aromatic, heterocyclic or alicyclic groupsor any combination thereof whereto the nitrogen of the NâO group can be attachedor wherein the nitrogen of the NâO group is part of these groups.The NâO group can be represented by the following generalstructures :SUBSTITUTE SHEET (RULE 26)1015202530CA 02265942 1999-03-1157WO 98/13452 PCTIUS97l16705OT 0(R1) x -r'«â<R2>y T(R3); or :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 thenitrogen of the N-O group can be attached or wherein the nitrogen of the N-Ogroup forms part of these groups. The N -0 group can be part of the polymerisableunit (P) or can be attached to the polymeric backbone or a combination of both.Suitable polyamine N-oxides wherein the N-O group forms part of thepolymerisable unit comprise polyamine N-oxides wherein R is selected fromaliphatic, aromatic, alicyclic or heterocyclic groups. One class of said polyamineN -oxides comprises the group of polyamine N-oxides wherein the nitrogen of theN-O group forms part of the Râgroup. Preferred polyamine N-oxides are thosewherein R is a heterocyclic group such as pyrridine, pyrrole, imidazole,pyrrolidine, piperidine, quinoline, acridine and derivatives thereof.Other suitable polyamine N-oxides are the polyamine oxides whereto the N-Ogroup is attached to the polymerisable unit. A preferred class of these polyamineN-oxides comprises the polyamine N-oxides having the general formula (I) whereinR is an aromatic,heterocyclic or alicyclic groups wherein the nitrogen of the N-Ofunctional group is part of said R group. Examples of these classes are polyamineoxides wherein R is a heterocyclic compound such as pyrridine, pyrrole, imidazoleand derivatives 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 molecularweight is within the range of 500 to 1000,000.slllSll|âlï¬ESllEEl(|lllE25)CA 02265942 l999-03- ll5 8W0 98/ 13452 PCT/US97/ 16705b) Cooolvmers of N-vinvlnvrrolidone and N-vinvlimidazoleSuitable herein are coploymers of Nâvinylimidazo1e and N-vinylpyrrolidone havingan average molecular weight range of from 5,000 to 50,000. The preferred5 copolymers have a molar ratio of N-vinylirnidazole to Nâvinylpyrr0lidone from 1to 0.2.SUBSTITUTE SHEET (RULE 25)W0 98/134521015202530CA 02265942 1999-03-1159PCT/U S97/ 16705c) PolyvinylpyrrolidoneThe detergent components or compositions herein may also utilizepolyvinylpyrrolidone ("PVP") having an average molecular weight of from 2,500to 400,000. Suitable polyvinylpyrrolidones are commercially available from ISPCorporation, New York, NY and Montreal, Canada under the product names PVPK-15 (viscosity molecular weight of 10,000), PVP K-30 (average molecular weightof 40,000), PVP K-60 (average molecular weight of 160,000), and PVP K-90(average molecular weight of 360,000). PVP K-15 is also available from ISPCorporation. Other suitable polyvinylpyrrolidones which are commerciallyavailable from BASF Cooperation include Sokalan HP 165 and Sokalan HP 12.d) PolyvinyloxazolidoneThe detergent components or compositions herein may also utilizepolyvinyloxazolidones as polymeric dye transfer inhibiting agents. Saidpolyvinyloxazolidones have an average molecular weight of from 2,500 to400,000.e) PolyvinylimidazoleThe detergent components or compositions herein may also utilizepolyvinylimidazole as polymeric dye transfer inhibiting agent. Saidpolyvinylimidazoles preferably have an average molecular weight of from 2.500 to400,000.Qptical brightenerThe detergent components or compositions herein also optionally contain fromabout 0.005% to 5% by weight of certain types of hydrophilic optical brighteners.Hydrophilic optical brighteners useful herein include those having the structuralformula:SUBSTITUTE SHEET (RULE 26)W0 98/ 134521015202530CA 02265942 1999-03-ll60 PCTIUS97/16705R. R2N 1.â? Nâ<N O n c=c N>-âN 1.1 H N â<R2 SO3M 503M R1wherein R1 is selected from anilino, N-2-bis-hydroxyethyl and NHâ2-hydroxyethyl; R2 is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, morphilino, chloro and amino; and M is a salt-fonning cation suchas sodium or potassium.When in the above formula, R1 is anilino, R2 is N-2âbis~hydroxyethyl and M is acation such as sodium, the brightener is 4,4â ,âbis[(4-anilino-6-(N-2-bis-hydroxyethy1)-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 CibaâGeigy Corporation. Tinopal-UNPAâGX is thepreferred hydrophilic optical brightener useful in the detergent compositionsherein.When in the above formula, R1 is anilino, R2 is N-2-hydroxyethyl-Nâ2-methylamino and M is a cation such as sodium, the brightener is 4,4'-bis[(4-anilino-6-(N-2-hydroxyethylâNâmethylamino)-s-triazineâ2-yl)amino]2 ,2 '-stilbenedisulfonic acid disodium salt. This particular brightener species iscommercially marketed under the tradename Tinopal 5BM-GX by CibaâGeigyCorporation.When in the above formula, R1 is anilino, R2 is morphilino and M is a cation suchas sodium, the brightener is 4,4â-bis[(4-anilinoâ6-morphilino-s-triazine-2-yl)amino]2,2'-stilbenedisulfonic acid, sodium salt. This particular brightenerspecies is commercially marketed under the tradename Tinopal AMS-GX by CibaGeigy Corporation.Polymeric Soil Release AgentKnown polymeric soil release agents, hereinafter "SRA", can optionally beemployed in the present detergent components or compositions. If utilized, SRA'sSUBSTITUTE SHEET (RULE 26)WO 98/13452101520253035CA 02265942 1999-03-ll61 PCTIUS97/16705will generally comprise from 0.01% to 10.0%, typically from 0.1% to 5%,preferably from 0.2% to 3.0% by weight, of the compositions.Preferred SRA's typically have hydrophilic segments to hydrophilize the surface ofhydrophobic ï¬bers such as polyester and nylon, and hydrophobic segments todeposit upon hydrophobic ï¬bers and remain adhered thereto through completion ofwashing and rinsing cycles, thereby serving as an anchor for the hydrophilicsegments. This can enable stains occurring subsequent to treatment with the SRAto be more easily cleaned in later washing procedures.Preferred SRA's include oligomeric terephthalate esters, typically prepared byprocesses involving at least one transesteriï¬cation/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 allylâderived sulfonated terminal moieties covalently attached tothe backbone, for example as described in US. 4,968,451, November 6, 1990 toJ .J . Scheibel and E.P. Gosselink. Such ester oligomers can be prepared by: (a)ethoxylating allyl alcohol; (b) reacting the product of (a) with dimethylterephthalate ("DMT") and 1,2-propylene glycol ("PG")transesteriï¬cation/oligomerization procedure; and (c) reacting the product of (b)in a two-stagewith sodium metabisulï¬te in water. Other SRA's include the nonionic endâcappedof U.S. 4,711,730,December 8, 1987 to Gosselink et al., for example those produced by1,2âpropylene/polyoxyethylene terephthalate polyesterstransesteriï¬catlon/oligomerization of poly(ethyleneglycol) methyl ether, DMT, PGand poly(ethyleneglycol) ("PEG"). Other examples of SRA's include: the partly-and fully- anionic-end-capped oligomeric esters of U.S. 4,721,580, January 26,1988 to Gosselink, such as oligomers from ethylene glycol ("EG"), PG, DMT andNa-3,6âdioxa-8-hydroxyoctanesulfonate; the nonionic-capped block polyesteroligomeric compounds of U.S. 4,702,857, October 27, 1987 to Gosselink, forexample produced from DMT, methyl (Me)âcapped PEG and EG and/or PG, or acombination of DMT, EG and/or PG, Me-capped PEG and Na-dirnethy1â5âSUBSTITUTE SHEET (RULE 25)W0 98/ 134521015202530CA 02265942 1999-03-ll62 PCT/US97l 16705sulfoisophthalate; and the anionic, especially sulfoaroyl, end-capped terephthalateesters of U.S. 4,877,896, October 31, 1989 to Maldonado, Gosselink et al., thelatter being typical of SRA's useful in both laundry and fabric conditioningproducts, an example being an ester composition made from m-sulfobenzoic acidmonosodium salt, PG and DMT, optionally but preferably further comprisingadded 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.;and the methyl cellulose ethers having an average degree of substitution (methyl)per anhydroglucose unit from about 1.6 to about 2.3 and a solution viscosity offrom about 80 to about 120 centipoise measured at 20°C as a 2% aqueous solution.Such materials are available as METOLOSE SMIOO and METOLOSE SM200,which are the trade names of methyl cellulose ethers manufactured by Shin-etsuKagaku Kogyo KK.Additional classes of SRA's include: (I) nonionic terephthalates using diisocyanatecoupling agents to link polymeric ester structures, see U.S. 4,201,824, Violland etal. and U.S. 4,240,918 Lagasse et al.; and (II) SRA's with carboxylate terminalgroups made by adding trimellitic anhydride to known SRA's to convert terminalhydroxyl groups to trimellitate esters. With the proper selection of catalyst, thetrimellitic anhydride forms linkages to the terminals of the polymer through anester of the isolated carboxylic acid of trimellitic anhydride rather than by openingof the anhydride linkage. Either nonionic or anionic SRA's may be used as startingmaterials as long as they have hydroxyl terminal groups which may be esteriï¬ed.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.;Other optional ingredientsSUBSTITUTE SHEET (RULE 26)CA 02265942 l999-03- 11W0 93/13452 63 PCT/US97/16705Other optional ingredients suitable for inclusion in the components orcompositions of the invention include perfumes, colours and ï¬ller salts, withsodium sulfate being a preferred ï¬ller salt.SUBSTITUTE SHEET (RULE 26)W0 98/ 13452101520253035CA 02265942 1999-03-ll64 PCT/US97/ 16705Near neutral wash pH detergent formulationWhile the detergent components and particularly the detergent compositionscomprising the components are operative within a wide range of wash pHs (e.g.from about 5 to about 12), they are particularly suitable when formulated toprovide a near neutral wash pH, ie an initial pH of from about 7.0 to about 10.5at a concentration of from about 0.1 to about 2% by weight in water at 20°C.Near neutral wash pH formulations are better for enzyme stability and forpreventing stains from setting. In such formulations, the wash pH is preferablyfrom about 7.0 to about 10.5, more preferably from about 8.0 to about 10.5, mostpreferably from 8.0 to 9ØPreferred near neutral wash pH detergent formulations are disclosed to EuropeanPatent Application 83.200688.6, filed May 16, 1983, J.H.M. Wertz and P.C.E.Gofï¬net.Highly preferred components or compositions of this type also preferably containfrom about 2 to about 10% by weight of citric acid and minor amounts (e.g., lessthan about 20% by weight) of neutralizing agents. buffering agents, phaseregulants, hydrotropes, such as salts of toluene sulphonate, xylene sulphonate orcumene sulphonate, enzyme stabilizing agents, suds regulants, opaciï¬ers, anti-oxidants, bactericides, dyes, perfumes and brighteners, such as those described inUS Patent 4,285,841 to Barrat et a1., issued August 25, 1981 (herein incorporatedby reference).Form of the component and the compositionsThe detergent component of the invention can be made via a variety of methods,including agglomeration or extrusion of a mixture of the various compoundscomprised, or to be comprised in the detergent component, but preferably viaspray-drying of a mixture or slurry comprising the water-soluble cationics and thecarboxylate-containing polyelectrolyte compounds. This can be done via anymethod of spray-drying, known in the art. Thus, the detergent component ispreferably a spray-dried granule or particle or powder.SUBSTITUTE SHEET (RULE 26)WO 98/13452101520253035CA 02265942 1999-03-1165PCT/US97I16705When the component is in the form of an agglomerated granule. the cationicwater-soluble compound is preferably combined with a carrier material.The detergent component preferably forms part of a detergent composition.The compositions in accordance with the invention can take a variety of physicalforms including granular, tablet, ï¬ake, pastille and bar forms. The compositionsare particularly the so-called concentrated granular detergent compositions adaptedto be added to a washing machine by means of a dispensing device placed in themachine drum with the soiled fabric load.The components or compositions can also be used in or in combination with bleachadditive compositions, for example comprising chlorine bleach.The mean particle size of the components of granular compositions in accordancewith the invention, comprising the water-soluble cationic clayâsoil removal/anti-redeposition compounds, should preferably be such that no more that 40% orpreferably not more than 15% of the particles are greater than 1.8mm in diameterand not more than 40% or preferably not more than 15% of the particles are lessthan 0.25mm in diameter. Preferably the mean particle size is such that from 10%to 50% of the particles has a particle size of from 0.2mm to 0.7mm in diameter.The term mean particle size as deï¬ned herein is calculated by sieving a sample ofthe composition into a number of fractions (typically 5 fractions) on a series ofsieves, preferably Tyler sieves. The weight fractions thereby obtained are plottedagainst the aperture size of the sieves. The mean particle size is taken to be theaperture size through which 50% by weight of the sample would pass.The bulk density of granular detergent compositions typically is of at least 500g/litre, more preferably from 600 g/litre to 1200 g/litre, preferably . When thedetergent component is a spray-dried granule, particle or powder, a lower bulkdensity of the composition containing the component is preferred. Bulk density ismeasured by means of a simple funnel and cup device consisting of a conicalfunnel moulded rigidly on a base and provided with a ï¬ap valve at its lowerextremity to allow the contents of the funnel to be emptied into an axially alignedcylindrical cup disposed below the funnel. The funnel is 130 mm high and hasinternal diameters of 130 mm and 40 mm at its respective upper and lowerSUBSTITUTE SHEET (RULE 26)WO 98113452101520253035CA 02265942 1999-03-ll66 PCT/US97I16705extremities. It is mounted so that the lower extremity is 140 mm above the uppersurface of the base. The cup has an overall height of 90 m, an internal height of87 mm and an internal diameter of 84 mm. Its nominal volume is 500 ml.To carry out a measurement, the funnel is filled with powder by hand pouring, theï¬ap valve is opened and powder allowed to overï¬ll 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,such as tabletting, briquetting or extrusion, preferably tabletting. Preferablytablets for use in dish washing processes, are manufactured using a standard rotarytabletting press using compression forces of from 5 to 13 KN/cmz, morepreferably from 5 to l1KN/cm2 so that the compacted solid has a minimumhardness of 176N to 275N, preferably from l95N to 245N, measured by a C100hardness test as supplied by I. Holland instruments. This process may be used toprepare homogeneous or layered tablets of any size or shape. Preferably tablets aresymmetrical to ensure the uniform dissolution of the tablet in the wash solution.Laundry washing methodMachine laundry methods herein typically comprise treating soiled laundry with anaqueous wash solution in a washing machine having dissolved or dispensed thereinan effective amount of a machine laundry detergent component but preferably acomposition comprising the component in accord with the invention. By aneffective amount of the detergent composition it is meant from 10g to 300g ofproduct dissolved or dispersed in a wash solution of volume from 5 to 65 litres, asare typical product dosages and wash solution volumes commonly employed inconventional machine laundry methods.In a preferred use aspect a dispensing device is employed in the washing method.The dispensing device is charged with the detergent product, and is used tointroduce the product directly into the drum of the washing machine before thecommencement of the wash cycle. Its volume capacity should be such as to beSUBSTITUTE SHEET (RULE 26)101520253035W0 98/13452CA 02265942 1999-03-1167PCT/US97/16705able to contain sufficient detergent product as would normally be used in thewashing method.The dispensing device containing the detergent product is placed inside the drumbefore the commencement of the wash, either before, or simultaneously with orafter the washing machine has been loaded with laundry. At the commencement ofthe wash cycle of the washing machine water is introduced into the drum and thedrum periodically rotates. The design of the dispensing device should be such thatit permits containment of the dry detergent product but then allows release of thisproduct during the wash cycle in response to its agitation as the drum rotates andalso as a result of its contact with the wash water.To allow for release of the detergent product during the wash the device maypossess a number of openings through which the product may pass. Alternatively,the device may be made of a material which is permeable to liquid butimpermeable to the solid product, which will allow release of dissolved product.Preferably, the detergent product will be rapidly released at the start of the washcycle thereby providing transient localised high concentrations of product in thedrum of the washing machine at this stage of the wash cycle.Preferred dispensing devices are reusable and are designed in such a way thatcontainer integrity is maintained in both the dry state and during the wash cycle.Especially preferred dispensing devices for use with the composition of theinvention have been described in the following patents; GB-B-2, 157, 717, GB-B-2, 157, 718, EP-Aâ020l376, EP-A-0288345 and EP-A-0288346. An article byJ .Bland published in Manufacturing Chemist, November 1989, pages 41-46 alsodescribes especially preferred dispensing devices for use with granular laundryproducts which are of a type commonly know as the "granulette Anotherpreferred dispensing device for use with the compositions of this invention isdisclosed in PCT Patent Application No. W094/11562.Especially preferred dispensing devices are disclosed in European PatentApplication Publication Nos. 0343069 & 0343070. The latter Applicationdiscloses a device comprising a ï¬exible sheath in the form of a bag extending froma support ring defining an oriï¬ce, the oriï¬ce being adapted to admit to the bagsufficient product for one washing cycle in a washing process. A portion of theSUBSTITUTE SHEET (RULE 26)WO 98/134521015202530CA 02265942 1999-03-ll68 PCTIUS97/16705washing medium flows through the oriï¬ce into the bag, dissolves the product, andthe solution then passes outwardly through the orifice into the washing medium.The support ring is provided with a masking arrangement to prevent egress ofwetted, undissolved, product, this arrangement typically comprising radiallyextending walls extending from a central boss in a spoked wheel conï¬guration, ora similar structure in which the walls have a helical form.Alternatively, the dispensing device may be a ï¬exible container, such as a bag orpouch. The bag may be of fibrous construction coated with a water impermeableprotective material so as to retain the contents, such as is disclosed in Europeanpublished Patent Application No. 0018678. Alternatively it may be formed of awaterâinsoluble synthetic polymeric material provided with an edge seal or closuredesigned to rupture in aqueous media as disclosed in European published PatentApplication Nos. 001 1500,â 001 1501, 0011502, and 0011968. A convenient formof water frangible closure comprises a water soluble adhesive disposed along andsealing one edge of a pouch formed of a water impermeable polymeric ï¬lm such aspolyethylene or polypropylene.Machine dishwashing methodAny suitable methods for machine dishwashing or cleaning soiled tableware,particularly soiled silverware are envisaged.A preferred machine dishwashing method comprises treating soiled articles selectedfrom crockery, glassware, hollowware, silverware and cutlery and mixturesthereof, with an aqueous liquid having dissolved or dispensed therein an effectiveamount of a machine dishwashing component or preferably composition,comprising the component in accord with the invention. By an effective amount ofthe machine dishwashing composition it is meant from 8g to 60g of productdissolved or dispersed in a wash solution of volume from 3 to 10 litres, as aretypical product dosages and wash solution volumes commonly employed inconventional machine dishwashing methods.SUBSTITUTE SHEET (RULE 26)WO 98/1345210152025303502265942 1999-03-ll69 PCT/US97l 16705Abbreviations used in ExamplesIn the detergent compositions, the abbreviated component identiï¬cations have thefollowing meanings:LASTASCxyASC46SASCxyEzSCxyEzQASQAS 1QAS 2APASoapSTSCFAATFAATPKFASTPPTSPPZeolite ANaSKS-6Citric acidBorateCarbonateBicarbonateSodium linear C11_13 alkyl benzene sulfonateSodium tallow alkyl sulfateSodium C1x - C13, alkyl sulfateSodium C14 - C15 secondary (2,3) alkyl sulfateSodium C1,â-C1), alkyl sulfate condensed with 2 molesof ethylene oxideC1xâC1y predominantly linear primary alcoholcondensed with an average of 2 moles of ethylene oxideR2.N+(CH3)2(C2H4OH) with R2 = C12 â C14R2.N+(CH3)2(C2H4OH) with R2 = C8 â C11R2.N+(CH3)2(C2H4OH) with R2 = C8C3 â C10 amido propyl dimethyl amineSodium linear alkyl carboxylate derived from an 0/20mixture of tallow and coconut fatty acidsSodium toluene sulphonateC12-C14 (coco) alkyl Nâmethyl glucamideC16-C13 alkyl N -methyl glucamideC12_C14 topped whole cut fatty acidsAnhydrous sodium tripolyphosphateTetrasodium pyrophosphateHydrated sodium aluminosilicate of formulaNa12(A1O2Si()2)12.27H2O having a primary particlesize in the range from 0.1 to 10 micrometers (weightexpressed on an anhydrous basis)Crystalline layered silicate of formula 8- Na2Si2O5Anhydrous citric acidSodium borateAnydrous sodium carbonate with a particle sizebetween 200nm and 900p.mAnhydrous sodium bicarbonate with a particle sizedistribution between 400p.m and l200umSUBSTITUTE SHEET (RULE 26)W0 98/134521015202530SilicateSulfateMg sulfateCitrateMA/AA 1MA/AA 2MA/AA 3AACMCellulose etherProteaseProtease IAlcalaseCellulaseAmylaseLipaseCA02265942 1999-03-ll70 PCT/US97I16705Amorphous sodium silicate (SiO2:Na2O = 2.0:1)Anhydrous sodium sulfateAnhydrous magnesium sulfateTriâsodium citrate dihydrate of activity 86.4%with a particle size distribution between 425nm and850;/.mCopolymer of 3:7 maleic/acrylic acid, averagemolecular weight about 70,000Copolymer of 4:6 maleic/acrylic acid, averagemolecular weight about 3,000Copolymer of 4:6 maleic/acrylic acid, averagemolecular weight about 12,000Sodium polyacrylate polymer of average molecularweight 4,500Sodium carboxymethyl celluloseMethyl cellulose ether with a degree of polymerizationof 650 available from Shin Etsu ChemicalsProteolytic enzyme, having 3.3% by weight of activeenzyme, sold by NOVO Industries A/S under thetradename SavinaseProteolytic enzyme, having 4% by weight of activeenzyme, as described in WO 95/10591, sold byGenencor Int. Inc.Proteolytic enzyme, having 5.3% by weight of activeenzyme, sold by NOVO Industries A/ SCellulytic enzyme, having 0.23% by weight of activeenzyme, sold by NOVO Industries A/S under thetradename CarezymeAmylolytic enzyme, having 1.6% by weight of activeenzyme, sold by NOVO Industries A/S under thetradename Terrnamyl 120TLipolytic enzyme, having 2.0% by weight of activeenzyme, sold by NOVO Industries A/S under thetradename LipolaseSUBSTITUTE SHEET (RULE 26)W0 98/13452101520253035Lipase (1)EndolasePB4PB1PercarbonateNOBSNAC-OBSTAEDDTPADTPMPEDDSPhotoactivatedPhotoactivatedBrightener 1Brightener 2HEDPPEGXPEOTEPAEPVICA 02265942 1999-03-1171 PCT/US97/16705Lipolytic enzyme, having 2.0% by weight of activeenzyme, sold by NOVO Industries A/S under thetradename Lipolase UltraEndoglucanase enzyme, having 1.5% by weight ofactive enzyme, sold by NOVO Industries A/SSodium perborate tetrahydrate of nominal formulaNaBO2.3H2O.H2O2Anhydrous sodium perborate bleach of nominal formulaNaBO2.H202Sodium percarbonate of nominal formula2Na2CO3.3H2O2Nonanoyloxybenzene sulfonate in the form of thesodium salt(6-nonamidocaproyl) oxybenzene sulfonateTetraacetylethylenediamineDiethylene triamine pentaacetic acidDiethylene triamine penta (methylene phosphonate),marketed by Monsanto under the Tradename Dequest2060Ethylenediamine-N,N'iâdisuccinic acid, (S,S) isomer inthe form of its sodium salt.Sulfonated zinc phthlocyanine encapsulated in bleach(1) dextrin soluble polymerSulfonated alumino phthlocyanine encapsulated inbleach (2) dextrin soluble polymerDisodium 4,4'âbis(2âsulphostyryl)biphenylDisodium 4 ,4 '-bis(4-anilino-6-morpholino-1 .3 .5âtriazin-2âyl)amino) stilbene-2:2â-disulfonate1,1-hydroxyethane diphosphonic acidPolyethylene glycol, with a molecular weight of x(typically 4,000)Polyethylene oxide, with an average molecular weightof 50,000Tetraethylenepentaamine ethoxylatePolyvinyl imidosole, with an average molecular weightof 20,000SUBSTITUTE SHEET (RULE 26)WO 98/134521015202530PVPPVNOPVPVIQEA1QEA2QEA3SRP1SRP2PEISilicone antifoamOpaciï¬erWaxCA02265942 1999-03-ll72 PCT/US97I16705Polyvinylpyrolidone polymer, with an averagemolecular weight of 60,000Polyvinylpyridine N-oxide polymer, with an averagemolecular weight of 50,000Copolymer of polyvinylpyrolidone and vinylimidazole,with an average molecular weight of 20,000MCSO4â bis((C2H5O)(C2H4O)n) (CH3) -N+âC5H12âNâ*'â(CH3) bis((C2H5O)-(C2H4O)n), whereinn=from 20 to 30Salt of bis((C2H5O)â(C2H4O)n) (CH3) N+ R1,wherein R1 is C4-C1; alkyl group and n=from 20 to30Salt of tri{ (bis((C2H5O)-(C2H4O)n)(CH3)-N +)-(CONC3H5)}-C3H5O, wherein n=from 20 to 26Anionically end capped poly estersDiethoxylated poly (1, 2 propylene terephtalate) shortblock polymerPolyethyleneimine with an average molecular weight of1800 and an average ethoxylation degree of 7ethyleneoxy residues per nitrogenPolydimethylsiloxane foam controller with siloxaneâoxyalkylene copolymer as dispersing agent with a ratioof said foam controller to said dispersing agent of 10:1to 100:1Water based monostyrene latex mixture, sold by BASFAktiengesellschaft under the tradename Lytron 621Paraffin waxIn the following examples all levels are quoted as % by weight of the composition:SUBSTITUTE SHEET (RULE 26)CA 02265942 l999-03- 11W0 98/13452 73 PCT/US97/16705Example 1The following high density granular laundry detergent compositions A to F ofparticular utility under European machine wash conditions are examples in accord5 with the invention:A B C D E FLAS . 8.0 8.0 8.0 8.0 8.0 8.0C25E3 3.4 3.4 3.4 3.4 3.4 3.4C46AS 1.0 2.0 2.5 â 3.0 4.0C68AS 3.0 2.0 5.0 7.0 1.0 0.5QAS â - 0.8 â - 0.8Zeolite A 18.1 18.1 16.1 18.1 18.1 18.1Zeolite MAP - 4.0 3.5 - â -Carbonate 13.0 13.0 13.0 27.0 27.0 27.0Silicate 1.4 1.4 1.4 3.0 3.0 3.0Sodium 26.1 26.1 26.1 26.1 26.1 26.1SulfateMA/AA 1 0.6 0.8 0.3 1.0 0.5 0.3CMC 0.2 0.2 0.2 0.2 0.2 0.2PB4 9.0 9.0 9.0 9.0 9.0 9.0TAED 1.5 1.5. 1.0 1.5 - 1.5Mn Catalyst â 0.03 0.07 - - -DTPMP 0.25 0.25 0.25 0.25 0.25 0.25SUBSTITUTE SHEET (RULE 28)CA 02265942 l999-03- 11WO 98/13452 74 PCT/US97/16705HEDP 0.3 0.3 0.2 0.2 0.3 0.3EDDS - - 0.4 0.2 - -QEA 1 1.0 0.8 0.7 1.2 - 0.5QEA 2 - - â - 1.0 0.5Protease 0.26 0.26 0.26 0.26 0.26 0.26Amylase 0.1 0.1 0.4 0.3 0.1 0.1Photoactivate 15 ppm 15 15 ppm 15 ppm 15 ppm 15d bleach ppm ppm(PPUI)Brightener 1 0.09 0.09 0.09 0.09 0.09 0.09Perfume 0.3 0.3 0.3 0.3 0.3 0.3Silicone 0.5 0.5 0.5 0.5 0.5 0.5antifoamMisc/minors to100%Density in 850 850 850 850 850 850g/litreSUBSTITUTE SHEET (RULE 25)CA 02265942 l999-03- 11WO 98113452 75 PCTlUS97l16705Example 2The following high density granular laundry detergent compositions G to L ofs particular utility under European machine wash conditions are examples in accordwith the invention:G H I J K LLAS 8.0 8.0 8.0 8.0 8.0 8.0C25E3 3.4 3.4 3.4 3.4 3.4 3.4C46AS 1.0 2.0 2.5 - 3.0 4.0C68AS 3.0 2.0 5.0 7.0 1.0 0.5QAS â - 0.8 - - 0.8Zeolite A 18.1 18.1 16.1 18.1 18.1 18.1Zeolite MAP - 4.0 3.5 - - -Carbonate 13.0 13.0 13.0 27.0 27.0 27.0Silicate 1.4 1.4 1.4 3.0 3.0 3.0Sodium Sulfate 26.1 26.1 26.1 26.1 26.1 26.1MA/AA 1 0.5 0.8 0.3 1.0 0.5 0.3CMC 0.2 0.2 0.2 0.2 0.2 0.2PB4 9.0 9.0 9.0 9.0 9.0 9.0TAED 1.5 1.5. 1.0 1.5 - 1.5Mn Catalyst â 0.03 0.07 â - -DTPMP 0.25 0.25 0.25 0.25 0.25 0.25SUBSTITUTE SHEET (RULE 26)CA 02265942 l999-03- 11W0 98/13452 76 PCTIUS97/16705HEDP 0.3 0.3 0.2 0.2 0.3 0.3EDDS - - 0.4 0.2 â -QEA 1 1.0 0.8 0.7 1.2 â 0.5QEA 2 â - â - 1.0 0.5Protease 0.26 0.26 0.26 0.26 0.26 0.26Amylase 0.1 0.1 0.4 0.3 0.1 0.1Photoactivated 15 15 15 15 15 15bleach (Ppm) Ppm PPm Ppm PDTâ Ppm PpmBrightener 1 0.09 0.09 0.09 0.09 0.09 0.09Perfume 0.3 0.3 0.3 0.3 0.3 0.3Silicone 0.5 0.5 0.5 0.5 0.5 0.5antifoamMisc/minors to100%Density in 850 850 850 850 850 850g/ litreSUBSTITUTE SHEET (RULE 26)CA 02265942 l999-03- ll77W0 98/ 13452 PCT/US97I16705Example 3The following granular laundry detergent compositions M to O of bulk density 750g/litre are compositions according to the invention:M N OLAS 5.25 5.61 4.76TAS 1.25 1.86 1.57C45AS - 2.24 3.89C25AE3S - 0.76 1.18C45E7 3.25 -1 5.0C25E3 â 5.5 -QAS 0.8 2.0 âQAS 1 0.4 1.0 2.5STPP 19.7 -V âZeolite A - 19.5 19.5NaSKSâ6/citric â 10.6 10.6acid (79:21)Carbonate 6.1 21.4 21.4Bicarbonate - 2.0 2.0Citric acid 0.3 0.2 -SUBSTITUTE SHEET (RULE 26)CA 02265942 l999-03- 11WO 98113452 78 PCT/US97I16705Silicate 6.8 - -Sodium sulfate 39.8 â 7.0PB4 5.0 12.7 -TAED 0.5 0.2 -DPDA - - 0.3NAC OBS 1.0 2.2 -DTPMP 0.25 0.2 0.2HEDP â 0.3 0.3Protease 0.26 0.85 0.85Lipase 0.15 0.15 0.15Cellulase 0.28 0.28 0.28Amylase 0.1 0.1 0.1MA/AA 0.5 0.8 0.4QEA 1 1.0 1.5 -QEA 2 - - 0.8CMC 0.2 0.4 0.4PVP â - 0.8SUBSTITUTE SHEET (RULE 26)CA 02265942 l999-03- 11W0 98/123452 79 PCT/US97/16705Photoactivated 15 ppm 27 ppm 27 ppmbleach (ppm)Brightcner 1 0.08 0.19 0.19Brightener 2 - 0.04 0.04Perfume 0.3 0.3 0.3Silicone 0.5 2.4 2.4antifoamMinors/misc to n.a. n.a.100%SUBSTITUTE SHEET (RULE 26)CA 02265942 l999-03- 11W0 98/13452 80 PCT/US97/16705Example 4The following detergent formulations of particular utility under European machinewash conditions are examples in accord with the invention.P Q R SBlown powderLAS 6.0 5.0 11.0 6.0TAS 2.0 - â 2.0Zeolite A - 27.0 - 20.0STPP 24.0 - 24.0 -Sulfate 9.0 6.0 13.0 -MA/AA 2 2.0 - - 4.0MA/AA 1 - 1.0 0.5 -Silicate 7.0 3.0 3.0 3.0CMC 1.0 1.0 0.5 0.6QEA 1 0.8 1.0 3.0 0.5QEA 2 - - - 0.5Brightener 0.2 0.2 0.2 0.2Silicone antifoarn 1.0 1.0 1.0 0.3DTPMP 0.4 0.4 0.2 0.4Spray onC45E7 â - - 5.0C45E2 2.5 2.5 2.0 -C45E3 2.6 2.5 2.0 -Perfume 0.3 0.3 0.3 0.2Silicone antifoam 0.3 0.3 0.3 -Dry additivesSulfate 3.0 3.0 5.0 10.0Carbonate 6.0 13.0 15.0 14.0PB1 - - - 1.5PB4 18.0 18.0 10.0 18.5TAED 3.0 2.0 - 2.0EDDS â 2.0 2.4 -Protease 1.0 1.0 1.0 1.0SUBSTITUTE SHEET (RULE 26)CA 02265942 l999-03- 11W0 98/ 13452 81 PCT/U S97/ 16705Lipase 0.4 0.4 0.4 0.2Amylase 0.2 0.2 0.2 0.4Photoactivated - - - 0.15bleachTotal 100.0 100.0 100.0 100.0SUBSTITUTE SHEET (RULE 26)CA 02265942 l999-03- ll82W0 98/13452 PCTIUS97/ 16705Example 5The following detergent formulations of particular utility under European machine5 wash conditions are examples in accord with the invention.T U V WBlown powderLAS 6.0 5.0 11.0 6.0TAS 2.0 - - 2.0Zeolite A 24.0 - â 20.0STPP â 27.0 24.0 -Sulfate 9.0 6.0 13.0 5.0QAS 1 0.5 0.8 - 1.0MA/AA 1 0.4 0.9 - -MA/AA2 - - 0.4 0.5QEA l 1.0 1.2 0.7 -QEA 3 â - - 0.5Silicate 1.0 7.0 3.0 3.0CMC 1.0 1.0 0.5 0.6Brightener 1 0.2 0.2 0.2 0.2Silicone antifoam 1.0 1.0 1.0 0.3Carbonate 5 .0 3 .0 - 4.0STS 0.3 0.5 â 0.2DTPMP 0.4 0.4 0.2 0.4Spray onBrightener 0.02 - - 0.02C45E7 - â - 5.0C45E2 2.5 2.5 2.0 -C45E3 2.6 2.5 2.0 -Perfume 0.5 0.3 0.5 0.2Silicone antifoam 0.3 0.3 0.3 -Dry additivesQEA â â â 0.5EDDS 0.3 - - -SUBSTITUTE SHEET (RULE 26)CA 02265942 l999-03- 11WO 98/13452 83 PCT/US97/16705Sulfate 2.0 3.0 5.0 10.0Carbonate 6.0 10.0 12.0 9.0Citric acid 2.5 - - 2.0QAS II 0.5 - - 0.5SKS-6 10.0 â - -Percarbonate 18.5 - - -PB4 - 18.0 10.0 21.5TAED 2.0 2.0 - 2.0NACâOBS 3.0 2.0 4.0 -Protease 1.0 1.0 1.0 1.0Lipase - 0.4 â - 0.2Lipase (1) 0.4 â 0.4 âAmylase 0.2 0.2 0.2 0.4Brightener 1 0.05 â - 0.05Misc/minor to100%SUBSTITUTE SHEET (RULE 25)CA 02265942 l999-03- 11W0 98l13452 84 PCT/US97/16705Example 6The following granular detergent formulations are examples in accord with theinvention.Blown powderLAS 23.0 8.0 7.0 9.0 7.0 7.0TAS â â â - 1.0 -C45AS 6.0 6.0 5.0 8.0 - -C45AES â 1.0 1.0 1.0 â -C45E35 â â â - 2.0 4.0Zeolite A 10.0 13.0 14.0 12.0 10.0 10.0MA/AA â 0.5 0.4 - â 0.3MA/AA (1) 0.9 â â â â -AA â â 0.1 1.0 - 0.2QAS 1 0.5 0.6 â - 1.0 1.0Sulfate 5.0 6.3 14.3 11.0 15.0 15.3Silicate 10.0 1.0 1.0 1.0 1.0 1.0QEA 1 0.9 1.1 â - - 0.5QEA 2 â - 1.0 1.5 â -QEA 3 â - â â - 0.5Carbonate 15.0 20.0 10.0 20.7 8.0 6.0PEG4000 0.4 1.5 1.5 1.0 1.0 1.0STS 0.2 - - 0.5 0.3 0.2DTPA â 0.3 0.3 â - 0.4Brightener 2 0.3 0.2 0.3 - 0.1 0.3Spray onC45E7 - 2.0 - - 2.0 2.0C25E9 3.0 - â - â -C23E9 - â 1.5 2.0 - 2.0Perfume 0.3 0.3 0.3 2.0 0.3 0.3AgglomeratesC45AS - 5.0 5.0 2.0 - 5.0LAS - 2.0 2.0 â - 2.0SUBSTITUTE SHEET (RULE 26)CA 02265942 l999-03- 11WO 98113452 85 PCT/US97/16705QEA 1 â - â - 0.8 âMA/AA 1 â - - - 0.8 âZeolite A - 7.5 7.5 8.0 â 7.5Carbonate â 4.0 4.0 5.0 - 4.0PEG 4000 - 0.5 0.5 - â 0.5Misc (water etc) - 2.0 2.0 2.0 - 2.0Dry additivesQAS (I) â â - - 1.0 -Citric acid - 0.4 - - 2.0 0.5PB4 â â - - 12.0 1.0PB1 4.0 1.0 3.0 2.0 â âPercarbonate - - â â 2.0 10.0Carbonate - 5.3 1.8 - 4.0 4.0NOBS 4.0 - 6.0 - - 0.6Methyl cellulose 0.2 - - - - -SKSâ6 8.0 - â - - âSTS â â 2.0 - 1.0 âCumene sulfonic - 1.0 â - â 2.0acidLipase 0.2 - 0.2 - 0.2 0.4Cellulase 0.2 0.2 0.2 0.3 0.2 0.2Amylase 0.2 â 0.1 - 0.2 -Protease 0.5 0.5 0.5 0.3 0.5 0.5PVPVI â â â - 0.5 0.1PVP - - â - 0.5 ~PVNO - - 0.5 0.3 - -QEA - - â â 1.0 -SRP1 0.2 0.5 0.3 - 0.2 -Silicone antifoarn 0.2 0.4 0.2 0.4 0.1 -Mg sulfate - â 0.2 - 0.2 -Misc/minors to100%SUBSTITUTE SHEET (RULE 26)CA 02265942 l999-03- ll86W0 98/ 13452 PCTIU S97! 16705Example 7The following nil bleach-containing detergent formulations of particular use in thewashing of coloured clothing, are examples according to the present invention were5 prepared:DD EE FFBlown PowderZeolite A 15.0 15.0 âSulfate 0.0 10.0 âLAS 3.0 â 3.0 -DTPMP 0.4 0.5 -CMC 0.4 0.4 -QEA 1 1.0 0.2 -QEA 2 - 1.0 -MA/AA 1 0.5 â âAA - 0.6 -Carbonate â 5.0 -STS - 0.2 -QAS 1 â 1.0 -Agglomerates 'C45AS - - 1 1.0LAS 6.0 5.0 -TAS 3.0 2.0 -Silicate 4.0 4.0 -Zeolite A 10.0 15.0 13.0QEA 1 - - 1.0CMC - - 0.5MA/AA - - 0.8Carbonate 9.0 7.0 7.0Spray OnPerfume 0.3 0.3 0.5C45E7 4.0 4.0 4.0C25E3 2.0 2.0 2.0Dry additivesSUBSTITUTE SHEET (RULE 26)CA 02265942 l999-03- 11W0 98/ 13452 87 PCT/US97/16705MA/AA â - 3.0NaSKSâ6 - - 12.0Citrate 10.0 - 8.0Bicarbonate 7 .0 3 .0 5 .0Carbonate 8.0 5 .0 7 .0PVPVI/PVNO 0.5 0.5 0.5Alcalase 0.5 0.3 0.9Lipase 0.4 0.4 0.4Amylase 0.6 0.6 0.6Cellulase 0.6 0.6 0.6Silicone antifoam 5.0 5.0 5.0Citric Acid - 1.0 -Sulfate 0.0 9.0 0.0Misc/minors to 100% 100.0 100.0 100.0Density (g/litre) 700 700 700SUBSTITUTE SHEET (RULE 25)CA 02265942 l999-03- ll88W0 98/13452 PCT/US97/ 16705Example 8The following granular detergent compositions of particular utility under Europeanwash conditions are examples in accord with the invention.EE FFCS. .MA/AA 1MA/AACMQEA 1QEABrightener 1DS yonC45Silicone antifDry additivesTPhotoactivated blProAmyCeSUBSTITUTE SHEET (RULE 26)W0 98I13452CA02265942 1999-03-1189Balance (Moisture andMisc.)Density (g/ litre)700700SUBSTITUTE SHEET (RULE 26)PCT/US97l16705W0 98/ 13452Example 9CA02265942 1999-03-1190PCT/US97/ 16705The following detergent compositions, are examples according to the presentinvention:GG HH IIBlown PowderZeolite A 15.0 15.0 15.0Sodium Sulfate 0.0 5.0 0.0LAS 3.0 3.0 3.0QAS - 1.5 1.5DTPMP 0.4 0.2 0.4CMC 0.4 0.4 0.4MA/AA 1 - - 2.0MA/AA 2 2.0 - -AA - 4.0 -AgglomeratesLAS 5.0 5.0 5.0TAS 2.0 2.0 1.0Silicate 3.0 3.0 4.0QEA 1 1.0 2.5 0.6Mn Catalyst 0.03 â âZeolite A 8.0 8.0 8.0Carbonate 8.0 8.0 4.0Spray OnPerfume 0.3 0.3 0.3C45E7 2.0 2.0 2.0C25E3 2.0 - -Dry additivesCitrate 5.0 - 2.0Bicarbonate - 3 .0 -Carbonate 8.0 15 .0 10.0Percarbonate - 7.0 10.0TAED 6.0 2.0 5.0SUBSTITUTE SHEET (RULE 26)CA 02265942 1999-03-11 0W0 98/ 13452 91 PCT/US97/16705PB1 14.0 7.0 10.0EDDS - 2.0 ~Polyethylene oxide of MW â - 0.2500,01)Bentonite clay â â 10.0Protease 1 .0 1 .0 1 .0Lipase 0.4 0.4 0.4Amylase 0.6 0.6 0.6Cellulase 0.6 0.6 0.6Silicone antifoam 5.0 5.0 5.0Dry additivesSodium sulfate 0.0 3.0 0.0Balance (Moisture and _ 100.0 100.0 100.0Misc.)Density (g/litre) 850 850 850SUBSTITUTE SHEET (RULE 26)CA 02265942 l999-03- 11W0 98/13452 92 PCT/US97/16705Example 10The following granular detergent formulations are exmaples in accord with theinvention.5JJ KK LL MMBase granuleZeolite A 30.0 22.0 24.0 10.0Sulfate 10.0 5.0 10.0 7.0MA/AA 1 - 0.5 - -AA 0.9 - 1.0 -MA/AA 2 - - - 1.0QEA 1 - 1.2 1.2 -QEA 3 1.5 - â 3.0QAS 2 - 1.0 0.5 -LAS 14.0 10.0 9.0 20.0C45AS 8.0 7.0 9.0 7.0C45AES - 1.0 1.0 -Silicate - 1.0 0.5 10.0Soap - 2.0 - âBrightener 1 0.2 0.2 0.2 0.2Carbonate 6.0 9.0 10.0 10.0PEG 4000 â 1.0 1.5 âDTPA - 0.4 â -Spray onC25E9 - - - 5.0C45E7 1.0 1.0 - -C23E9 - 1.0 2.5 -Perfume 0.2 0.3 0.3 âDry additivesCarbonate 5.0 10.0 18.0 8.0PVPVI/PVNO 0.5 - 0.3 -Protease 1.0 1.0 1.0 0.5Lipase 0.4 - - 0.4Amylase 0.1 - - 0.1SUBSTITUTE SHEET (RULE 26)CA 02265942 l999-03- 11WO 98113452 93 PCT/US97l16705Cellulase 0.1 0.2 0.2 0.1NOBS - 4.0 - 4.5PB1 1.0 5.0 1.5 6.0Sulfate 4.0 5 .0 - 5 .0SRPI ~ 0.4 â âSud supressor - 0.5 0.5 -Misc/minor to 100%SUBSTITUTE SHEET (RULE 26)CA 02265942 l999-03- ll4WO 98/13452 9 PCT/US97/16705Example 11The following granular detergent compositions are examples in accord with theinvention.NN 00 PP QQ RR SS TT UUBlown powderZeolite A 20.0 - 15.0 15.0 15.0 15.0 15.0 15.0STPP - 20.0 â - - - - -Sulphate - â 15.0 15.0 15.0 15.0 15.0 15.0Carbonate â - 5.0 5.0 5.0 5.0 5.0 5.0TAS - - 1.0 1.0 1.0 1.0 1.0 1.0LAS 6.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0Silicate 3.0 ' 8.0 - â â â - -QEA 1 1.2 1.5 0.9 0.9 0.9 0.9 0.9 0.9QAS 1 1.2 - 0.9 â 0.9 â - âQAS - 1.5 - 0.9 â 0.9 - -MA/AA 1 1.7 1.7 0.5 0.5 0.5 0.5 0.5 0.5CMC 0.4 0.4 0.2 0.2 0.2 0.2 0.2 0.2Brightener 1 0.2 0.2 0.1 0.1 0.1 0.1 0.1 0.1DTPMP 0.2 0.2 0.1 0.1 0.1 0.1 0.1 0.1STS â 1.0 1.0 1.0 â - 1.0 -Spray onC45E7 5.0 5.0 4.0 4.0 4.0 4.0 4.0 4.0Silicone antifoam 0.3 0.3 0.1 0.1 0.1 0.1 0.1 0.1Perfume 0.2 0.2 0.3 0.3 0.3 0.3 0.3 0.3Dry additivesQEA 1.0 1.0 â - - â â âCarbonate 14.0 9.0 10.0 10.0 10.0 10.0 10.0 10.0PB1 1.5 2.0 - â â â â âPB4 18.5 13.0 13.0 13.0 13.0 13.0 13.0 13.0TAED 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0QAS 1 1.0 1.0 - â - - 1.0 1.0Photoactivated 15 15 15 15 15 15 15 15bleach ppm ppm ppm ppm ppm ppm ppm ppmSUBSTITUTE SHEET (RULE 26)CA 02265942 l999-03- 11W0 98/13452 95 PCT/US97l16705SKS-6 â â 3.0 3.0 3.0 3.0 3.0 3.0Protease 1.0 1.0 0.2 0.2 0.2 0.2 0.2 0.2Lipase 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2Amylase 0.4 0.4 0.2 0.2 0.2 0.2 0.2 0.2Cellulase 0.1 0.1 0.2 0.2 0.2 0.2 0.2 0.2Sulfate 10.0 20.0 5.0 5.0 5.0 5.0 5.0 5.0Misc/minors to100%Density (g/litre) 690 690 690 690 690 690 690 690SUBSTITUTE SHEET (RULE 26)CA 02265942 l999-03- 11W0 98/ 13452 96 PCT/US97/16705Example 12The following laundry bar detergent compositions are examples in accord with theinvention.VV WW XX YY ZZ AB AC ADLAS â â 19.0 15.0 21.0 6.75 8.8 âC28AS 30.0 13.5 ~ â â 15.75 11.2 22.5Sodium laurate 2.5 9.0 - - - - - -Zeolite A 2.0 1.25 â - - 1.25 1.25 1.25Carbonate 20.0 3.0 13.0 8.0 10.0 15.0 15.0 10.0Calcium 21.5 â â - - â - -carbonateSulfate 5.0 â â - - â â -TSPP 5.0 - 5.0 - 5.0 5.0 2.5 5.0STPP 5.0 15.0 - - - 5.0 8.0 10.0Bentonite clay - 10.0 - - 5.0 - - âDTPMP - 0.7 0.6 - 0.6 0.7 0.7 0.7MA/AA 1 0.4 1.0 â - 0.2 0.4 0.5 0.4MA/AA 2 - - 0.9 1.2 0.8 0.8 - -SRPI 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3Protease â 0.12 - 0.08 0.08 â - 0.1Lipase - 0.1 â 0.1 - â - -Amylase - â 0.8 - - - 0.1 -Cellulase - 0.15 - â 0.15 - - -PEO - 0.2 - 0.2 0.3 - - 0.3Perfume 1.6 - - â â - - -SUBSTITUTE SHEET (RULE 26)W0 98/ 1345210Example 13CA 02265942 1999-03-ll97 PCT/US97Il6705The following compact high density (0.96Kg/1) dishwashing detergentcompositions N N to SS are examples in accord with the invention and theabbreviated component identiï¬cations, used in the dish washing detergentcompositions, have the following meanings:MetasilicateNonionicPAACBZPParafï¬nBTABismuth nitrateTerpolymer480NSodium metasilicate (SiO2:Na2O ratio = 1.0)C13-C15 mixed ethoxylated/propoxylated fattyalcohol with an average degree of ethoxylation of 3.8and an average degree of propoxylation of 4.5 soldunder the tradename Plurafac LF404 by BASF GmbH(low foaming)Pentaamine acetate cobalt (III) saltBenzoyl PeroxideParaffin oil sold under the tradename Winog 70 byWintershall.BenzotriazoleBismuth nitrate salt_ Terpolymer of average molecular weight approx.7,000, comprising acrylic:maleic:ethy1acrylic acidmonomer units at a weight ratio of 60:20:20Random copolymer of 3:7 acrylic/methacrylic acid,average molecular weight about 3,500SUBSTITUTE SHEET (RULE 26)CA 02265942 l999-03- ll98W0 98/13452 PCT/US97/16705AE AF AG AH AI AJSTPP 24.80 24.80 25.00 28.39 28.50 20.00Citrate - - - - 10.00 10.00Carbonate - â 17.50 17.50 - -QEA1 0.5 1.5 2.0 1.0 1.3 0.8Silicate 20.36 20.36 14.81 14.81 14.81 âMetasilicate 2.50 2.50 2.50 - - -PB1 7.79 7.79 9.74 14.28 9.74 -PB4 - - - - 10.4Percarbonate - â - - - 6.70Non-ionic 1.50 1.50 2.00 1.50 2.00 2.60TAED 2.39 2.00 2.70 2.00 3.60 4.00HEDP 0.46 0.46 1.00 - 0.83 âDETPMP - - 0.65 - â âPAAC - - - 0.20 - -BZP ~ â â 4.44 - -Parafï¬n 0.50 0.50 0.50 0.50 - 0.20Protease 2.20 2.20 2.20 2.20 2.00 0.50Amylase 1.50 1.50 1.20 1.50 1.00 1.10BTA 0.30 0.30 0.30 0.30 - -Bismuth Nitrate - - 0.30 â - âTerpolymer - - - 4.00 - âMA/AA 2 0.5 1.0 1.00 0.50 0.7 0.8Sulphate 8 .44 8.44 20.77 - 23 .24 1.00Misc: inc moistureto balancepH (1% solution) 10.90 10.90 11.00 10.80 10.90 9.60SUBSTITUTE SHEET (RULE 26)
