CA2226628A1 - Detergent compositions comprising cation ester surfactant and enzyme - Google Patents

Abstract

There is provided a detergent composition suitable for use in laundry washing methods comprising (a) a cationic ester surfactant; and (b) a cellulolytic enzyme present at a level of from 0.01 % to 5.0 % by weight of said detergent composition, on a 1000CEVU/g basis.

Description

W O 97/03157 PCT~US96111285 DETERGENT COMPOSITIONS COMPRISING CATION ESTER SURFACTANT
AND ENZYME

Technical field The present invention relates to detergellt compositions cont~inin~ a cationic ester surf~ct~nt and a cellulolytic enzyme, which are suitable for use in laundry washing methods.

Back~ioulld to the invention The s~ti~f~ctQry removal of greasy soils/stains, that is soils/stains having a high proportion of triglycericlec or fatty acids, is a ch~llPnge faced by the form~ tor of detef~ellt compositions for use in m~rhinP laundry w~hin~ methods. Surf~ct~nt components have tr~lition~lly been employed in delerge,lt products to facilitate the removal of such greasy soils/stains. In particular, surf~ct~nt ~yslellls co~ ,ising cationic esters have been described for use in greasy soil/stain removal.

Other known delergellt compounds are cellulolytic enzymes, such as cell~ ces and endolases. They are known to be employed in de~e~
compositions as sorL~ aids. The cellulolytic enzymes are responsible for controlled catalytic removal of celllllose material, cont~in~ in fabrics.
This is often re~e~led to as 'depilling' of the fabric surface, which i~alL~i fabric softness.

For e~cample, EP-B-21,491 discloses delerge~lt compositions co.~ a nonionir/c~tionir, surf~ct~nt ...i,~ e and a builder ...i~ .e co~lising mino~ilir~te and polycarboxylate builder. The c~tionic surfactant may be a cationic ester. Improved particulate and greasy/oily soil removal is described.
US-A~,228,042 discloses biodegradable cationic surf~ct~nts, including cationic ester sllrf~ct~nts for use in delel~c~t compositions to provide greasy/oily soil removal. The combination of these cationic surf~ct~nts with nonionic sllrf~ct~nts in compositions ~lesi~n~l for particnl~te soil removal is also described.

US-A~,260,529 discloses laundry detergent compositions having a pH of no greater than 11 cont~inin~: cationic ester surfactant and nonionic surf~ct~nt at defined weight ratios.

Celllll~e in the cont~t of detergcllls has been disclosed in WO-92/1305 and EP-A495257. Cell~ e in the context of q~l~tern~ry ~mmonillm softe-nin~ compounds has been described in EP-A~9~554 and in the context of soflç~ clay in a dete~gcllt composition in EP-A-495 258 and EP-A 177165.

The removal of greasy soils/ stains from older, frequently washed fabric, especially cotton fabric, can partirlll~rly give rise to problems. These fabrics tend to suffer from resi(lll~l grease, deposited on the (cotton) fibres of the fabric, which can give the fabric a dingy, yellow appearance.

The Applicants have now found that this problem can be ~m~liorated by inrlnsion of ce~ olytic enzymes in a delelge~t compo~ition~ com~iising c~tinnir~ ester sllrf~c~nt~. Delerg~t composition~ employing both c~tionic ester surf~ct~nt and celllllolytic enzyme have been shown to deliver a surpAsingly better cle~ninf~ and softf~nin~ pe~ro~ nr-e than that of deler ~llt composition~ employing either of the two components individually.

Two mPçh~ni~m~ are believed to be responsible for these benefits.
Firstly, the greasy stain/soil removal from the st~ineA fabric sllrf~ce by the c~tionic ester surf~c-t~nt is believed to facilitate the cellulolytic CA 02226628 l998-0l-l2 W O 97/031S7 PCTnUS96/11285 'depilling' of the surface by the ce~ olytic enzyme, whereby an r i~l)roved softness and cle~nin~ pelro~ ance is achieved. Secondly, it is believed that the cationic ester surf~ct~nt interacts with free surf~ct~nt , - monomers present in the wash solution, especially with anionic surf~ct~nt monomers. Thereby, the amount of free surf~ct~nt monomers is re~lce~l~
Free surfactant monomers are known to inhibit the enzyme activity. Thus, re-lnction of the free surf~ct~nt monomer concentration in the wash solution by the c~tionic ester suff~ct~nt prevents the ~hibition of the activity of cellulolytic enzymes. Thereby, the enzyme pelro~ ce will be ted.

All docllm~nts cited in the present description are, in relevant part, incorporated herein by feference.

S~lmm~ry of the Invention The detel~ e~t composition of the present invention comprises (a) a c~tionic ester surf~ct~nt; and (b) a ce-lllllolytic ~y~e present at a level of from 0.01% to 5.0% by weight of the deter~ent composition, on a 1000 CEVU/g basis.

In a ~rerel~ed aspect, the c~tionic ester surf~ct~nt is selecte~l from ~hose having the form~

R5 1 +
Rl ~(CH~no (X~U ( C H2 )m (Y)v--(CH2 )t--N--R3 M
b - a lE

WO 97/031~7 PCTnUS96111285 wherein Rl is a Cs-C31 linear or br~nche~l alkyl, alke~yl or alkaryl chai~
or M-. N+(R6R7Rg)(CH2)S; X a~d Y, indepenl3Pntly, are selec~d from the group consistin~ o~ COO, OCO, O, CO, OCOO, CONH, NHCO, OCONH and NHCOO wherein at least one of X or Y is a COO, OCO, OCOO, OCONH or NHCOO group; R2, R3, ~4, R6, R7, a~d R8 are independenfly selected from the group con~i~tin~ of alkyl, all~enyl, hydro~yalkyl, hydroxy-alkenyl and alkaryl groups having from 1 to 4 carbon ~tom.~; and R5 is indepen~1ently H or a Cl-C3 all~yl group;
wherei~ the values of m, n, s and t indepen~l~ntly lie in the range of from O to 8, the value of b lies in the range from 0 to 20, and ~he values of a, u and v illdepende~tly are either 0 or 1 with the proviso that at least o~e of u or v must be l; and wherein M is a counter anion.

Det~iled description of the i~vention Cationic ester sur~actant AD essenti~1 çlement of the deler~ellt composition~ of the i~ventio~ is a c~tionic ester surf~ct~nt The catiol~ic ester surfactant is pre~erably present at a level of from 0.1% to 20.0~i, more ~i~,felably from 0.5% to 105~i, most plefe~bly firom 1.t)% to 5.0% by weight of the de~Gr~ t compositi~ n The c~tiQnic ester sllrfa~t~nt of ~e present inve~tion is a, pf~felably water dispersible, compou~d having surf~ct~nt properties co~p,isi~g at least one ester ~i.e. -COO-) linkage and at least one c~tionic~l1y charged group.

Suitable cationic ester surf~ct~nt~ including cholin~. ester surfact~nt~, have for e~cample been disclosed ill US Patents No.s 4228042, 4239660 a~d 4260529.

CA 02226628 l998-0l-l2 W O 97/031S7 PCTnUS96/11285 In one preferred aspect the ester linkage and cationically charged group are separated from each other in the surfactant molecule by a spacer group coneieting of a chain comprising at least three atoms (i.e. of three atoms chain length), prerefably from three to eight atoms, more ~refe~ably from three to five atoms, most preferably three atoms. The atoms forming the spacer group chain are selected from the group coneieting of carbon, nitrogen and oxygen atoms and any miY~l~es thereof, with the proviso that any nitrogen or oxygen atom in said chain comlects only with carbon atoms in the chain. Thus spacer groups having, for example, -O-~- (i.e. peroxide), -N-N-, and -N-O- linkages are eYclu~3e~1, whilst spacer groups having, for example -CH2-0- CH2-and -CH2-NH-CH2- linkages are included. In a prererled aspect the spacer group chain comprises only carbon atoms, most ~refelably the chain is a hydrocall~yl chain.

Preîelied cationic ester surf~ct~nte are those having the form R5 1 +
Rl C}(CH~nO b ~u ( C H2 )m--(Y)v--(CH2 )t--7 R3 M

- a wherein Rl is a Cs-C31 linear or br~n~he-l alkyl, alkenyl or alkaryl chain or M-. N+(R6R7R8)(CH2)S; X and Y, indepen~ently, are selecte~1 from the group coneietin~ of COO, OCO, O, CO, OCOO, CONH, NHCO, OCONH and NHCOO wherein at least one of X or Y is a COO, OCO, OCOO, OCONH or NHCOO group; R2, R3, R4, R6, R7, and R8 are indepen~1ently selecte~l from the group con~ietin~ of alkyl, alkenyl, hydroxyalkyl and hydroxy-alkenyl groups having from 1 to 4 carbon atoms and alkaryl groups; and Rs is indepen-lently H or a Cl-C3 alkyl group; wherein the values of m, n, s and t indepçn~lçntly lie in the range of from 0 to 8, the value of b lies in the range from 0 to 20, and the values of a, u and v indepçn~lçntly are either 0 or 1 with the proviso that at least one of u or v must be l; and wherein M is a c~un~r anion.

CA 02226628 l998-0l-l2 W O 97/03157 PCT~US96/11285 Preîeldbly M is selected from the group Con.Cisting of halide, me~yl slllf~te, sulfate, and nitrate, more preferably methyl sn1f~te, çhlorifle~ -bromide or iodide.

In a pr~relled aspect, the cationic ester surf~ct~nt is selected from those having the formnl~:

R1 1 5 (X)(CH2)m--N--R3 M-b a wherein Rl is a Cs-C31 linear or br~nch~l alkyl, alkenyl or alkaryl chain; X is se-lectecl from the group consi~tin~ of COO, OCO, OCOO, OCONH and NHCOO; R2, R3, and R4 are indepen~lçntly selecte~l from the group con~i~tin~ of alkyl and hydroxyalkyl groups having from 1 to 4 call.on atoms; and Rs is indepon~lently H or a Cl-C3 alkyl group;
wherein the value of n lies in the range of from 0 to 8, the value of b lies in the range from 0 to 20, the value of a is either 0 or 1, and the value of m is from 3 to 8.

More ~refelably R2, R3 and R4 are indepen-lently selecte~ fro m a Cl-4 alkyl group and a Cl-C4 hydro~yalkyl group. In one ~rGfe~red aspect at least one, pler~dbly only one, of R2, R3 and R4 is a hydro~cyalkyl group.
The hydro~cyalkyl ~rereldbly has from 1 to 4 carbon atoms, more prererably 2 or 3 carbon atoms, most ~rereldbly 2 carbon atoms. In another prefel~ed aspect at least one of R2, R3 and R4 is a C2-C3 al~,rl group, more ~ felably two C2-C3 alkyl groups are present.

Highly ~lc;ferred water dispersible c~tionic ester surf~ct~nts are the esters having the form~
J

W 097/031S7 PCT~US96/11285 R1--C--O--(CH2)m--I +--CH3 M- -where m is from 1 to 4, ~rere~ably 2 or 3 and whereiIl Rl is a Cll-Clg linear or br~nch~o~l alkyl chaiIl.

Particularly ~refelled choline esters of this type include the stearoylcholine ester q~te n~-y methylammonium h~ es (Rl=C17 alkyl), p~lmitoyl choline ester quaternary methyl~mmonium h~ lec (Rl=Cls alkyV, myristoyl choline ester qu~tern~-y methyla_monium h~ es (Rl=C13 alkyl), lauroyl choline ester methyl~mmonillm h~ les (Rl=Cll alkyl), cocoyl choline ester quaternary methyl~mmonium h~ s (Rl=Cll C13 alkyl), tallowyl choline ester qn~tern~ry methyl~mmoninm h~ les (Rl =Cls C17 aLkyl), and any mi~ res ~hereof.

Other sllit~ble cationic ester surf~ct~nt~ have the strl~ctllr~l form below, wherein d may be from 0 to 20.

Rl--O--CR__~CH2)~--C--O--CH2CH2--I+--CH3 M-M-CH3- ~ +CHz - CH2- O -C--~CH2)- ~ - O -CH2 - CHZ- ~ -CH3M

ID a ~refelled aspect the c~tionic ester surf~ct~nt is hydrolysable under the contlition~ of a laundry wash method.

The parti~nl~rly ~refelled choline esters, given above, may be ~)f ~ ~red by the direct e~le~ tion of a fatty acid of the desired ch~ length with ~lim~ yl~ oeth~nol~ in the presence of an acid catalyst. The reaction CA 02226628 l998-0l-l2 product is then quaternized with a methyl halide, preferably in the presence of a solvent such as ethanol, water, propylene glycol or preferably a fatty alcohol ethoxylate such as Clo-Clg fatty ~lcohol ethoxylate having a degree of ethoxylation of from 3 to 50 ethoxy groups per mole fol~ing the desired c~tionic m~teri~l. They may also be plc~ared by the direct esterific~tion of a long chain fatty acid of the desired chain length together with 2-haloethanol, in the presçnce of an acid catalyst m~teri~l. The re~ction product is then q~-~terni7e~l with trimethyl~mine, ~~ the desired cationic material.

Cellulolytic e-~yllle Another esse~t~l component of the deler~ t compositiQn of ~he ~)~GSC~t invention is a celll~lolytic enzyme, that is an enzyme having a cellulolytic activity.

The delergellt compositions of the present invention co~lise the cellulolytic enzyme at a level of from 0.01% to 5.0% by weight, more prefelably from 0.3% to 4% by weight and most ~ref~ldbly from 0.5% to 3% by weight of the deler e~t composition, on a lOOOCEVU/g basis.

Herein the terms "ce~ e" and "celluloly-tic" denote an e~yme with cell~-lolytic activity. This means that the enzyme catalyses the hydrolysis of celll~lose, and specificly the cellulose fibres of fabric. The ce~ olytic e~yme may be a co~onent oc~ p in a cell~ e sy~le pro~ ce(1 by a given microor~ni~m, such a cellnl~e ~y~le~ mostly coll,ylising several dirrerent ce~ lolytic enzyme compoQents inclll-lin those usually i(lentifi~ as e.g. cellobiohydrolases, e~c~cellobiohydrolases, endo~h-c~n~es, ,B-~lnco.c~ es.
l;vely, the celllllolytic enzyme may be a single component, i.e. a component esse-nti~lly free of other cell-~ e components usually OC~ in a cell~ e ~ysk;~ produced by a given microorg~ni~m, the single component being a recombinant component, i.e. proAl-ce-l by cloning of a DNA sequence encoding the single component and subse-CA 02226628 l998-0l-l2 W O 97/03157 PCT~US96/11285 quent cell transformed with the DNA sequence and expressed in a host, cf. e.g. ~nt.~ tional Patent AppIications WO 91/17243 and WO
9I/17244 which are hereby incorporated by refere~ce. The host is pre~er-ably a heterologous host, but the host may under cell~ con~litionc also be the homologous host.

It is contell,plated that the cellulolytic enzyme may have an e~o-mode of action, the term "exo mode of action" being int~n~lecl to mean initi~ting degradation of cellulose from t_e non-rerl~1cin~ chain ends by removing cellobiose units.
.~lt~rn~tively, it is co~te~l~lated that the cellulolytic en~yme may have an endo-mode of action, the "endo-mode of action" being intentle~1 to mean hydrolysing amorphous regions of low cryst~11inity in cçll-~lose fibres.
The cç111110lytic enzyme herein may be obtained from a microorg~nicm source by use of any suitable teçhnique. For inet~nce~ a ce1h110lytic enzymese plepalation may be obtained by fe m~ont~tion of a microor~nicm and subsequent isolation of the prc~al~ion from the fermente~ broth or microorg~ni~m by methods known in the art, but more erelably by use of recombinant DNA teçhniques as known in the art.
Such method normally complises cultivation of a host cell transformed with a recombinant DNA vector capable of expressing and Call,~i~g a DNA sequence enCof1ing the cellulolytic enzyme in question, in a culture mecli11m under con~ition~ permittinp the expression of the enzyme and re-covering the e~y~c from the culture.

Preferably, the cç11~101ytic enzyme is a fungal or b~rteri~1 cç11~ e component, i.e. of fungal or b~cteri~1 origin.

It is coi-te...~ ted tllat the cellulolytic enzyme may be derived or isolated and p11rifie~1 from microor~ni~m~ which are known to be c~r~l~le of pro~lncin~ cellulolytic enzymes, e.g. species of Humicola, Bacillus, 1 choderma. Fus~liu~, Mycelio~ht~ora, Phanerochaete, Schizo~hyllum, Penicillium, As~erYillus, and Geotricum. The derived co~ol.ents may be either homologous or heterologous co~ollents. rrefe~ably, the W O 97103157 PCT~US96/1128S

components are homologous. However, a heterologous component which is il.lllllllloreactive with an antibody raised ~in~t a highl.y pn-ifi cellulolytic enzyme component possessin~ the desired property or pro~
erties and which heterologous component is derived from a specific mi-croor~ni~m is also ~l~relr~d.

Pler~ d ce-llnlolytic enzymes herein may be any of those disclosed in the published European Patent Application No. EP-A-271 004, ~he cellulolytic enzyme having a non~egrading inde~c (NDI) of not less ~han 500 and being an alkalo~?hilic celllllolytic enzyme having an opLi~u.ll pH
not less than 7 or whose relative activity at a pH of not less than 8 is 50%
or over of the activity under optimum conclition~ when carbo~cy methyl ce.lllllose (CMC) is used as a substrate; the celllllolytic enzyme ~rer~ bly being selected from the group con~ tin~ of ~lk~line cçlllll~e K (pro~lnce~l by Bacillus sp. KSM-635, FERM BP 1485); :~lk~line cellnh~e K-534 (pro~lce l by Bacillus sp. KSM-534, F~RM BP 1508); ~lk~line celll~ e K-539 (produced by Bacillus sp. KSM-539, FERM BP 1509); :~lk~lin~
celllll~e K-577 (pro~11lce~1 by Bacillus sp. KSM-577, FERM BP 1510);
~lk~lin~ ce~ e K-521 (pro~cefl by Bacillus sp. KSM-521, FERM BP
1507); ~lk~line cell~ e K-580 (pro~l~lce-l by Bacillus sp. KSM-580, FERM BP 1511); ~lk~line ce~ ee K-588 (pro~ ce~ by R~ us sp.
KSM-588, FERM BP 1513); ~lk~lin~o. cel~ ee K-597 (pro~l~ce~1 by Bacillus sp. KSM-597, FERM BP 1514); ~lk~line celll~ e K-522 (pro~ ce~ by Bacillus sp. KSM-522, FERM BP 1512); CMCaee I, CMCase II (bo~h pro~ ce~l by Bacillus sp. KSM-635, F~RM BP 1485);
~lk~line ce.lllll~ee E-II and ~lk~line cell~ se E-m (both pro~lnce~l by Bacillus sp. KSM-522, FERM BP 1512).

A conve.lient celllllolytic e~y~e useful in the delerg~t compos~ n of the present invention may be an endoglllc~n~ee component which is im-munoreactive with an antibody raised ~g~inst a highly pnrifie~ 43kD
endo~ c~n~se derived from Numicola insolens, DSM 1800, or which is a homologue or delivalive of the 43kD endo~lnc~n~ee exhibiting cellulolytic activity. A ~refe~l~d endoP:lllc~n~ee component has the amino acid sequence ~1i.eclose~l in PCT Patent Applic~tion No. WO 91/17243, SEQ ID~2, which is shown in the appended SEQ ID NO:4, or a variant of W O 97/03157 PCT~US96/11285 said endoPl~lc~n~e having an amino acid sequence being at least 60%, ~rere~dbly at least 70%, more preferably 75%, more preferably at least 80%, more prefel~bly 85%, especially at least 90% homologous with said sequence.

Another prc;r~lled endo~ c~n~e component co~lises an amino acid sequence encoded by the partial DNA sequence disclosed in PCT Patent Applic~tion No. W093/11249; SEQ ID~l 1, which is showD in ~he appended SEQ ID NO:5, or a variant of said endo~ c~n~e having an amino acid sequence being at least 60%, preferably at least 70%, more preferably 75%, more preferably at least 80%, more ~refeldbly 85%, especially at least 90% homologous with said sequence.

Yet another ~rert;rred endoElnc~n~se component colllylises an amino acid sequence enco~le~ by the partial DNA sequence ~1isclose~l in PCT Patent Application No. WO 93/11249, SEQ ID#9, which is hereby inco~o~ated by reference.
Yet another preferred endoPhlc~n~e component comrri~e~ an amino acid sequence enCo~l~ by t~e partial DNA sequence (1i~clo~ef1 in PCT Patent Applic~tiQn No. WO93/11249, SEQ l[D#7, which is hereby incorporated by reference. In e~cample 1 below, the endoPl~lc~n~e component is rerelled to as EG m.
tPrn~tively~ the celllllolytic enzyme may be an endo~lllc~n~ce component which is ~ oreactive with a~ antibody raisesl ~ n~t a highly pllrifi~l 60kD endo~ c~n~e derived from R~ci~1r~ ~us, NCIMB 40250, or which is a homologue or derivative of t~e 60kD
endo~ c~n~e e~hihit~ cell-ll~e activity. A ~lefe~red endogll~n~ce component has the amino acid sequence ~lieclose~l in PCT Patent Applica-tion No. WO 91/10732, SEQ ID~7, which is shown i~ the appended SEQ
ID NO:6, or a variant of said e~do lllc~n~e having an amino acid sequence beiIIg at least 60%, ~rcfel~bly at least 70%, more preferably 75%, more ~lcfe~ably at least 80%, more ~rcferably 85%, especially at least 90% homologous with said sequence.

W O 97/03157 PCT~US96/11285 Additional delerg~l~t components The delergenl compositions of the invention may also cont~in ~ ition~l v ~ delelgc.ll components. The precise nature of these ~ itio-n~l compont--nte, and levels of incorporation thereof will depend on the physical form of the composition, and the precise nature of the washing operation for which it is to be used.

The compositions of the invention preferably contain one or more additional delerg~;~t components selected from ~ ion~l surf~ct~nte, ble~ches, builders, organic polymeric compounds, ~ itional enzymes, suds ~up~lcssors, lime soap dispersants, soil suspension and anti- ~
redeposition agents and corrosion inhibitors.

Additional surfactant The detergcnt compositions of the invention yrefel~bly co~ .. an ition~l surf~ct~nt selecteA from anionic, nonionic, non-ester c~tic!nic~
~mrholytic, ~mphoteric and ;cwill~-- ;onic surf~ct~nte a~d m~ res thereof.

A typical listing of ~nionic, nonionic, ~mpholytic~ and icwi~~r;onic classes, and species of these surfactants, is given in U.S.P. 3,929,678 issued to ~ ~n~hlin and ~ellrin~ on December 30, 1975. Further e~camples are given in "Surface Active Agents and Detergents" (Vol. I and II by ScLw~l;~, Perry and Berch). A list of suitable cationic surf~ct~nts is given in U.S.P. 4,259,217 issued to Murphy on March 31, 1981.

Where present, ~mrholytic, ~mrhoteAc alld ;~wiuerol~ic surf~ct~r~te are generally used in combin~ti- n with one or more ~nionic and/or nonionic surf~ct~nte.
Anionic surfactant The delelge~t compo~eitione in accord with the present invention eîelably compri~e an ~ldition~l ~nionic surf~cPnt. Fsse-nti~lly aIly ~nioniC surf3ct~nte useful for delelsive purposes can be comprised in the delergellt composition. These can incl~lde salts (inclu~1in~ for e~cample, so~ m, pot~Ccillm~ ammonium, and substit~lte~ ~mmonillm salts such as mono-, di- and triethanol~mine salts) of the anionic s~llf~, slllf~n~e, carbo~cylate and sarcosinate surf~et~nts. Anionic slllf~te surfactants are ~r~

Other ~nionic surf~ct~ntc include the isethionates such as the acyl isethion~tes, N-acyl taurates, fatty acid ~mi-les of methyl t~llri~le, alkyl succinates and sulfosuccinates, monoesters of sulfosuccinate (especially saturated and vnc~t~lrated C12-C18 monoesters) diesters of sulfosuccinate (especially saturated and lln.c~t lrated C6-C14 diesters), N-acyl sarCocin~tec~ Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydroge~ated rosin, and resin acids and hydrogenated resin acids present in or derived from tallow oil.

Anionic sulfate surf~ct~nt ,Anionic s llf~te surf~ct~nt~ suitable for use herein include the linear and br~nr-hed pAmary and seCon~l~ry alkyl slllf~tes, alkyl ethoxyslllf~tes, fatty oleoyl ~lycerol slllf~tes, alkyl phenol ethylene o~ide ether slllf~tes, ~he Cs-C17 acyl-N-(Cl-C~ alkyl) and -N-(Cl-C2 hydro~yalkyl) ~lnc~mine slllf~tes, and sl~lf~tes oiE alkylpolys~cçh~ri~les such as the snlf~s of alkylpoly~lncosi~e (the nonionir non~vlf~ted compounds being ~1escrihed herein).

Alkyl s~lf~te surf~ct~nts are ~e~l~bly selected from the linear and br~n~-he~ Cl~Clg alkyl slllf~tes, more ~lere~dbly the Cll-Cls br~n~-h~3 chain alkyl s~lf~tec and the C12-C14 linear chain alkyl sl1lf~es.

Alkyl etho~cyslllf~tp- surf~ct~nte are preferably selecte~l from the group con~i~tin~ of the Cl~Cl~ alkyl slllf~tes which have been etho~ylated with from 0.5 to 20 moles of ethylene oxide per molecule. More ~er~l~bly, the alkyl etho~ysulfate s~ ct~nt is a Cll-Clg, most ~erefably Cll-Cls alkyl slllf~te which has been etho~ylated with from 0.5 to 7, ~fefeiably from 1 to 5, moles of ethylene o~cide per mol~clllP.

CA 02226628 l998-0l-l2 W O 97/03157 PCTrUS96/11285 A particularly ~rere~led aspect of the invention employs miytllres of the yrere~r~d alkyl sl-lf~te and alkyl ethoxysulfate surfact~nt~. Such mi~l..fes have been disclosed in PCT Patent Applic~tion No. WO 93/18124.

Anionic sulfonate surfactant ~nionic sulfonate surfact~nts suitable for use herein incl~lde the salts of Cs-C20 linear alkylben7~-nt~ sulfonates, aLkyl ester slllfon~tes, C6-C~
primary or secondary alkane sulfonates, C6-C24 olefin sl~lro..~tes, sulfonated polycarbo~ylic acids, alkyl glycerol slllfon~tes, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfonates, and any mi~tnres thereof.

Anionic carboscylate surfactant Suitable ~nioniC carboxylate surf~ct~nt~ include the alkyl etho~y carboxylates, the alkyl polyethoxy polycarboxylate surf~ct~nt~ and the soaps ('alkyl carbo~yls'), especially certain secondary soaps as ~les~ribe~
herein.
Suitable alkyl etho~y carboxylates include those with the formula RO(CH2CH20)~C CH2COO M+ wherein R is a C6 to Clg alkyl group, ranges *om O to 10, and the ethoxylate distribution is such that, on a weight basis, the amount of m~teri~l where ~ is 0 is less than 20 % and M
is a c-~tion. Suitable alkyl polyethoxy polycarboxylate surfac~ant~e inC~ ç
those having the form~ RO-(CHRl-CHR2-O)-R3 wherein R is a C6 to Clg alkyl grollp, ~ is from 1 to 25, Rl and R2 are selecte~3 from the group conei~tin~ of hydrogen, methyl acid ra~ic~l, s~ccinic acid ra-liG~l, hydro~ys~lccinic acid r~ l, and .~.ix~ ~.es thereof, aIId R3 is se~ected from the group con~i~tin~ of hydrogen, substit~ te~ or lln~llbsl;L.~
hydrocarbon having between 1 and 8 carbon atoms, and mi~ res thereof.

Suitable soap surf~ct~nt~ include the secon~l~ry soap surfact~nt~ which conl~ a carbo~cyl unit connecte~l to a secon~l~ry carbon. r~r~r~
seContl~ry soap surf~ct~ntc for use herein are water-soluble members selecte~l from the group con~istin~ of the water-soluble salts of 2-methyl-WO 97/03157 PCTnJS96/11285 l-lm~lec~noic acid, 2-ethyl-l-~1ec~noic acid, 2-propyl-1-non~nQic acid, 2-butyl-l-octanoic acid and 2-pentyl-1-hep~noic acid. Certain soaps may also be inclll~le l as suds ~u~ressors.
Alkali metal sarcosinate surfactant Other suitable ~nionic surfactants are the alkali metal sarcosin~tes of formula R-CON (Rl) CH2 COOM, wherein R is a Cs-C17 linear or br~n-~-h~ alkyl or alkeIlyl group, Rl is a Cl-4 alkyl group and M is an alkali metal ion. rlererred e~camples are the myristyl and oleoyl methyl sarCocin~te~c in the form of their sodium salts.

Alkoxylated nonionic surfactant Fcsçnti~lly any alkoxylated nonionic surf~ct~nts are suitable herein. The ethoxylated and propo~ylated nonionic surf~ct~nts are ~refelled.

~erel,ed alkoxylated s~ ct~nts can be selecte~l from the cl~sses of the nonionic conrlçn~tes of alkyl phenols, nonionic etho~cylated alcohols, nonionic ethoxylated/propoxylated faKy alcohols, nonionic etho~cylate/propo~ylate con~çnC~tes with propylene glycol, and the nonionic etho~ylate conl1enc~tion products with ~ro~ylene o~cide/ethylene rli~min~ ~Mncts~

Nonionic alko~cylated alcohol surfactant The con~lçnc~tion products of aliphatic alcohols with from 1 to 25 moles of alkylene o~ide, partic~ rly ethylene oxide and/or propylene o~ide, are suitable for use herein. The alkyl chain of the ~liph~tic alcohol can either be straight or br~n~h~l~ pr;~ y or secondary, and generally cc~ inc from 6 to 22 carbon atoms. Par~ic~l~rly ~lerell~d are the con~1çn~ti~n productc of alcohols having an alkyl group cnnt~ining from 8 to 20 carbon atoms with from 2 to 10 moles of ethylene o~ide per mole of alcohol.

Nonionic E~olyhydroxy fatty acid amide surfactant CA 02226628 l998-0l-l2 W O 97/03157 PCTrUS96/11285 Polyhydroxy fatty acid ~mitle~ suitable for use herein are those having the structural formula R2CONRlZ wherein: Rl is H, Cl-C4 hydrocarbyl, 2-hydro~y ethyl, 2-hydroxy ~r~yl, ethoxy, propoxy, or a mixtllre thereof, efelable Cl-C4 alkyl, more ~rer~lably Cl or C2 alkyl, most ylefe~dbly Cl alkyl (i.e., methyl); and R2 is a Cs-C31 hydrocarbyl, ~referably straight-chain Cs-Clg alkyl or alkenyl, more ~refe,ably straight-chain Cg-C17 alkyl or alkenyl, most prefel~bly straight-chain Cll-C17 alkyl or alkenyl, or mi~ct~lre thereof; and Z is a polyhydro~yl~drocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connecte~ to the chain, or an alkoxylated derivative (~refelably ethoxylated or propoxylated) thereof. Z prereldbly will be derived from a reducing sugar in a reductive ~min~tion re~ction; more preie~ably Z is a glycityl.

Nonionic fatty acid amide surfactant Suitable fatty acid amide surf~ct~nts include those having ~che form~
R6CoN(R7)2 wherein R6 is an alkyl group cont~inin~ from 7 to 21, ,~efelably from 9 to 17 carbon atoms and each R7 is selecte~1 from the group con~i~tin~ of hydrogen, Cl-C4 alkyl, Cl-C4 hydroxyalkyl, and -(C2H40)XH, where ~c is in the range of from 1 to 3.
Nonionic alkylpolysaccharide surfactant Suitable alkylpolys~cch~ri(les for use herein are disclosed in U.S. Patent 4,565,647, ~ 1~n~lo, issued January 21, 1986, having a hydrophobic group cont~inin~ from 6 to 30 carbon atoms and a polys~cch~ri~le, e.g., a poly~lycoside, hydrophilic group cont~inin~ from 1.3 to 10 ~cch~ le units.
rrere~fed alkylpolyglycosi~les have the formula R20(CnH2nO)t(glycosyl)~

wherein R2 is selecte~ from the group con~i~tin~ of alkyl, alkylphenyl, hydro~cyalkyl, hydro~cyalkylphenyl, and mi~ es thereof in which the W O 97/03157 PCT~US96/11285 alkyl groups contain from 10 to 18 carbon atoms; n is 2 or 3; t is from O
to 10, and x is from 1.3 to 8. The glycosyl is prefelably derived from glucose.

Amphoteric su~factant Suitable ~mrhoteric surf~ct~nts for use herein include the amine o~ide surf~ct~nts and the alkyl amphocarboxylic acids.

Suitable amine oxides incll7cle those compounds having the formula R3(oR4),CNO(RS)2 wherein R3 is selected from an alkyl, hydroxyal~l, acyl~mi~opropoyl and alkyl phenyl group, or m~ res thereof, co~ ...in~ ~
from 8 to 26 carbon atoms; R4 is an alkylene or hydro~yalkylene group co.~ ;n~ from 2 to 3 carbon atoms, or mixt~lres thereof; ~ is from O to 5, yrerelably from O to 3; and each R5 is an alkyl or hydro~cyalkyl group cont~inin~ from 1 to 3, or a polyethylene oxide group cont~inin~ from 1 to 3 ethylene oxide groups. rrert;-red are C10-C18 alkyl ~1im~thyl~tnin~
oxide, and Cl~lg acyl~mi~lo alkyl ~lim~thyl~mine oxide.

A suitable example of an alkyl ~pho-licarboxylic acid is Miranol(TM) C2M Conc. m~nilf~ctll~ed by Miranol, Inc., Dayton, NJ.
Zwitterionic surf7/ct?lnt Zwitterionic surf~cPnts can also be incorporated into the detergent compositions hereof. These surf~cPnt~ can be broadly tlescribed as delivalives of secon~3~ry and tertiary ~mines~ de~ival ives of heterocyclic seCon~ y and tertiary ~mines, or deliv~ives of ~ te~ mmonillm qn~te~ phosphonillm or tertiary sulr~,~u ~ compounds. Ret~into and s~ ine surf~ct~nts are e~emplary z~vitfçrionic sllrf~ct~nts for use herein.
,i Suitable bet~ines are those compounds having the formula R(R')2N+R2COO- wherein R is a C6-Clg hydrocarbyl group, each Rl is typically Cl-C3 alkyl, and R2 is a C1-Cs hydrocarbyl group. ~refe~led bet~in~s are C12 18 t3inn~thyl-ammonio he~no~te and the C1~1g CA 02226628 l998-0l-l2 W O 97/03157 PCTrUS96/11285 acy1~midopropane (or ethane) dimethyl (or diethyl) bet~ine~e. Complex betaine surf~ct~nte~ are also suitable for use herein.

Cationic surfactants ~ddition~l c~ionic surf~ct~nte can also be used in the detergent compositione herein. Suitable c~tioniC surfactants include the qll~te~
~mmonillm surf~ct~nts sel~cted from mono C6-C16, ~)fcrel~bly C6-C10 N-alkyl or alkenyl ~mmonil~m surf~ct~nfe wherein the re.~ N
positions are sul~s~;luie~3 by methyl, hydroxyethyl or hydroAyyr~
groups.

CA 02226628 l998-0l-l2 W O 97/03157 PCTnUS96/1128S

Alk~qlinity In che deter CllL compositions of the present invention yre~rably a ~lk~linity ~y~Lelll is present to achieve optimal c~tionic ester ~ ct~nt pelro~ ee. The ~ linity ~yslt;lll comprises compo~ents capable of providing ~lk~linity species i~ solution. By ~lk~linity species it is meant herein: carbonate, bicarbonate, hydro~ide, lhe various .~ilie~te ~nion~, percarbonate, perborates, perphosphates, persulfate and per.eilic~te.
Such ~lk~linity species can be formed for example, when ~lk~lin~ salts selected from alkali metal or ~lk~lin~ earth carbonate, bicarbo~ate, hydroxide or silicate, including cryst~lline layered sili~te, salts and any mixb1res thereof are dissolved in water.
F~mrles of carbonates are the ~lk~line earth and alkali metal carboIIates, including sodium carbonate and sesqui-carbonate and any .~ res thereof with ultra-fine calcium carbonate such as are disclosed in Oe Patent Applic~tion No. 2,321,001 published on November 15, 1973.
Suitable silic~tes includle the water soluble sodium silic~tes with an SiO2:
Na20 ratio of from 1.0 to 2.8, with ratios of from 1.6 to 2.0 being ~rer~led, and 2.0 ratio being most ~le~l,ed. The ~ilic~tes may be ill the form of either the anl~ydl~ us salt or a hydrated salt. Sodium sili~te with an SiO2: Na20 ratio of 2.0 is the most preferred .~ilic~te~
P~erelled cryst~ n~ layered silic~tes for use herein have ~e general formula NaMSix02x+ 1-YH20 wherein M is so~ m or hydrogen"c is a ~umber from 1.9 to 4 and y is a -number from 0 to 20. Cryst~lline layered sor3i~lm silic~tes of this ~ype are disclosed in EP-A~164~514 and methods for their ~r~aldlion are disclosed Ln DE-A-3417649 and DE-A-3742043. Herein, ~ in ~he general formula above ~rerel~bly has a value of 2, 3 or 4 and is ~lefe~ably 2. The CA 02226628 l998-0l-l2 W O 97/03157 PCT~US96/11285 most l,refel~ed m~teri~l is ~-Na2Si20s, available from Hoechst AG as - NaSKS-6.

W O 97/03157 PCTnUS96/11285 Water-soluble builder compound The de~er~ t compo~ition~ of the present invention ~re~r~bly contain a water-soluble builder compound, typically present at a level of from 1%
to 80% by weight, ~ler~lably from 10% to 70% by weight, most prerelably from 20% to 60% by weight of the composition.
Suitable water-soluble builder compounds include the water soluble monomeric polycarbo~ylates, or their acid forms, homo or copolymeric polycarboxylic acids or their salts in which the polycarboxylic acid comprises at least two carboxylic radicals separated from each other by not more that two carbon atoms, borates, phosphates, and m~ res of any of the foregoing.
The carboxylate or polycarboxylate builder can be momomeric or oligomeAc in type although monomeric polycarbo~ylates are generally yrererred for re~onC of cost and pelr~ ce.

Suitable carboxylates cont~inin one carboxy group include the water soluble salts of lactic acid, glycolic acid and ether deliv~Lives thereof.
Polycarboxylates co~ two carboxy groups include the water-soluble salts of succinic acid, m~lonic acid, (ethylenedioxy) ~ cetir acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid and r,. .,.~ . ;C acid, as well as the ether carboxylates and the sulfinyl carboxylates. Polycarboxylates cont~inin~ three carbo~y groups include, in particular, water-soluble citrates, ~c~ tes and citraconates as well as succi~aLe deliva~ives such as the carbo~ymethylo~ysuccin~tes described in British Patent No.
1,379,241, lacto~cysuccin~tes described in British Patent No. 1,389,732, and ~minosllccin~tes ~lesc-ribe~l in Netherl~n-1s Appli5~tion 7205873, and the oxypolycarbo~ylate m~teri~l~ such as 2-o~ca-1,1,3-1?ropa~e tricarbo~ylates ~3esc-rihed in British Patent No. 1,387,447.

W O 97/03157 PCTnUS96/11285 Polycarboxylates cont~inin~ four carboxy groups include o~ydisuccin~tes disclosed in British Patent No. 1,261,829, 1,1,2,2-ethane tetracarboxylates, 1,1,3,3-p~opane tetracarboxylates and 1,1,2,3-~ro~ane tetracarbo~ylates. Polycarboxylates cont~inin~ sulfo s~lbstit~çnts incl~ e the sulfosuccinate delivalives disclosed in British Patent Nos. 1,398,421 and 1,398,422 and in U.S. Patent No. 3,936,448, and ~he slllfons~te~
pyrolysed citrates described in British Patent No. 1,439,000. r~ere~
polycarboxylates are hydroxycarboxylates cont~inin~ up to three carbo~cy groups per molecule, more particularly citrates.

The parent acids of the monomeric or oligomeric polycarboxylate ch~ tin~ agents or mi~rt~lres thereof with their salts, e.g. citric acid or citratefcitric acid miX~-~res are also co~te~ lated as useful builder components.

Borate builders, as well as builders cont~inin~ borate~ g ,..~e. ;~1 that can produce borate under delergent storage or wash con~liti~ n~ are useful water-soluble builders herein.
Suitable examples of water-soluble phosphate builders are the alkali metal tripolyphosph~tes~ sotlillm, pot~C~illm and ~mmonillm pyropho~h~te, so~ m and pot~ lm and ~mmo~ m pyrophosphate, so~lillm and pot~sinm orthophosph~te, so~ lm polymeta/phosphate in which the degree of polymeri7i~tion ranges from about 6 to 21, and salts of phytic acid.
Partially soluble or insoluble builder compound The deter~ent composition~ of the present invention may cont~in a partially solllble or in~ol~lble builder compound, typically ~lesent at a level of from 1% to 80% by weight, ~lefe~ably from 10% to 70% by weight, most prefelably from 20% to 60% weight of the com~osition.
F~y~mrles of largely water insoiuble builders include the so~ m ~lnminosilic-~tes.

W O 97/03157 PCT~US96/11285 Suitable ~ minosilic~t~. zeolites have the unit cell formula - ~
Naz[(Al02)z(SiO2)y]. ~H2O wherein z and y are at least 6; ~he molar ratio of z to y is from 1.0 to 0.5 and x is at least 5, ~rerelably from 7.5 to 276, more preferably from 10 to 264. The ~lnmino~ilic~t~ material are in hydrated form and are ~rerelably cryst~llin~., cnnt~ining from 10% to 28%, more prefelably from 18% to 22% water in bound form.
The ~hlminosilic~t~ zeolites can be naturally occ~rrinP: m~teri~lc, but are eferably synthetically derived. Synthetic cryst~lline ~ minosilic~te ion e~c.h~n~e m~teri~lc are available under the ~le~i~n~til7n~ Zeolite A, 7eolite B, Zeolite P, Zeolite X, Zeolite HS and mi~ res thereof. Zeolite A has t~e forml]l~

Na 12 [A102) 12 (sio~)l2]- ~cH2O
wherein ~c is from 20 to 30, especially 27. Zeolite X has the formula Na86 [(Alo2)86(sio2)lo6l. 276 H20.
Organic pero~cyacid bleaching ~ysle A preferred feature of delefgent compositions of the invention is aIl organic pero~yacid ble~chin~ ~y~le~. In one preferred e~ecllti~n the ble~chin~ ~y~elll cont~in.s a hydrogen pero~cide source and an orgaI~ic pero~cyacid bleach ~iG~ or compoul~d. The pro~ ctior of the organic pero~yacid occurs by an in situ re~ctinn of the precursor with a source of hydrogen pero~cide. r~fe,led sources of hydrogen pero~cide inClllf3ç
inorganic pelllyd~ate ble~ches. In an ~ tive ~refe~fed e~pcntion a ~rerol ed organic pero~yacid is incorporated directly into the composition. Composition~ cont~inin~ lures of a hydrogen pero~ide source and organic pero~yacid precursor in combin~tion with a pr~,folmed .
organic pero~cyacid are also envisaged.
-CA 02226628 l998-0l-l2 W O 97/03157 PCTrUS96/11285 Inor~anic pelhydlate bleaches Inorganic perhydrate salts are a plere.led source of hydrogen peroxide.
These salts are normally incorporated in the form of the alkali metal, prefef~bly sodium salt at a level of from 1% to 40% by weight, more ~referably from 2% to 30% by weight and most preferably from 5% to 25 % by weight of the compositions.
Fx~mples of inorganic perhydrate salts include perborate, percarbonate, perphosphate, perslllf~te and persilicate salts. The inorganic perhydrate salts are normally the alkali metal salts. The inorganic pelLydrate salt may be included as the cryst~llin~ solid without additional protection- For certain pelLydlate salts however, the ~lefelled e~eclltione of such granular colllyositions utilize a coated form of the m~teri~l which provides better storage stability for the perhydrate salt in the granular product. Suitable co~tin~e com~ise inorganic salts such as alkali metal silicate, carbonate or borate salts or mi~t~lres thereof, or organic m~teri~l.e such as wa~es, oils, or fatty soaps.

Sodium pellJo~ate is a prerell~d pelLyd~ate salt and can be in the form of the monol~ydrate of nominal formula NaB02H202 or the tetrahydrate NaB02H202-3H20-Alkali metal percarbonates, particularly sodium percarbonate are~referl~l pell~Lates herein. Sodium percarbonate is an ~rl~lition compound having a formula correspon~lin~ to 2Na2C03.3H202, and is available commercially as a cryst~llin~o solid.

Pot~csil~m pero~ymonopersl~lf~te is another inorganic pelhydlate salt of use in the detergent compositions herein.

W O 97/03157 PCT~US96/11285 Pero~yacid bleach precursor Peroxyacid bleach precursors are compounds which react with hydrogen pero~ide in a perhydrolysis re~ction to produce a pero~yacid. Generally pero~yacid bleach precl~rsors may be representer1 as Il X-C--L

where L is a leaving group and X is essenti~lly any fimCtion~lity~ such that on perhydroloysis the structure of the peroxyacid pro-1uce~ is o Il X-C-OOH

Peroxyacid bleach precursor compounds are plererably incoIporated at a level of from 0.5~ to 20% by weight, more p~efeli1bly from 1% to 15%
by weight, most preferably from 1.5% to 10% by weight of the detef ent composition~

Suitable pero~yacid bleach precursor compounds typically cont~in one ormore N- or O-acyl groups, which precursors caIl be selected from a wide range of classes. Suitable classes include anhydrides, esters, imi~les~
l~ct~m~ and acylated derivatives of imitl~oles and n~imP~. P.Y~mrles of useful m~ter~ e within these classes are disclosed in GB-A-1586789.
Suitable esters are ~lisclose~l in GB-A-836988, 864798, 1147871, 2143231 and EP-A~170386.

Leavin~ ~roups T

The leaving group, herçin~ter L group, must be snmciently reactive for the perhydrolysis re~ction to occur within the O~ u~ time frame (e.g., a wash cycle). However, if L is too reactive, this activator will be difficlllt to st~ e for use ill a ble~ching composition.

W O 97/03157 PCT~US96/11285 - . rrereiled L gr~,ups are s~l-octe~l from the group con~i~ting of:- _0~ o~Y , and --~SR3Y

--N--C--R1 3 Nl--C--Cl H--R4 IR3 r --O--C H=C--C H=C H2 --~C H=C--C H=C H2 -~C--R1 _~,C H¦~ R4 ~C~

O O

--O--C=CHR4 , and N S--CH--R4 R3 o and mi~ res thereof, whereill Rl is an alkyl, aryl, or alkaryl group cont~inin~ from 1 to 14 c~1,41, atoms, R3 is an alkyl chain cont~ininf~
from 1 to 8 carbon atoms, R is H or R, and Y is H or a solubilizing group. Any of Rl, R3 and R4 may be substi1~lte~1 by essçnti~lly any ~ln~.tion~l group incl~ in~, for example alkyl, hydroxy, alko~y, halogen, amine, nitrosyl, amide and ~mmonillm or alkyl ~ ----onium groups The p~efe~red solubilizing groups are -S03-M +, -C02~ +, -S04-M +, -N+(R3)~ and 0<--N(R3)3 and most ~refefably -S03-M+ and -C~2 M wherein R3 is an alkyl chain cnnt~inin~ from 1 to 4 carbon atoms, M is a cation which provides solubility to the bleach a~ilivalor and CA 02226628 l998-0l-l2 W O 97/03157 PCTnUS96/11285 X is an anion which provides solubility to the bleach aclivalor.
Preferably, M is an allkali metal, ammonium or s~lbstitnte~ ~rnmQninm c~tion, with so~ lm and pot~sillm being most preferred, and X is a halide, hydro~ide, methylsulfate or acetate anio~.

Alkyl percarboxylic acid bleach precursors Alkyl percarboxylic acid bleach precursors form percarboxylic acids o~
perhydrolysis. rrefelled ~re.;~isors of t~is type provide per~cetic acid on perhydrolysis.

Prefelled alkyl percarboxylic precursor compounds of the imide ~gpe include the N-,N,NlNl tetra acetylated alkylene ~i~mine~ wherein the alkylene group cont~in.~ from 1 to 6 carbon atoms, par~ic~ rly ~hose compoullds i~ which the alkylene group co~ 1, 2 and 6 carbon atoms.
Tetraacetyl ethylene tli~mine (TAED) is par~ic~ y ~refe~

Other prefe~red alkyl percarboxylic acid precursors inr~ e sodium 3,5,5-tri-methyl h~noyloxyben7~ne sulfonate (iso-NOBS), sodium non~noylo~yben7.one sulfonate (NOBS), sodium aceto~yben~ snlfon~te (ABS) and pent~cetyl ~1YCQSe.

Amide sub~liluled alkyl pero~cyacid precursors Arnide SU~ ;L~'l~ allkyl peroxyacid precursor compounds are sYi~hle herein, incl~ in~ those of the following general formlll~e R1 C N--R2--C--L R1 N C R2_C L
O or 1 5 wherein Rl is an alkyl group with from 1 to 14 carbon atoms, R2 is an alkylene group co~ n;.~ from 1 to 14 carbon atoms, and R5 is H or an alkyl group cont~inin~ 1 to 10 carbon atoms and L can be essenti~lly any leaving group. Amide s~ll,s~ LeA bleach activator compounds of this type are ~lescribed in EP-A4170386.

W O 97/03157 PCT~US96/11285 Perbenzoic acid precursor Perben_oic acid precursor compounds provide perbenzoic acid on pclLy~olysis. Suitable O-acylated perbenzoic acid precursor compounds incl~lde the s~bsti~lte~ and unsub~ le~l ben_oyl o~yl,c~ e sulfonates, and the benzoylation products of sorbitol, glucose, and all s~cch~rides with benzoylating agents, and those of the i_ide type including N-ben_oyl sUcci~ e~ tetrabenzoyl ethylene ~ niine and the N-benzoyl sul~s~
ureas. Suitable imi~l~7Qle type perbenzoic acid precursors include N-benzoyl imiA~7ole and N-ben_oyl bPn7imi~l~7ole. Other useful N-acyl group-cont~inin~ perbenzoic acid precursors include N-benzoyl pyrroli~lone, dibenzoyl t~llrinP and benzoyl pyroPl~ ..ic acid.

Cationic ~eroxyacid prc~ ors ~'~tioni~ pero~cyacid precursor compounds produce c~tionic pero~yacids on perhydrolysis.

Typically, c~tionic pero~yacid precursors are formed by sllb~ the pero~cyacid part of a suitable peroxyacid precursor co~ ,d with a positively chargcd filnction~l group, such as an ammonium or alkyl onillm group, ~rcrelably an ethyl or methyl ~mmonillm group.
r~tionic pero~yacid ~rec.,.~ors are cypically present in the solid deLel~nt compositionc as a salt with a suitable anion, such as a halide ion.

The pero~yacid ~r~.-lsor compound to be so c~tioni~lly sl~bs~ eA may be a pe~ ~oic acid, or snl~ leA delivalive thereof, plC- ~sor compound as ~esc~ihed hereinbefore. ~ ;vely, the pero~cyacid ~e~ ulsor co~ ~d may be an alkyl percarboxylic acid precursor compound or an amide sllbsti~lte~l alkyl peroxyacid precursor as ~esc-rihe~l herein~er c~tioni~ pero~cyacid precursors are ~lesc-ribed in U.S. ratc~ 4,904,406;
4,751,015; 4,988,451; 4,397,757; 5,269,962; 5,127,852; 5,093,022;

. CA 02226628 l998-0l-l2 W O 97103157 PCT~US96/11285 5,106,528; U.K.1,382,594; EP 475,512, 458,396 and 284,292; and JP 87-318,332.

W O 97/03157 PCTnUS96/11285 ~ Fx~mples of ~refelled c~tionic peroxyacid precursors are described in UK Patent Applic~tion No. 9407944.9 and US Patent Appli~.~tinn Nos.
- 08/298903, 08/298650, 08/298904 and 08/298906.

Suitable c~tionic peroxyacid precursors include any of the ammonium or alkyl ~mmonillm sul~ i~ alkyl or benzoyl oxyben7Pnp~ fQn~tes, N-acylated caprol~ct~m~, and monobenzoyltetraacetyl ~ cose l)e~yl peroxides. Plefelled c~tiQnic peroxyacid precursors of the N-acylated caprol~ct~m class incl~ e the trialkyl ~mmonillm methylene ben_oyl caprol~ct~m.~ and the trialkyl ~mmoninm methylene alkyl caprol~ct~m~.

Benzoxazin or~anic peroxyacid precursors Also suitable are precursor co~pou~ds of the bPn~o~7in-type, as disclosed for e~ample in EP-A-332,294 and EP-A482,807, partic~ rly those having the formlll~

~ 4C - R1 wherein Rl is H, alkyl, alkaryl, aryl, or arylalkyl.
Plero~ ed organic pero~yacid The organic pero~cyacid ble~hin~ ~y~le~ may co~ i.., in ~ tion to, or as an ~l~ern~tive to, an organic peroxyacid bleach ~re~ursor con~ d, a efol~ed organic pero~syacid, typically at a level of from 1% to 15% by weight, more prerciably from 1 % to 10% by weight of the composi~ion CA 02226628 l998-0l-l2 W O 97/03157 PCTrUS96/11285 A plere~led class of organic peroxyacid compounds are the amide substi~lt~l compounds of the following general form~ P:
R~ C N R2 C OOH R1 N C R2 C OOH

G R5 o or R5 O O
wherein Rl is an alkyl, aryl or alkaryl group with from 1 to 14 carbon atoms, R2 is an alkylP~ne, arylene, and alkarylene group co.~ from 1 to 14 carbon atoms, and RS is H or aD al}yl, aryl, or alkaryl group co,~ .nE 1 to 10 carbon atoms. Amide substil~lted organic pero~syacid compounds of this type are described in EP-A-0170386.

Other organic pero~yacids include diacyl and tetraacylpero~cides, especially dipero~y~o~ec~nP~ioc acid, dipero~yl~h~<lec~n~lioc acid and diperoxyh~s~rlec~nP~lioc acid. Mono- and diper~el~ic acid, rnon~ and diperbrassylic acid and N-~hth~loyl~minoperoxicaproic acid are also suitable herein.
Bleach catalyst The compositions opti~n~lly cont~in a transition metal co.~ ..in~ bleach catalyst. One suitable type of bleach catalyst is a catalyst ~y~lem co~ising a heavy metal cation of tlefin~d bleach catalytic activity, such as copper, iron or m~nf~nese cations, an ~n~ y metal catio~ having little or no bleach cataLlytic activity, such as zinc or ~l~..n;.)...~ c~tir)n~ and a seq~e~ having ~lefino~ stability c~n~t~nts for the catalytic and ~n~ ry metal c~tinn~ partic~ rly ethylen~li~minP-tetr~cetic acid, ethylçnP~i~minetp~tra(met~yl~pnp~l~hosphonic acid) and water-soluble salts thereof. Such catalysts are disclosed in U.S. Pat. 4,430,243.

Other ~pes of bleach catalysts in~ e the m~n~nP-se-based comple~ces Close~ in U.S. Pat. 5,246,621 and U.S. Pat. 5,244,594. r~c~
examples of these catalysts incl~ e Mnl[V2(u-o)3(l~4~7-trimptlly~ 4~7 fri~7~CYclonon~np)2-(l?F6)2~ Mnm2(u-o)l(u-oAc)2(l~4~7-trim~thyl-W O 97/03157 PCTrUS96/11285 1~4~7-tri~7~cyclonon~ne)2-(clo4)2~ MnIV4(u-0)6(1,4,7-~ cyclononane)4-(C104)2, Mn~MnIV4(u-O)l(u-OAc)2 (1,4,7-trimethyl-l~4~7-triazacyclonon~ne)2-(clo4)3~ and ~ res thereof.
Others are ~esc-ribe~l in European patent applic~tion publir~tion no.
549,272. Other lig~nAs suitable for use herein inclllAe 1,5,9-trimethyl-l,5,9-t~i~7~cyc10~l0Aec~ne, 2-methyl-1,4,7-tri~7~cyclonon~ne, 2-methyl-1 ,4,7-tri~7~cyclonQn~ne, 1 ,2,4,7-tetramethyl-1 ,4~7-tri~r~ycl~non~n~
and mixblres thereof.

For examples of suitable bleach catalysts see U.S. Pat. 4,246,612 and U.S. Pat. 5,227,084. See also U.S. Pat. 5,194,416 which te~rh~s mononuclear m~n~nese (IV) complexes such as Mn(1,4,7-trim~thyl-1 ,4,7-tri~7~cyclonon~ne)(OCH3)3 (PF6). Still ano~her type of bleach catalyst, as disclosed in U.S. Pat. 5,114,606, is a water-soluble comple~
of m~n~nese (III), and/or (IV) with a ligand which is a non-carbo~cylate polyLydro~y co.~-~u.llld having at least three con~ec~tive C-OH xrou~s.
Other e~camples inclnAe bimlc-le~ Mn complexed with tetra-N~nt~te and bi_N~l~nt~te li~nAs, inrl~ldinE N4Mnm(u-0)2MnIVN4)+and [Bipy2Mnm(u-0)2MnIVbipy2]-(Cl04)3 .

Further suitable bleach catalysts are described, for e~ample, in European patent appli~tion No. 408,131 (cobalt comple~c catalysts), European patent applic~tion~, public~tion nos. 384,503, and 306,089 (m~t~
porphyrin catalysts), U.S. 4,728,455 (m~ng~nese/mlllti~lent~te ligand catalyst), U.S. 4,711,748 and European patent applic~tion, publit~.~tion no. 224,952, (absorbed m~n~nese on ~lnminosilic~te catalyst), U.S.
4,601,845 (~lnminosiliG~te support with m~n~n~se and zinc or m~n~inm salt), U.S. 4,626,373 (m~n~neselligand catalyst), U.S.
4,119,557 (ferric comple~c catalyst), C:el~an Pat. specific~tion 2,054,019 (cobalt rh~l~nt catalyst) ~n~ n 866,191 (tr~n~ition metal-co.~ P
salts), U.S. 4,430,243 (c-h~ nts with m~n~n~se c~tion~ and non-catalytic metal c~tion~)~ and U.S. 4,728,455 (m~n~nPse ~lllcon~e catalysts).

WO 97/03157 PCT~US96/11285 Heavy metal ion se~estrant The deLe~gent compositions of the invention ~rer~ldbly cont~in as an optional component a heavy metal ion sequestrant. By heavy metal ion sequestrant it is meant herein components which act to sequester (chçl~te) heavy metal ions. These components may also have calcium and m~n~sinm ch~l~tion c~r~city~ but preferentially they show selectivity to binding heavy metal ions such as iron, m~n~n~se and copper.

Heavy metal ion sequestrants are generally present at a level of from 0.005% to 20%, ~lereldbly from 0.1% to 10%, more lJfeferably from 0.25% to 7.5% and most ~lereidbly from 0.5~i to 5% by weight of the compositionc.

Suitable heavy metal ion sequestrants for use herein inc]~lde organic phosph~n~tes, such as the amino alkylene poly (alkylene phoSph~n?tes)~
alkali metal et_ane l-hydro~cy disphosphonates and nitrilo trimothylene phosphon~tes.

rr~r~ m~ n~ the above species are diethylene tri~mine penta (methylene ph~sphon~te)~ ethylene rli~mine tri (methylene ph~phQnate) h~ m~thylene f~i~minF~ tetra (methylene phosphon~te) and hydro~y-ethylene 1,1 ~1iphQsph~n~te Other s~it~le heavy metal ion seql~estr~nt for use herein in~hlde nitrilotri~cetic acid and poly~ oc~rboxylic acids such as ethyl~-n~i~minntet~ce~ic acid, ethylçn~,tri~mine pçnt~cetiC acid, ethylen~i~mine ~ cciniG acid, ethyl~-ne~ rnine ~ lt~riG acid, 2-hy~l~oAy~ro~ylen~Ai~m~ cçinic acid or any salts thereof. R~per~ y ~fefer~ed is ethylenpA~ l;lle-N~N~ llcçinic acid (EDDS) or the alkali metal, ~lk~lin-o earth metal, ~mmonillm, or sul)sl;~ mmoninm salts thereof, or .~ ...e3 ~hereof.

W O 97/03157 PCT~US96/11285 Other suitable heavy metal ion seque~hall~ for use herei~ are imin~ ce~ic acid derivatives such as 2-hydro~y~yl ~i~cetic acid or glycelyl imino ~i~cetiC acid, ~escribed in EP-A-317,542 and EP-A-399,133. The iminQ~ cetic acid-N-2-hydro~y~yl snlf~ nic acid and aspartic acid N-carboxymethyl N-2-hydro~y~r~yl-3-snlfonic acid seque~h~ts described in EP-A-516,102 are also suitable herein. The ~-~1~ninP-N,N'~ cetic acid, aspartic acid-N~N~ cetic acid, aspartic acid-N-mono~cetic acid and iinol1is~lccinic acid seques~ esc-rihed in EP-A-509,382 are also suitable.

EP-A 476,257 ~escrihes suitable amino based sequesh~ts. EP-A-510,331 ~escribes suitable sequestrants derived from coll~P-n, ~e~alin or c~-~çin- EP-A-528,859 ~1escribes a suitable alkyl imino~ cetic acid seqlles~nt. Dipicolinic acid and 2-phosphQnobutane-1,2,~tricarboxylic acid are alos suitable. Glyc~ le-N,N'~i~llccinic acid (GADS), ethy1~pnp~ minp-N-Nl~~ lt~ric acid (EDDG) and 2-hydroAy~ro~yl~PnP~ p~-N-N~ llccinic acid (HPDDS) are also suitable.
Enzyme ,~nothP~r ~,lefe~led ingredient useful in the delelgent compositions is one or more ~ tion~l e~yllles.

Pr~r~lf~ 1iti~?n~1 ~ylllatic m~teri~lC include the commercially available lip~es, cutin~es~ amylases, neutral and ~lk~line proteases, e~el~es, ~ec~ es~ 1~ct~es and perosi~es collve~-~ion~lly incorporated into delergelll compo~itions. Suitable e~y es are Aiscll~sed in US Pal~ls 3,519,570 and 3,533,139.

Prefelled commercially available protease enzymes incl~lde those sold under the tr~ n~mes ~1C~ e~ Savinase, Prim~e, Dl~lc~y ~ and Esperase by Novo ~n~1~lstries A/S (De~ ), those sold under the tr~len~m~ S~t~e, ~c~1 and ~S~rem by Gist-Broc-~les, those sold by GenPncor T.~le.. ~tion~l, and those sold under the tr~den~me W O 97/031S7 PCT~US96/11285 Opticlean and Optimase by Solvay Enzymes. Protease enzyme may be incorporated into the composition~ in accordance with the invencion at a level of from 0.0001% to 4% active enzyme by weight of ~he composition Prefelred amylases inrlu~l~, for example, a-amylases obtained from a special strain of B lirhP--iro~ , described in more detail in GB-1,269,839 (Novo). r~ere,red commercially av~ ble amylases in for e~ample, those sold under the tr~-le.n~mP. Rapidase by Gist-Broc~rle and those sold under t~e tr~f~çn~me Term~myl and BAN by Novo ~nrlll~tries A/S. Amylase enzyme may be incorporated into the composition in accordance with the invention at a level of from 0.0001%
to 2% active enzyme by weight of the composition.
Lipolytic enzyme may be pres~t at levels of active lipolytic enzyme of from 0.0001% to 2% by weight, ylefe~ably 0.001% to 1% by weight, most ~lefelably from 0.001% to 0.5% by weight of the cO~ ,O~;~;on.~.
The lipase may be fungal or b~cteri~l in origin being obt~in~ for e~mrle, from a lipase~ prodllrin~ strain of Humicola sp., Thermolllyces sp. or Pseudomonas sp. inrhl~inp Pseudomonas ~seudoalcalipenes or Pseudomas fluo~esce.ls. ~ ir~e from che~nic~lly or ~enetic~lly mo~ifi~
of ~hese s~ains are also useful herein. A ~r~ fefr~l lipase is derived from Pseudomonas pseudoalc~ enes, which is ~lesc-ribed in Gr~ted European Patent, EP-B~218272.
~no~h~o~r ~ elr~d lipase herein is obtained by cloning tlle gene from Hulllicola lanu~inosa a~d eA~ess~g the gene in As~er~illus orvza, as host, as ~lesc-ribe~l in L~r~e~ Patent Appli~ ~tion, EP-A~258 068, which is co.. ~F-rcially av~ b1p from Novo l~nrl~lstri A/S, Bagsvaerd, D~,.. ~.l~, under ~hè trade name Lipolase. This lipase is also described in U.S.
Patent 4,810,414, Huge-Jensen et al, issued March 7, 1989.
Or~nic polymeric compound CA 02226628 l998-0l-l2 W O 97/03157 PCT~US96/11285 Organic polymeric compounds are prefe~red ~ itional components of the detergent composition~ in accord with the invention, and are ~rere~dbly present as components of any partic~ te components where they may act ~ - such as to bind the partic~ te component together. By organic polymeric compound it is meant herein essenti~lly any polymeric organic c~ c,~d commonly used as dispefsa~ts, and anti-redeposition and soil suspPn.~ion agents irl detergent composi~inn~ including any of the high molecnl~r weight organic polymeric compounds described as clay flocc~ ti~
agents herein.

Organic polymeric compound is typically incorporated in the delelv.~t compositions of the invention at a level of from 0.1 % to 30%, ~rer~l~bly from 0.5 % to 15%, most ~refelably from 1 % to 10% by weight of the compositit~n~.
F~r~mples of organic polymeAc compounds include the water soluble organic homo- or co-polymeric polycarboxylic acids or their salts in which the polycarboxylic acid co~ ises at least two carbo~yl r~liç~
se~a.ated from each other by not more than t~,vo CZ;~ tQmC. Polymers of the latter type are disclosed in GB-A-l ,596,756. ~ mrles of such salts are polyacrylates of MWt 2000-5000 and their copolymers with m~leic anhydride, such copolymers having a molecvl~r weight of from 20,000 to 100,000, espec~ ly 40,000 to 80,000.
The poly~no compounds are usefill herein including those derived from aspartic acid such ~ those ~ closed in EP-A-305282, EP-A-305283 and EP-A-351629.

Terpolyll.e~ co~ monomfer units selected from m~leic acid, acrylic acid, poly~partic acid and vinyl alcohol, partiC~ rly those having an average molec~ r weight of from 5,000 to 10,000, are also suitable herein.

Other organic polymeric compounds suitable for incol~olatio~ in the de~er~ t co l~os;~;onc herein include celllllose deliv~lives such as CA 02226628 l998-0l-l2 W O 97/031S7 PCT~US96/1128S

methylce~ ose, carboxymethylcellulose, hydro~y~io~ylmethylcelllllose and hydro~yelhylcçlllllose.
Further usefill org~c polymeric compou~ds are the poly~ ylene glycols, particularly those of molec~ r weight 1000~ 00, more par~ic~ rly 2000 to 8000 and most prefe~ably about 4000.

Suds ~u~pressing ~y~

The delergellt compositions of the invention, when formnl~te~l for use in m~hine washing compositions, ~refel~bly comprise a suds ~u~ressing ~y~lelll present at a level of from 0.01 5~o to 15 %, plererably from 0.0~ %
to 10%, mostpre~er~blyfromO.1% toS% byweightofthecolu~os;l;on Sllit~ble suds ~u~ ess~g Sy~ S for use herein may co...~ e essP.nti~11y any known ~ ;rO~... compound, incl~l~lin~, for e~ample ~ilicon~ ;fo~
compou~ds and 2~ c~nol ~ ~;rO~ compounds.
By ~ ..1; rO~ compoundl it is meant herein any compound or ...; ~ . es of compounds which act such as to depress the ~o~ or sll~lsin~ produced by a solution of a del~f~e~t co~osilion, particularly in the ~rese-~r,e of ~git~tion of that solution.
Part~ r1y ~,~er~ ; rO~ l . . compounds for use herein are ~ con~
alllifoa~ compounds ~efineA herein as any ~ ;rO~ compound incl~ inp a silicone compQnent. Such silicone ~ntifo~m compounds also t~pically CQ~ a silica component. The term ''~ cQn~n as used herein, aIld in general throughout the inr1~1stry, encomp~sses a variety of relatively high molec~ r weight poly~e.~ co.~l~;ni~g siloxane ~ts and hydrocarbyl group of various types. P1ere l~d silicone ~.~I;rO~ comrounds are the ~ilo~nes, partiGlll~rly ~he poly~limethylsilo~anes having trimethylsilyl end bloclrin~ units.
Other sllit~ble anLifo~ compounds inrl~lde the m~noc~bo~ylic fatty acids and soluble salts thereof. These m~teri~ are described iD US
Patent 2,954,347, issued Se~le ~ber 27, 1960 to Wayne St. John. The CA 02226628 l998-0l-l2 W O 97/03157 PCTnUS96/11285 monocarboxylic fatty acids, and salts thereof, for use as suds ~u~pfessor - typically have hydrocarbyl chains of 10 to 24 carbon atoms"L,lefelably 12 to 18 carbon atoms. Suitable salts incl~ e the alkali metal salts such as so~inm~ pot~csillm, and l;~l.i-..~ salts, and ~mmonillm and k~nol~mmnnillm salts.

CA 02226628 l998-0l-l2 W O 97/03157 PCT~US96/11285 Other suitable al liroam compounds include, for example, high molec~ r weight fatty esters (e.g. fatty acid triglycerides), fatty acid esters of monovalent alcohols, ~liph~tir Clg-C40 ketones (e.g. ~Learolle) N-alkylated amino tri~in~s such as tri- to hexa-alkylmel~min~c or di- to tetra alkyl~ mine chlortri~7in~s formed as products of Cy~uliC chloride with two or three moles of a primary or secondary amine cont~inin~ 1 to 24 carbon atoms, propylene oxide, bis stearic acid amide and monostearyl di-alkali metal (e.g. so~ m, pot~Ccillm, lithillm) phosphates and phosphate esters.

A ~lererled suds ~uy~ressing ~y~lem comprises (a) ~ntiro~ compound, p~efe~ably silicone ~ irO~ ... compound, most ~rerelably a silicone antifoam compound comrr combination (i) poly~limtot~yl siloxane, at a level of from 50% to 99%, p-er~;rably 75 % to 95 % by weight of the silicone anlirvam compound; and (ii) silica, at a level of from 1% to 50%, preferably 5% to 25%
by weight of the silicone/silica antifoam compound;

wherein said silica/silicone anLiÇoam compound is incorporated at a level of from 5% to 50%, ~lefelably 10% to 40% by weight;

(b) a dispers~nt compound, most preferably comrricin~ a .~iliconP
glycol rake copolymer with a polyoxyalkylene contpnt of 72-78 %
and an ethylene oxide to propylene o~cide ratio of from 1:0.9 to 1:1.1, at a level of from 0.5% to 10%, prerelably 1% to 10% by weight; a particularly preferred silicone glycol rake copolymer of this type is DCO544, commercially av~ hle from DOW Corning under the tr~-len~me DCO544;

W O 97/03157 PCT~US96111285 (c) an inert carrier fluid compound, most plefe.ably comprising a C16-- Clg ethoxylated alcohol with a degree of ethoxylation of from 5 to 50, prefel~bly 8 to lS, at a level of from 5% to 80%, ~lcrel~bly 10% to 70%, by weight;

A highly ~rere,~ed partic~ te suds suppressing ~y~le~ is described in EP-A-0210731 and comprises a silicone antifoam compound and an organic carrier m~tPri~l having a mPltin~ point in the range 50~C to 85~C, wherein the organic carrier m~teri~l comprises a monoester of glycerol and a fatty acid having a carbon chain cont~ining from 12 to 20 carbo~
atoms. EP-A~210721 discloses other preferred particulate suds supplessing ~y~Le~s wherein the organic carrier m~teri~l is a fatty acid or alcohol having a carbon chain cont~ining from 12 to 20 carbon atoms, or a mixtll-e thereof, with a melting point of from 45~C to 80~C.

Clay softenin~ ~y~le The deter~ nt compositione may cont~in a clay soÇl~~ y~
compriein~ a clay mineral compound and optionally a clay ~occ~ tinp agent.
The clay mineral compound is ~rereldbly a sm~ctite clay compound.
Smoctite clays are llieclose~l in the US Patents No.s 3,862,058, 3,948,790, 3,954,632 and 4,062,647. European Patents No.s EP-A-299,575 and EP-A-313,146 in the name of the Procter and Gamble Com~a ly ~lescribe s~lit~hle organic polymeric clay flocc~ tin~ agents.

Polymeric dye transfer inhibitin~ a~ents The deterxellt comFositione herein may also co ~iise from 0.01 % to 10 %, ~rert~ably from O.OS % to O.S % by weight of polymeric dye t~ansfer inhibiting agents.
The polymeric dye transfer inhibiting agents are ~lefeldbly selecte~1 from polyamine N-o~cide polymers, copolymers of N-vinylpylrolidone and N-vinylimi~l~7ole, polyv~yl~ylrolidonepolymers or comhin~tions thereof.

CA 02226628 l998-0l-l2 W O 97/03157 PCT~US96/11285 a) Polyamine N-oxide polymers Polyamine N-o~ide polymers suitable for use herein cont~in units having the following structure formula:
p I

(I) Ax R

wherein P is a polymf~ri.~ble unit, and A is NC, CO, C, -O-, -S-, -N-; x is O or 1;

R are aliphatic, etho~cylated aliphatics, aromatic, heterocyclic or alicyclic groups or any combination thereof w~ereto the nitrogen of the N-O group can be ~tt~hP~l or wherein the nitrogen of the N-O group is part of these U~S.

The N-O group can be represente~ by the following general structures:
o t o (R1 ) X - I -(R2)Y
(R3)z or N-(R1 )x wherein Rl, R2, and R3 are ~liph~tir groups, aromatic, heterocyclic or alicyclic groups or combin~tion~ thereof, ~ or/and y or/and z is O or 1 and wherein the nitrogen of the N-O group can be ~thC-hç~l or wherein the nitrogen of the N-O group forms part of these groups. The N-O group can _ CA 02226628 l998-0l-l2 W O 97/03157 PCT~US96/11285 be part of the polymerisable unit (P) or can be ~che~ to the polymeric backbone or a combination of both.
Suitable polyaine N-oxides wherein the N-O group form~ part of the polymori~ble unit co~L"ise polyamine ~-oxides wherein R is selecte~
from aliphatic, aromatic, alicyclic or heterocyclic groups. One class of said polyamine N-oxides comprises the group of polyamine N-o~cides wherein the nitrogen of the N-O group forms part of the R-group.
Preferred polyamine N-oxides are those wherein R is a heterocyclic group such as pyrri~lin.o., pyrrole, imit1~7ole, pyrrolidine, pipericlinP, quinoline, acridine and derivatives thereof.

Other suitable poly~ine N-oxides are the polyamine oxides whereto the N-O group is ~tt~ch~l to the polymtoris~ble unit. A prefelr~ class of these polyamine N-oxides comprises the polyamine N-oxides having the general formula (I) wherein R is an aromatic,heterocyclic or alicyclic groups wherein the nitrogen of the N-O filnctional group is part of said R
group. F.x~mples of these classes are polyamine oxides wherein R is a heterocyclic compound such as pyrricline, pyrrole, imi~ ole and derivatives thereof.
The polya~e N-oxides can be obt~in~l in ~lmost any degree of polymeris~tisn The degree of polymPri~tion is ~ot cri~ l provided the m~teri~l has the desired water-solubility and dye-suspenf1in~E~ power.
Typically, the average molecular weight is within the range of 500 to 1000,000.
b) Co~olymers of N-vhlyl~yllolidone and N-vinylimid~zole Suitable herein are coploymers of N-vinylimi~ ole and N-vi~yl~ylr~ Qne having an average molecular weight range of from 5,000 to 50,000. The prererr~l copolymers have a molar ratio of N-vinylimi~ole to N-vi~yl~yirolidone from 1 to 0.2.

c) Polyvinyl~yr~olidone W O97/03157 PCTrUS96/11285 The de~erge~ compositions herein may also utilize polyvinylpyrrolidone ("PVP") having an average mol~c~ r weight of from 2,500 to 400,000.
Suitable polyvi-lyl~ylloliAon~s are commercially vailable from ISP
Corporation, New York, NY and Montreal, ~ n~ under the product names PVP K-15 (viscosity molecular weight of 10,000), PVP K-30 (average molec -l~r weight of 40,000), PVP K-60 (average mLolec~
weight of 160,000), and PVP K-90 (average molecular weight of 360,000). PVP K-15 is also available from ISP Corporation. Other suitable polyvi~y~ylrolidones which are commercially available from BASF Cooperation include Sokalan HP 165 and Sokalan HP 12.
d) Polyvinylo~azolidone The de~er~e.lt compositions ~erein may also utilize polyvinylo~cazoli~lon~e as polymeric dye transfer inhibiting agents. Said polyvmylo~azoli~1Onçe have an average molec~ r weight of from 2,500 to 400,000.
e) Poly~inylilllidazole The delel~en~ compositione herein may also utilize polyvinylimi~ ole as polymeric dye transfer inhibiting agent. Said polyvinylimi~ oles prererably have aII average moleclll~r weight of from 2,500 to 400,000.
Qptical bri~htener The delergellt compos;tion~ herein also optionally cont~in from about 0.005% to 5% by weight of certain t~pes of hydrophilic optical bri~.htç~ s.

Hydrophilic optical bripht~onçrs usefill herein in~ fiç those having the structural ft rmll1~

CA 02226628 l998-0l-l2 W O 97/03157 PCT~US96/11285 Rl R2 N~ ~HI Hl ~ I ~NNO~N

R2 SO3M SO3M Rl wherein Rl is selecte~ from ~nilino, N-2-bis-hydro~y~yl and NH-2-hydroxyethyl; R2 is sel~cteA from N-2-bis-hydroxyethyl, N-2-hydro~yel~yl-N-methyl~mino, morphilino, chloro and amino; and M is a salt-fo~ g cation such as sodium or potassium.

When in the above formula, Rl is ~nilino, R2 is N-2-bis-hydro~yt;lllyl and M is a cation such as sodium, the brightener is 4,4',-bis[(4-~nilino-~(N-2-bis-hydro~yethyl)-s-tri~7in~-2-yl)amino]-2,2'-stilben~li~ulfonic acid and dico~ m salt. This particular brightener species is cornmercially m~rkete l under the tr~dçn~mo Tinopal-UNPA-GX by Ciba-Geigy Corporation. Tinopal-UNPA-GX is the preferred l~ydrophilic optical bri~htener useful in the delelgent compositions herein.
When in the above formula, Rl is ~nilino, R2 is N-2-hydro~ye~yl-N-2-methyl~mino and M is a cation such as sodium, the bri~htençr is 4,4'-bis[(4-slnilin~6-(N-2-hydro~y~ yl-N-methyls3min~:?)-s-tri~7in~-2-yl)~min~]2,2'-stilben~i~ll1fonic acid disodium salt. This particular bri~htener species is commercially marketed under the tr~ien~me Tinopal SBM-GX by Ciba-Geigy Corporation.

When in the above form~ , Rl is ~nilino, R2 is morphilino and M is a cation such as so~ m, the bri~htener is 4,4'-bis[(4-~nilino-~morphilino-s-tri~7in~-2-yl)~mino]2,2'-stilben~Aielllfonic acid, sodium salt. This particular bri~htPner species is commercially m~rlrPte~l under the tr~-lPn~me Tinopal AMS-GX by Ciba Geigy Corporation.
Cationic fabric sorl~ning agents r~tionic fabric s~rLt~ agents can also be incorporated into composition~ in accordance with t~e present invention. Suitable c~tiQnic CA 02226628 l998-0l-l2 WO 97/03157 PCT~US96/11285 fabric so1~:çnin~ agents include the water insoluble tertiary ~min~.~ or dilong chain amide materials as disclosed in GB-A-l 514 276 and EP-B~
011 340.

Cationic fabric softeninE age~ts are typically incorporated at total levels of from 0.5 % to 15 % by weight, normally from 1 % to 5 % by weight.

Other optional in~redients Other optional ingre~liçnt~ suitable for inclusion in the compo~itione of the invention include perfumes, colours and filler salts, with so~ m s~llf~te being a prefelled filler salt.
pH of the compositions The present compositions ~efefably have a pH me~llred as a 1%
solution in ~iistill~ water of at least 8.5.0, ~refeidbly from 9.0 to 12.5, most ~referably from 9.5 to 11Ø

Form of the compositions The composition~ in accordance with the invention can take a variety of physical forms inc~ ing granular, tablet, bar and liquid forms. The composition~ are particularly the so-called concçntrated granular de~er ellt compositions adapted to be added to a washing m~hin~ by means of a dispensin~ device placed in the m~hine drum with the soiled fabAc load.

In general, granular dete~g~t compositions in accordance with the present invention can be made via a variety of methods inclll-ling dry mi~ing, spray drying, agglomeration and gr~mll~tion.

The mean particle size of the components of granular composition~
accordance with the invention should ~rerel~bly be such that no more that 5 % of particles are greater than 1 .7mm in ~ mçtçr and not more than 5 %
of particles are less than 0.15mm in diameter.
-CA 02226628 l998-0l-l2 W O 97/03157 PCTrUS96/11285 The term mean particle size as defined herein is c~lcul~te~l by sieving a sample of the compo~ition into a number of fr~ctinn~ (typically 5 - fractions) on a series of Tyler sieves. The weight fr~ction~ thereby obtained are plotted ~g~in~t the aperture size of the sieves. The mean particle size is taken to be the aperture size through which 50% by weight of the sample would pass.

The bulk density of granular deter~;ent compositions in accordance with the present invention typically have a bulk density of at least 600 g/litre, more pref~ldbly from 650 g/litre to 1200 g/litre. Bulk density is m~ red by means of a simple funnel and cup device co~ci~tin~ of a conic~l funnel moulded rigidly on a base and provided with a flap valve at its lower e~lie~y to allow the contents of the funnel to be emptied into an a~cially ~lignP~ cy1inrlric~l cup disposed below the funnel. The funnel is 130 mm high and has intern~ meters of 130 ~ and 40 mm at its respective upper and lower e~tremi~ies. It is mounted so that the lower e~e~ily is 140 mm above tlle upper surface of the base. The cup has an overall height of 90 mm, an ;.~t~ height of 87 _m and an intk~ meter of 84 mm. Its nominal volume is 500 ml.
To carry out a mP~ rem~nt~ the funnel is filled with powder by hand pouring, the flap valve is opened and powder allowed to overfill the cup.
The filled cup is removed from the frame and excess powder removed from the cup by p~sin~ a straight edged implem~nt eg; a knife, across its upper edge. The filled cup is then weighed and the value ob~in~ for the weight of powder doubled to provide a bulk density in g/litre. Replicate m~nrem,nt~ are made as required.

Surf~ct~nt a~lomerate particles The c~tioni~ ester surf~ct~nt herein, ~rere~dbly with ~ jtion~l surf~ct~nts, is p~e~l~bly present in granular composition~ in the form of surf~ct~nt agglomerate particles, which may take the form of flakes, prills, marumes, noodles, ribbons, but preferably take the form of granules. The most preferred way to process the particles is by CA 02226628 l998-0l-l2 W O 97/03157 PCTrUS96/11285 agglomerating powders (e.g. ~hlminosilic~te~ carbonate) with high active surf~ct~nt pastes and to control the particle size of the reslllt~n~ - ~
agglomerates within specified limits. Such a process i~volves mixint~ an effective amount of powder with a high active surf~ct~nt paste in one or more agglomerators such as a pan agglomerator, a Z-blade mi~er or more ~refelably an in-li~e mixer such as ~chose m~nnf~ctllred by .~çhll i (Holland) BV, 29 Chroomstraat 8211 AS, Lelystad, Neth~rl~n~ls~ and Gebruder Lodige Maschin~nh~ll GmbH, D4790 Paderbom 1, F.l~enPrstrasse 7-9, Postfach 2050, Germany. Most ~rc;fe~ably a high shear mixer is used, such as a Lodige CB (Trade Name).

A high active surf~ct~nt paste colu~rising from 50% by weight to 95% by weight, pfef~lably 70% by weight to 85% by weight of surf~ct~nt is typically used. The paste may be pumped into the agglomerator at a tempelalule high enough to m~int~in a pnmp~le viscosity, but low enough to avoid degr~ tion of the anionic surf~ct~nt~ used. An operating temperature of the paste of 50~C to 80~C is typical.

Laundry washin~ method ~ hine laundry methotls herein ~pically co~lise treating soiled laundry with an aqueous wash solution in a washing m~t~hine having dissolved or dispensed therein an effective amount of a m~chinp laundry delergellt composition in accord with the invention- By an effective amount of the dele~gent composition it is meant from 40g to 300g of product dissolved or dispersed in a wash solution of volume from S to 65 litres, as are typical product dosages and wash solution volllm.
commonly employed in convention~l m~Chin~ laundry methods.

In a plefeLred use aspect a dispen~inP device is employed in the washing method. The dispen~in~ device is charged with the delerge~t product, and is used to introduce the product directly into the drum of the washing m~c.hine before ~che comm~ncempn~ of the wash cycle. Its volume capacity should be such as to be able to contain s~lmcient detergent product as would normally be used in the washing method.

W O 97/03157 PCTnUS96/11285 Once the washing m~chinP, has been loaded with laundry the dispP-neinP
device cont~inin~ the detergellt product is placed inside the drum. At the commPncement of the wash cycle of the washing machine water is introduced into the drum and the drum periodically rotates. The tlesi~n of the dispensing device should be such that it permits cont~inmP-nt of the dry detergent product but then allows release of this product ~ll)rin~ the wash cycle in response to its ~it~tion as the drum rotates and also as a result of its contact with the wash water.

To allow for release of the detergent product ~ rinp ~he wash the device may possess a number of openings through which the product may pass.
,Altern~tively, the device may be made of a material which is permeable to liquid but impermeable to the solid product, w_ich will allow release of dissolved product. Preferably, the detelgent product will be rapidly rele~ee~ at the start of the wash cycle thereby providing tr~neiPnt loc~lieecl high concentrations of product in the drum of the washing m~chinP, at this stage of the wash cycle.

r~erelled dispensing devices are reusable and are ~leei~nP,~l in such a way that co..l~inP,r integrity is m~int~ine~l in both the dry state and ~ rinp the wash cycle. Especially yle~red dispçneinP: devices for use with the composition of the invention have been described in the following GB-B-2, 157, 717, GB-B-2, 157, 718, EP-A~201376, EP-A~288345 and EP-A~288346. An article by J.Bland published in ~r~mlf~ctllring rhPmiet, November 1989, pages 4146 also ~esc-ribes especially ~r~rerred dispeneinP: devices for use with granular laundry products which are of a type commonly know as the Hgr~mllet~e". Another ~re~lled dispeneing device for use with the compositions of this invention is disclosed in PCT
Patent Applis~tion No. WO94/11562.

Especially ~f~ rel~ed diSppneing devices are disclosed in Euro~ean Patent Application Public~tion Nos. 0343069 & 0343070. The latter Applic~tis~n ~iecloses a device colllylising a flexible sheath in the form of a bag ç~rten-ling from a support ring ~lefinin~ an orifice, the orifice being adapted to admit to the bag sllfficie-n~ product for one washing cycle in a WO 97/03157 ~CTn~S96111285 washing process. A portion of the washing mçt~ m flows through t~e orifice into the bag, dissolves the product, and the solution then passes outwardly through the orifice into the washing m~ m The support ring is provided with a m~kin~ arrangemet to prevent egress of wetted, undissolved, product, this arrangement typically comprising radially e~rtçnllin~ walls e~ct~nf1ing from a central boss in a spoked wheel configuration, or a simil~r structure in which the walls have a helical form.
,A1tern~tively, the dispensing device may be a fle~ible cont~iner~ such as a bag or pouch. The bag may be of fibrous construction coated with a water impermP~ble protective material so as to retain the co~ ts, such as is disclosed in European published Patent Application No. 0018678.
~ltern~tively it may be formed of a water-insoluble synthetic polymeAc m~teri~l provided with an edge seal or closure ~lesi~n~cl to l~lu~
aqueous media as ~ close~ in European published Patent Application Nos. 0011500, 0011501, 0011502, and 0011968. A convenient form of water frangible closure co~ ises a water soluble adhesive disposed along and se~lin~ one edge of a pouch formed of a water imperme~ble polymeric film such as polyethylene or polyplo~ylene.
Pack~gin~ f~r the compositions Commercially m~rk~te~ executions of the bleaching compositions can be packaged in any suitable container including those constructed from paper, cardboard, plastic m~teri~ls and any suitable l~min~tes. A
yrefelred p~clr~Pin~ e~ecution is described in Europearl Application No.
94921505.7.

Abbreviations used in E~camples II1 the de~ergellt compo~ition~ the abbreviated component i~lentifi~tion~
have the following m~-~ning.

L~S : Sodium linear C12 alkyl ben7en~ slllfion~te TAS : Sodium tallow alkyl ~ulf~te CA 02226628 l998-0l-l2 W O 97/03157 PCT~US96/11285 C45AS : Sodium C14-C1s linear alkyl s~llf~te CxyEzS : Sodium Clx-C1y br~n~.hetl alkyl sl-lf~te con~en~e-l with z moles of ethylene o~ide C45E7 : A C1~1s predomin~ntly linear ~lima"~ alcohol con~lPn.~e-l with an average of 7 moles of ethylene oxide C25E3 : A C12_1s br~nc~hP~ primary ~lcohol contlPn~e~3 with an average of 3 moles of ethylene o~ide C25E5 : A C12 15 br~n~he~l primary alcohol con~len~e~
with an average of 5 moles of ethylene oxide ClEQ I : RlcoocH2cH2~N+(cH3)3 with R1 = Cll-CEQ II : RlCOOCH2CH2CH2N+(CH3)3 withRl =
Cll-C13 CEQ m RlCOO CH2 CH2 N+(CH3)2 (CH2CH20H) with R1=C11-C13 CEQ IV Rl COOCH2CH2 N+ (cH3cH2)2 (CH3) with Rl =cll-cl3 QAS R2.N+(CH3)2(C2H4OH) with R2 = C12 - C14 Soap .~o~linm linear alkyl carboxylate derived from an 80/20 mi~ e of tallow and coconut oils.
TFAA : C16-C1g alkyl N-methyl f~lnc~mi~e TPKFA : C12-C14 topped whole cut fatty acids STPP : Anhydrous sodium tripolyphosphate Zeolite A : Hydrated Sodium ~lllminosilic~te of formula Nal2(Alt)2Si~2)12. 27H20 having a pi;ma particle size in the range from 0.1 to 10 micrometers NaSKS-6 : Cryst~lline layered silic~te of formula ~ -Na2Si205 Citric acid : Anhydrous citric acid .. Carbon~te : Anhydrous so~ lm carbonate with aparticle size between 20011m and 900~m Bicarbonate : Anhydrous sodium bicarbonate with a particle size distribution between 40011m and 120011m CA 02226628 l998-0l-l2 WO 97/03157 PCTnUS96/11285 Silicate : Amorphous Sodium SiIicate (SiO2:Na20; 2.0 ratio) Sodium sulfate: Anhydrous sodium sulfate Citrate : Tri-sodium citrate dihydrate of activity 86.4%
with a particle size distribution between 42511m and 850 ,um MA/AA : Copolymer of 1:4 maleic/acrylic acid, average molecnl~r weight about 70,000.
CMC : Sodium carboxymethyl celhllose Protease : Proteolytic enzyme of activity 4KNPU/g sold by NOVO Industries A/S under the tr~len~m~
Savinase Alcalase : Proteolytic enzyme of activity 3AU/g sold by NOVO Tnrlustries A/S
Cell~ e : Cellulytic enz~yme of activity 1000 CEW/g sold by NOVO ~nrl~ls~ries A/S under the tr~-len~m~
Carezyme Amylase : Amylolytic enzyme of activity 60KNU/g sold by NOVO Industries A/S under the tr~len~mP
Termamyl 60T
Lipase : Lipolytic enzyme of activity 100kLU/g sold by NOVO ~n~ stries A/S under the tr~tlen~me Lipolase Endolase : Endo~hln~se enzyme of activity 3000 CEVU/g sold by NOVO ~n-lllstries A/S
PB4 : Sodium perborate tetrahydrate of n~)min~l formula NaB02.3H20 H202 PB1 : Anhydrous sodium perborate bleach of nominal formula NaBO2.H2O2 Percarbonate : Sodium Percarbonate of nominal formula 2Na2C03.3H202 NOBS : Nonanoyloxyben7ene sulfonate in the form of the so~ m salt.
TAED : Tetraacetylethylene.li~mint~.

CA 02226628 l998-0l-l2 W O 97/03157 PCT~US96/11285 DTPMP : Diethylene tri~mine penta (methylene phosphonate), marketed by Monsanto under the Trade name Dequest 2060 Photoactivated: Sulfonated Zinc Phthlocyanine encaps~ te~3 in bleach dextrin soluble polymer Bright.o.ner 1 : Disodium 4,4'-bis(2-sulphostyryl)biphenyl Bri~htener 2 : Disodium 4,4'-bis(~nilino-~morpholino-1.3.5-triazin-2-yl)amino) stilbene-2:2'~isulfonate.
HEDP : l,l-hydroxyethane diphosphonic acid PVNO : Polyvinylpyridine N-oxide PVPVI : Copolymer of polyvinylpyrolidone and vinylimi~ ole SRP 1 : Sulfobenzoyl end capped esters with o~yeL}~ylene oxy and terephtaloyl backbone SRP 2 :Diethoxylated poly (1, 2 propylene terepht~l~te) short block polymer Silicone anliroal-l : Poly~limethylsiloxane foam controller with silo~cane-oxyaLkylene copolymer as dispersing agent with a ratio of said foam controller to said dispersing agent of 10:1 to 100:1.

CA 02226628 l998-0l-l2 W O 97/03157 PCTrUS96/11285 In the following Fx~mI~les all levels are quoted as % by weight of the composition:

Example 1 The following laundry d~rg~ compositions A to F were prepared in accord with the inVenti-)n:

A B C D ~ F
LAS 8.0 8.0 8.0 8.0 8.0 8.0 C E Q I - 0.8 4.5 2.0 - 0.7 C E Q II 6.0 0.5 - 0.7 2.0 0.8 Q AS - - 0.8 - - 0.8 Zeolite A 18.1 18.1 18.1 18.1 18.1 18.1 Carbonate 13.0 13.0 13.0 27.0 27.0 27.0 Silic~te 1.4 1.4 1.4 3.0 3.0 3.0 Sodiu m sulf~te 26.1 26.1 26.1 26.1 26.1 26.1 PB4 9.0 9.0 9.0 9.0 9.0 9.0 T~ED 1.5 1.5. 1.5 1.5 1.5 1.5 D ETP M P 0.250.25 0.25 0.25 0.250.25 H E D P 0.3 0.3 0.3 0.3 0.3 0 3 W O 97/03157 PCT~US96/11285 Protease 0.26 0.26 0.26 0.26 0.26 0.26 Amylase 0.1 0.1 0.1 0.1 0.1 0.1 Cellulase 0.3 0.1 0.7 0.5 1.2 1.0 MA/AA 0.3 0.3 0.3 0.3 0.3 0.3 CMC 0.2 0.2 0.2 0.2 0.2 0.2 Photoactivated 15 15 15 15 15 15 bleach (ppm) ppm ppm ppm ppm ppm ppm Bri~ht~n~r 1 0.09 0.09 0.09 0.09 0,09 0 09 Perfume 0.3 0.3 0.3 0.3 0.3 0.3 Silicone anliroa-ll 0.5 0.5 0.5 0.5 0.5 0,5 Misc/miIlors to 100%

Density in g/litre 850 850 850 850 850 850 PCTnUS96/11285 Example 2 The following granular laundry detergent compositio~s G to I of bulk density 750 g/litre were prepared in accord with the iIlven~ion:

G H
LAS 5.25 5.61 4.76 TAS 1.25 1.86 1.57 C45AS - 2.24 3.89 C25AE3S - 0.76 1.18 C45E7 3.25 - 5.0 C25E3 - 5.5 CEQ II 0.8 - 2.8 CEQ m 0.7 2.0 0.5 STPP 19.7 Zeolite A - 19.5 19.5 NaSKS-6/citric acid - 10.6 10.6 (79:21) Carbonate 6.1 21.4 21.4 Bicarbonate - 2.0 2.0 ~Silic~te 6.8 W O 97/03157 PCT~US96/11285 Sodium sulfate 39.8 - 14.3 PB4 5.0 12.7 TAED 0.5 3.1 DETPMP 0.25 0.2 0.2 Protease 0.26 0.85 0.85 T.ip~ee 0.15 0.15 0.15 Cell~ ee 0.7 0.9 1.2 Amylase 0.1 0.1 0.1 MA/AA 0.8 1.6 1.6 CMC 0.2 0.4 0.4 Photoactivated bleach15 ppm27 ppm 27 ppm (ppm) BriP:htto.n~or 1 0.080.19 0.19 Bri~ht~ Fr2 - 0.04 0.04 Perfume 0.3 0.3 0-3 Silicone ~ ;rO~......... o,5 2.4 2.4 Minors/misc to 100%

W O 97/03157 PCTrUS96/11285 Example 3 The following deler~ellt formulations, according to the present invention were prepared, where J is a phosphorus-cont~inin~ d~ter~ent composition, K is a zeolite-cont~inin~ de~lge~t compositio~ and L is a compact delelgel,t composition:

J K L
Blown Powder STPP 24.0 - 24.0 Zeolite A - 24.0 -C45AS 9.0 6.0 13.0 MA/AA 2.0 4.0 2.0 LAS 6.0 8.0 11.0 TAS 2.0 CEQ I - 2.0 CEQ II - - 2.0 CEQ m 2.0 Silicate 7.0 3.0 3.0 C~C 1.0 1.0 0.5 Bri~ht~n~r 2 0.2 0.2 0.2 Soap 1.0 1.0 1.0 DTPMP 0.4 0.4 0.2 Spray On C45E7 2.5 2.5 2.0 C25E3 2.5 . 2.5 2.0 Silicone ~ ;rO~ 0.3 0 3 0 3 Perfilme 0.3 0.3 0.3 Dry additives Carbonate 6.0 13.0 15.0 PB4 18.0 18.0 10.0 PB1 4.0 4.0 0 TAED 3.0 3.0 1.0 Photoactivated bleach 0.02 0.02 0.02 ~'elhl1~.~e 0.8 1.2 0.6 Protease 1.0 1.0 1.0 CA 02226628 l998-0l-l2 W O 97/03157 PCTrUS96/11285 Lipase 0.4 0.4 0.4 Amylase 0.25 0.30 O. lS
Dry mixed so~ lm 3,0 3.0 5 0 slllf~te, R~l~nce (Moisture & 100.0 100.0 100.0 Miscellaneous) Density (~/litre) 630 670 670 ~ .

=
=

W O 97/03157 PCT~US96/11285 Example 4 The following nil bleach-cont~inin~ d~Lergeut form~ ti~n~ of particularuse in the washing of colored clothing, according to the ~rese~t invention were prepared:
M N O
Blown Powder Zeolite A 15.0 15.0 Sodium sulfate 0.0 5.0 LAS 3.0 3.0 CEQ I 0.5 0.5 0.5 CEQ II 1.0 1.5 0.S
C~Q IV 0.5 1.5 2.0 DTPMP 0.4 0.5 CMC 0.4 0.4 MA/AA 4.0 4.0 Agglomerates C45AS - - 11.0 LAS 6.0 5.0 TAS 3.0 2.0 Silicate 4.0 4.0 ZeoliteA 10.0 15.0 13.0 CMC - _ o.5 MA/AA - - 2.0 Carbonate 9.0 7.0 7.0 Spray On P~lrullle 0.3 0.3 0.5 C45E7 4.0 4.0 4.0 C25~3 2.0 2.0 2.0 Dry additives MA/AA - - 3.0 NaSKS-6 - - 12.0 Citrate 10.0 - 8.0 .
Bicall,vl,ate 7.0 3.0 5.0 Carbonate 8.0 5.0 7.0 PVPVI/PVNO 0.5 0.5 0.5 W O 97/03157 PCT~US96/11285 Alcalase 0.5 0.3 0 g . ~ ir~e 0.4 0.4 0.4 Amylase 0.6 0.6 0.6 Cell~ e 0.6 0.9 0.2 Silicone anliÇoam 5.0 5.0 5.0 Dry additives Sodium sulfate 0.0 9.0 0 0 R~l~nce (Moisture and 100.0 100.0 100.0 Miscell~neous) Density (g/litre) 700 700 700 WO 97/03157 PCT~US96/11285 Example 5 The following d~erg~t form~ tions, according to t~le present inventio~
were prepared:
P Q R S
LAS 20.0 14.0 24.0 22.0 QAS 0.7 1.0 - 0.7 TFAA - 1.0 C25E5/C45E7 - 2.0 - 0.5 C45E3S - 2.5 CEQ m 0.7 - 3.5 1.5 CEQ IV 1.5 2.4 - 1.5 STPP 30.0 18.0 30.0 22.0 Silicate 9.0 5.0 10.0 8.0 Carbonate 13.0 7.5 - 5.0 Bicarbonate - 7.5 DTPMP 0.7 1.0 SRP 1 0.3 0.2 - 0.1 MA/AA 2.0 1.5 2.0 1.0 CMC 0.8 0.4 0.4 0.2 Protease 0.8 1.0 0.5 0.5 Amylase 0.8 0.4 - 0.25 T ip~ce 0.2 0.1 0.2 0.1 Celh71~e 0.15 0.1 0.2 0.1 Photoactivated70ppm 45ppm - 10ppm bleach (ppm) Bri~htener 1 0.2 0.2 0.08 0.2 PB 1 6.0 2.0 NOBS 2.0 1.0 R~l~nGe 100 100 100 100 (Moisture and cell~neQus) W O 97/031~7 PCT~US96/11285 E~ample 6 J
The following delelgent form~ tionc, according to the present invention - were~r~
T U V

Blown Powder Zeolite A 30.0 22.0 6.0 Sodium snlf~te 19.0 5.0 7.0 MA/AA 3.0 3.0 6.0 LAS 14.0 12.0 22.0 C45AS 8.0 7.0 7.0 CEQ II - 0.4 2.5 CEQ IV 1.5 1.5 0.5 Silicate - 1.0 5.0 Soap - - 2.0 Bri~htrner 1 0.2 0.2 0.2 Carbonate 8.0 16.0 20.0 DTPMP - 0.4 ' 0.4 Spray On C45E7 1.0 1.0 1.0 Dry additives PVPVI/PVNO 0.5 0.5 0.5 Protease 1.0 1.0 1.0 ~.ip~se 0.4 0.4 0.4 Amylase 0.1 0.1 0.1 Cellulase 0.1 0.2 0.4 NOBS - 6.1 4.5 PBl 1.0 5.0 6.0 .~o~ m slllf~te - 6.0 R~l~nre (Moisture 100 100 100 and ~i~ce~ neous) i, CA 02226628 l998-0l-l2 W O 97/03157 ~ '11285 Example 7 The following high density and bleach-cont~inin~ dele~gellt form~ ti~-nc, according to the present invention were prepared: ~

W X Y
Blown Powder ZeoliteA 15.0 15.0 15.0 Sodi~m sulfate 0.0 5.0 0,0 LAS 3.0 3.0 3.0 CEQ II 0.9 0.5 CEQ III 0.9 1.2 2.5 QAS - 1.5 1.5 DTPMP 0.4 0.4 0.4 CMC 0.4 0.4 0.4 MA/AA 4.0 2.0 2.0 Agglomerates LAS 5.0 5.0 5.0 TAS 2.0 2.0 1.0 Silicate 3.0 3.0 4.0 Zeolite A 8.0 8.0 8.0 Carbonate 8.0 8.0 4.0 Spray On Perfilme 0.3 0.3 0.3 C45E7 2.0 2.0 2.0 C25E3 2.0 - -Dry additives Citrate 5.0 - 2.0 Bicall~onate - 3.0 Carbonate 8.0 15.0 10.0 TAED 6.0 2.0 5.0 - r PBl 14.0 7.0 10.0 Polyelllylene o~ide of MW - - 0.2 5,000,000 Be.. -ol-;Le clay - - 10.0 Protease 1.0 1.0 1.0 W O 97/03157 PCT~US96/1128S

Lipase 0.4 0.4 0.4 Amylase 0.6 0.6 0.6 Cellulase 0.6 0.4 1.0 r Silicone antifoam 5.0 5.0 5.0 Dry additives Sodium s~llf~te 0.0 3.0 0.0 R~l~n~e (Moisture and 100.0 100.0 100.0 cell~neous) Density (~/litre) 850 850 850 .~ .

W O 97/03157 PCT~US9611128 Example 8 The following high density de~e~ent form~ tions, according to ~he present invention were prepared:

Z AA
Agglomerate C45AS 11.0 14.0 CEQ IV 2.5 2.2 Zeolite A 15.0 6.0 Carbonate 4.0 8.0 MA/AA 4.0 2.0 ¢MC 0.5 0.5 DTPMP 0.4 0.4 Spray On C25E5 5.0 5.0 Perfume 0.5 0.5 Dry Adds HEDP 0.5 0.3 SKS 6 13.0 10.0 Citrate 3.0 1.0 TAED 5.0 7.0 P'erca~onate 20.0 20.0 ~RPl 0.3 0.3 Protease 1.4 1.4 ~ ir~e 0.4 0.4 Cellulase 0.4 0.6 Amylase 0.6 0.6 Silicone anliroa~ 5.0 5.0 Bri~h~F.nçr 1 0.2 0.2 -Bri~h~F.~Pr 2 0.2 R~l~nre (Moisture and 100 100 l~i.ccell~nPous) Density (~/litre) 8~0 850 CA 02226628 l998-0l-l2 W O 97/03157 PCTrUS96/11285 Example 9 The following liquid deter~;e~t form~ tion~, accor~ g to the present { ~ invention were ~l~aled:
AB AC AD AE AF AG AH AI

LAS l0.13.0 9.0 - 25.0 C25AS 4.0 1.0 2.0 10. - 13.0 18.0 15.0 C25E3S 1.0 - - 3.0 - 2.0 2.0 4.0 C25E7 6.0 8.0 13. 2.5 - - 4.0 4.0 o TFAA - - - 4.5 - 6.0 8.0 8.0 CEQ I 0.4 1.0 0.8 0.4 2.0 1.5 1.0 2.5 CEQ II 0.6 1.2 0.7 0.4 1.2 0.5 2.5 1.5 QAS - - - - 3.0 1.0 TP~FA 2.0 - 13. 2.0 - 15.0 7.0 7.0 o Rapeseed fatty acids - - - 5.0 - - 4.0 4.0 Citric acid 2.0 3.0 1.0 1.5 1.0 1.0 1.0 1.0 Dodecenyl/tetr~lecenyl 12. 10.0 - - 15.0 succinic acid 0 Oleic acid 4.0 2.0 1.0 - 1.0 F.th~n~l 4.0 4.0 7.0 2.0 7.0 2.0 3.0 2.0 1,2 rro~aQediol 4.0 4.0 2.0 7.0 6.0 8.0 10.0 13.-Mono Fth~nQl Amine - - - 5.0 - - 9.0 9.0 TA Fth~n~l Amine - - 8 NaOHuptopH 8.0 8.0 7.6 7.7 8.0 7.5 8.0 8.2 E~ho~ylated 0.5 - 0.5 0.2 - - 0.4 0.3 tetraethylene P~
D TP M P 1.0 1.0 0.5 1.0 2.0 1.2 1.0 S~UP 2 0.3 - 0.3 0.1 - - 0.2 0.1 P V N O - - - - - - - 0.10 W O 97/03157 PCTnUS96/11285 Protease 0.5 0.5 0.4 0.2 - 0.5 0.3 0.6 S
Alc~ e - - - - 1.5 ~,ir~e - 0.10 - 0.0 - - 0.150.15 ' ' Amylase 0.2 0.25 0.6 0.5 0.25 0.9 0.6 0.6 Cellnl~e 0.4 0.3 0.2 0.5 0.9 1.0 0.15 0.15 Endolase - - - 0.1 0 0.07 Boric acid 0.1 0.2 - 2.0 1.0 1.5 2.5 2.5 Na formate - - 1.0 Ca chloride - 0.015 - 0.0 Be.-tQ~ e clay - - - - 4.0 4.0 - -Suspen~linP clay SD3 - - - - 0.6 0.3 R~l~nc.e (Moisture and 100 100 100 100 100 100 100 100 Miscellaneous)

Claims

WHAT IS CLAIMED IS:
1. A detergent composition comprising (a) a cationic ester surfactant; and (b) a cellulolytic enzyme present at a level of from 0.01% to 5.0% by weight of said detergent composition, on a 1000CEVU/g basis.

2. A detergent composition according to Claim 1 wherein said cationic ester surfactant is present at a level from 0.1% to 20.0% by weight of the detergent composition.

3. A detergent composition according to either of Claims 1 or 2 wherein said cellulolytic enzyme is present at a level from 0.3 % to 4.0% by weight of the detergent composition, on a 1000 CEVU/g basis.
4. A detergent composition according to any of Claims 1 to 3 wherein the cationic ester surfactant is selected from those having the formula:

wherein R1 is a C5-C31 linear or branched alkyl, alkenyl or alkaryl chain or M-~ N+(R6R7R8)(CH2)s; X and Y, independently, are selected from the group consisting of COO, OCO, O, CO, OCOO, CONH, NHCO, OCONH and NHCOO wherein at least one of X or Y is a COO, OCO, OCOO, OCONH or NHCOO group; R2, R3, R4, R6, R7, and R8 are independently selected from the group consisting of alkyl, alkenyl, hydroxyalkyl, hydroxy-alkenyl and alkaryl groups having from 1 to 4 carbon atoms; and R5 is independently H or a C1-C3 alkyl group; wherein the values of m, n, s and t independently lie in the range of from 0 to 8, the value of b lies in the range from 0 to 20, and the values of a, u and v independently are either 0 or 1 with the proviso that at least one of u or v must be 1; and wherein M is a counter anion.

5. A detergent composition according to Claim 4 wherein R2,R3 and R4 are independently selected from the group consisting of -CH3 and -CH2CH2OH.

6. A detergent composition according to Claim 4 wherein both R2 and R3 are C2-C3 alkyl groups.

7. A detergent composition according to Claim 4 wherein the cationic ester is selected from the choline esters having the formula:

wherein m is from 1 to 4 and R1 is a C11-C19 linear or branched alkyl chain.

9. A detergent system according to any of Claims 1 to 8 wherein an alkalinity system is provided, comprising components selected from the group consisting of carbonates, bicarbonates, silicates and any mixtures thereof.

10. A method of washing laundry in a domestic washing machine in which a dispensing device containing an effective amount of a solid detergent composition according to any of Claims 1 to 9 is introduced into the drum of the washing machine before the commencement of the wash, wherein said dispensing device permits progressive release of said detergent composition into the wash liquor during the wash.