CA2226620A1 - Detergent compositions - Google Patents

Abstract

There is provided a detergent composition suitable for use in laundry and dish washing methods comprising (a) a cationic ester surfactant; and (b) an amylolytic enzyme present at a level of from 0.05 % to 5.0 % by weight of said detergent composition, on a 120KNU/g activity basis.

Description

W O97/03160 rCTrus96/11105 Deterpent compositions .

Technical field The present invention relates to deler~ent compositions cont~inin~ a cationic ester surf~ct~n~ and an amylolytic enzyme which are suitable for use in laundry and dish w~hin~E methods.

Back~loulld to the invention The s~ti~f~ctory removal of greasy soils/stains, that is soils/stains having a high proportion of triglycerides or fatty acids, is a ch~llenge faced by the form~ tor of detergent compositions for use in machine laundry washing metho~ls. Surfactant components have traditionally been employed in detergent products to facilitate the removal of such greasy soils/stains. In particular, surf~ct~nt systems comprising cationic esters have been described for use in greasy soil/stain removal.

Another known delergent component are amylolytic enzymes. Amylolytic enzymes or amylases are known in the art to contribute to stain/soil removal.

For example, EP-B-21,491 discloses detergent compositions cont~ining a nonionic/cationic surfactant mixtllre and a builder mixtllre comprising ~lnminosilicate and polycarboxylate builder. The cationic surf~ct~nt may be a cationic ester. Improved particulate and greasy/oily soil removal is described.

WO 97/03160 PCT~US96/11105 US-A~,228,042 discloses biodegradable cationic surf~ct~nts, including c~tioniC ester surfactants for use in detelgent compositions to provide greasy/oily soil removal. The combination of these cationic surf~ct~nts with nonionic surfact~nts in compositions ~le~i~n~-l for particulate soil removal is also described.

US-A4,260,529 discloses laundry detergent compositions having a pH of no greater than 11 cont~inin~ cationic ester surf~ct~nt and nonionic surfactant at defined weight ratios.

The removal of greasy soils/ stains from older, frequently washed fabric, especially cotton fabric, can be especially problematic. These fabrics tend to suffer from reeidll~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 ~meliorated by the inclusion of amylolytic enzymes in a delergel.t composition, cont~inin~ c~tionir ester ell-f~ct~nts. Delerg~t compo.eitione employing both cationic ester surf~ct~nt and amylolytic enzyme provide a surprisingly better cle~nin~ perform~nce (especially by removal of reeiflll~l grease, c~llein~ the 'dingy' appearance of the fabric) than that of detergent compositions employing either of the two components individually. The cl~o~nin~ benefits are especially apparent after frequent washing of the fabAcs.

Two mech~niems are believed to be responsible for these benefits.
Firstly, the greasy stain/soil removal from the st~ine~l fabric surface by the c~tionic ester surfactant can facilitate the amylolytic degradation of polysacch~ride and starch material, comprised in stains/soils on the fabric, whereby an improved cleaning performance is achieved. Secondly, it is believed that the c~tionic ester surf~ct~nt interacts with free surf~ct~ntmonomers present in the wash solution, especially with ~nionic surf~ct~nt monomers. Thereby, the amount of free surf~ct~nt m~ nomers is re~llceA.
Free surf~ct~nt monomers are known to inhibit the enzyme activity. Thus, re~llction of the free surf~ct~nt monomer concentration in the wash solution by the c~tionic ester surf~ct~nt prevents the inhibition of the W O 97/03160 PCTrUS96/11105 activity of the amylolytic enzymes. Thereby, the amylolytic enzyme pe~ror~ance will be ~eeiete~l All docllmtonts cited in the present description are, in relevant part, incorporated herein by referellce.

S~lmm~ry of the Invention The detergent composition of the present invention comprises (a) a cationic ester surfactant; and (b) an amylolytic enzyme present at a level of from 0.05% to 5.0% by weight of said delergellt composition, on a 120 KNU/g activity basis.

In a preferred aspect, the cationic ester surf~ct~nt is selected from those having the formula:

R15 1 +
Rl - (3 (CH~nO (X)U--(CH2)m--(Y)V--(CH2)t--N--R3 M
- a ~4 wherein Rl is a Cs-C31 linear or br~nch~ alkyl, alkenyl or alkaryl chain or M-. N+(R6R7R8)(CH2)S; X and Y, indepen~lently, are selected from the group coneieting 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 indepe-n~l~ntly selPctecl from the group con~i~tin~ of alkyl, alkenyl, hydroxyalkyl, hydro~y-alkenyl and alkaryl groups having from 1 to 4 carbon atoms; and Rs is indepen~lently H or a Cl-C3 alkyl group;
wherein the values of m, n, s and t indepen~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 W O 97/03160 PCT~US96/11105 and v indepen~lently 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.
The other essenti~l component of the d~ler~ ent composition of the invention is an amylase enzyme, incorporated into the compositions at a level of from 0.05 % to 5 %, more preferably from 0.1 % to 2%, most preferably from 0.2% to 1 % active enzyme by weight of the composition, on a 120KNU/g activity basis.

Detailed description of the invention Cationic ester surf~ct~nt An es~enti~l elçmPnt of the deterg~t compositions of the invention is a c~tionic ester surfactant. The cationic ester surf~ct~nt prererably is present at a level of from 0.1 % to 20.0%, more preferably from 0.5% to 10%, most preferably from 1.0% to 5.0% by weight of the detel~ellt composition.

The c?tioni~ ester surf~ct~nt of the present invention is a, preferably water dispersible, compound having surf~ct~nt properties COLtl~)liSlrlg at least one ester (i.e. -COO-) linkage and at least one c?tionic~lly charged group.

Suitable cationic ester surfactants, including choline ester surf~ct~nts, have for example been disclosed in US Patents No.s 4228042, 4239660 and 4260529.

In one preferred aspect the ester linkage and cationically charged group are separated from each other in the surf~ct~nt molecule by a spacer group con~i.stinp of a chain comprising at least three atoms (i.e. of three atoms chain length), preferably from three to eight atoms, more preferably from three to five atoms, most preferably three atoms. The atoms forming the spacer group chain are selected from the group con~icting of carbon, nitrogen and oxygen atoms and any mi~ctures W O97/03160 PCTrUS96/11105 thereof, with the proviso that any nitrogen or oxygen atom in said chain connects only with carbon atoms in the chain. Thus spacer ~ou~s having, for example, -O-O- (i.e. peroxide), -N-N-, and -N-O- linkages are excluded, whilst spacer groups having, for example -CH2-O- CH2-and -CH2-NH-CH2- linkages are included. In a preferred aspect the spacer group chain comprises only carbon atoms, most preferably the chain is a hydrocarbyl chain.

Plefelled cationic ester surfactants are those having the formula:

1~2 R~
Rl-- ~(CH)nO (X)U--( C H2 )m--(Y)v--(CH2 )t--N--R3 M
- a P'4 wherein Rl is a Cs-C31 linear or branched alkyl, alkenyl or alkaryl chain or M-. N+(R6R7Rg)(CH2)S; X and Y, indepenclently, are selecte~ from the group conci~ting 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 indepçn-lPntly selected from the group con~i~tin~ of alkyl, alkenyl, hydroxyalkyl and hydroxy-alkenyl groups having from 1 to 4 carbon atoms and alkaryl groups; and Rs is indepen~1ently H or a Cl-C3 alkyl group; wherein the values of m, n, s and t indepen~lPntly 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 indepen~lently are either 0 or 1 with the proviso that at least one of u or v must be l; and wherein M is a counter anion.

Preferably M is selected from the group consisting of halide, methyl sulfate, sulfate, and nitrate, more preferably methyl slllf~te, chloride, bromide or iodide.
In a preferred aspect, the cationic ester surf~ct~nt is selected from those having the formula:

CA 02226620 l998-0l-l2 PCT~US96/11105 R1 ~--(CH)nO (X) (CH2)m--N R3 M
b a P'4 CA 02226620 l998-0l-l2 W O 97/03160 PCTrUS96/11105 wherein Rl is a Cs-C31 linear or branched alkyl, aLkenyl or alkaryl chain; X is selected from the group consisting of COO, OCO, OCOO, OCONH and NHCOO; R2, R3, and R4 are indepen~ently selected from the group con~i~ting of alkyl and hydroxyaLkyl groups having from 1 to 4 carbon atoms; and Rs is independently 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 ~refeldbly R2, R3 and R4 are indepen-lently selected from a Cl-C4 alkyl group and a Cl-C4 hydroxyaLkyl group. In one ~refelled aspect at least one, ~-eferably only one, of R2, R3 and R4 is a hydro~yalkyl group.
The hydroxyalkyl preferably has from 1 to 4 carbon atoms, more ylefe~ably 2 or 3 carbon atoms, most preferably 2 carbon atoms. In another ~rere.l~d aspect at least one of R2, R3 and R4 is a C2-C3 alkyl group, more pferelably two C2-C3 alkyl groups are present.

Highly ~refelled water dispersible cationic ester surf~ct~nt~ are the esters having the formula:
O Cl H3 R1--C--~--(CH2)m--N+--CH3 M-where m is from 1 to 4, preferably 2 or 3 and wherein Rl is a Cll-Clg linear or br~ncheA alkyl chain.

W O97/03160 PCT~US96/11105 Particularly preferred choline esters of this type inc111(7e the stearoyl choline ester quaternary methyl 7mmoninm h~ 7ee (Rl=C17 a~yl), palmitoyl choline ester quaternary methyl,7mmonium h~1it1es (Rl=Cls a~yl), myristoyl choline ester quaternary met7ly1,7mmoni11m h~71i~7es (Rl =C13 al~yl), lauroyl choline ester methyk7mmoni17m h~ 7.~.e (Rl=Cll a kyl), cocoyl choline ester quaternary methy1,7mmoni17m h71i~7es (Rl=Cll C13 alkyl), tallowyl choline ester quaternary methyl 7mmonil7m h~ 7es (Rl =Cls C17 allyl), and any mixtures thereof.

Other suitable cationic ester surf~ct~nt~ have the structural formulas below, wherein d may be from 0 to 20.

Rl--o_c8_(CH2)a--C--O--CH2CH2--1+ CH3 M-M CH3--~--CH~ CH2--O--C--( CH2 )d C--O--CH2--CH2--~--CH3M

In a preferred aspect the c~tionic ester surfactant is hydrolysable under the conrlition~ of a laundry wash method.

The particularly ~er~lled choline esters, given above, may be prepared by the direct eslel;~ç~tion of a fatty acid of the desired chain length with dimethyl~min- ethanol, in the presence of an acid catalyst. The reaction product is then q~l~tP.rni7~cl 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 alcohol etho~cylate having a degree of ethoxylation of from 3 to 50 etho~cy groups per mole formin~ the desired cationic material. They may also be prepared by the direct esterification of a long chain fatty acid of the desired chain length together with 2-haloethanol, in the presence of an W O97/03160 PCTrUS96/lllOS

acid catalyst material. The reaction product is then quater~zed with trimethyl~mine, ~o~g the desired c~tionic material.

W O97/03160 PCT~US96/11105 AmylolytiG enzyme The second eSsenti~l component of the compositions is an amylolytic enzyme or amylase enzyme, which is an enzyme having amylolytic activity.
The amylase enzyme is incorporated into the compositions in accordance with the invention at a level of from 0.05% to 5%, more ~rererably from O.l ~o to 3 %, most prefe~ably from 0.2% to 1 % active enzyme by weight of the composition, on a 120KNU/g activity basis.

The units of 'Kilo Novo Units/gram (KNU/g)' are a well known means of defining amylolytic enzyme activity and are described in GB-1,269,839 A (Novo). In more detail, 1 KNU is the amount of enzyme which breaks down 5.25 grams of starch (Merck, Amylum Solubile Erg. B.6, Batch 9947275) per hour in the method described in GB-1,269,839 A, which has the following st~n~1~rd conditions:

Substrate Soluble starch Calcium content in solvent 0.0043 M
Reaction time 7-20 mimltes Temperature 37~C
pH 5.6 The amylase enzyme may be fungal or bacterial in origin. Amylases obtained by ch~mical or genetic manipulation of fungal or bacterial derived strains are also useful herein. The amylase enzyme is ~lercl~bly an a-amylase.

Preferred amylases include, for example, a-amylases obtained from a special strain of B. licheniformis, described in more detail in GB-1,269,839 A. Reported deposit numbers for B. licheniformis strains capable of producing a-amylases include NCIB 8061, NCIB 8059, ATCC
6634, ATCC 6598, ATCC 11945, ATCC 8480 and ATCC 9945a.

W O 97/03160 PCTrUS96/11105 Preferred commercially available a-amylases include for example, those sold under the tr~çn~nle Rapidase and Maxamyl by Gist-Brocades; those sold under the tr~lçn~m~ Taka-Therm L-340 by Miles Laboratories, F.lkh~rt, Tn~ n~; those sold under the tr~den~me Rohalase AT by Rohm and Haas, West phil~-lelphia, PA; and those sold under the tr~-len~mes Termamyl 60T and 120T, Flln~myl and BAN by Novo Tntlll~tries A/S.

In a pfe~erred aspect, the amylases have been ~iesi~n~l to have improved stability, particularly having i~proved stability to o~id~tion, for e~cample in a bleaching envirc~ Pnt~ and improved thermal stability. Stability can be measured using any of the tec_nical tests known in the art including those refeired to in WO 94/02597 A. Stability-çnh~nce~l amylases are commercially available from Novo Tn~ stries A/S or from Gen~ncor International.

Highly preferred amylases with enh~nce~l oxidative stability are derived using site-directed mutagenesis from one or more of the Baccillus amylases, especialy the B~cilllls a-amylases, regardless of whether one, two or multiple amylase strains are the immto~ te precursors. P~felled amylases of this type are described in WO 94/02597 A, and comprise a t in which substitution is made, using ~l~ninç or threonine, prefelably threonine, of the methionine residue located in position 197 of the B. liçheniformis a-amylase, sold under the tr~len~m~ Term~myl, or the homologous position variation of a .~imil~r parent amylase, such as B.
amyloliquefaciens, B.subtilis, or B .stearothermophilus.

Other ~refelled amylases having enh~nced oxidative stability, derived from B.licheniformis NCIB806, are described by Gentoncor Tnt~rn~tion~
in a paper entitled "O~idatively Resistant a-Amylases" which was presented at the 207th American Chemical Society National Meeting, March 13-17 1994, by C. Mitchin~on. Methionine (Met) was identifi~
as the most likely residue to be motlifiecl. Met was s~bstit~lted, one at a time, in positions 8, 15, 197, 256, 304, 366 and 438 le~-lin~ to specific mllt~ntS~ particularly important being M197L and M197T with the M197T variant being the most stable expressed variant.

CA 02226620 l998-0l-l2 W O 97/03160 PCTnUS96/11105 Other preferred amylases having enh~nced oxidative stability inc~ Af~
those described in WO 94/18314 A (Genencor International) and WO
94/02597 A (Novo). Any other oxidative stability-enh~nced amylase can be used, for example as derived by site-directed mutagenesis from known chim~ric, hybrid or simple mllt~nt parent forms of av~ ble amylases.
Other enzyme modifications are acceptable including those described in WO 95/09909 A (Novo).

It will be appreciated that enzymes for incorporation into solid delelgt;llt compositions are general!y sold commercially as enzyme prills cont~inin~
active enzyme supported on a variety of inert host materials, which for example, can include aLkali metal sl-lf~te~, carbonates and silicates.
Optionally, organic binder m~t~ri~lc are also incorporated. In a preferled aspect, the calcium content of these enzyme prills is ...;..i...~e~l to ensure good in-product storage stability of the enzyme.

Additional de~el~ellt components The delergent compositions of the invention may also contain ~ldition~l delergent components. The precise nature of these ~d~lition~l components, 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 ~A(litional delerge~t components selected from ~AAitional surf~ct~nt~, ble~c-hes, builders, organic polymeric compounds, ~ itional enzymes, suds ~uppressors, lime soap dispelsal,ls, soil suspension and anti-redeposition agents and corrosion inhibitors.

Additional surfactant The deleigent compo~ition~ of the invention pleferably contain an z~A(lition~l surf~ct~nt selected from anionic, nonionic, non-ester cationic, ampholytic, amphoteric and zwitterionic surfactants and mi~t~res thereof.
-W O 97/03160 PCTrUS96/11105 A typical listing of anionic, nonionic, ampholytic, and zwitterionic classes, and species of these surfactants, is given in U.S.P. 3,929,678 issued to T.~llphlin and Heuring on December 30, 1975. Further examples are given in "Surface Active Agents and Detefgellts" (Vol. I and II by Schwall;c, Perry and Berch). A list of suitable cationic surf~ct~nt.~ is given in U.S.P. 4,259,217 issued to Murphy on March 31, 1981.

Where present, ampholytic, amphoteric and zwitteronic surf~ct~nts are generally used in combination with one or more anionic and/or nonionic surfactants.

Anionic surfactant The detergent compositions in accord with the invention yrefelably comprise an additional anionic surf~ct~nt Essentially any anionic surf~ct~nt~ useful for detersive purposes can be co~ lised in the detergent composition. These can include salts (including, for example, sodium, pot~ m, ammonium, and substitllte~l arnmonium salts such as mono-, di- and trieth~nol~min~ salts) of the anionic slllf~te, sulfonate, carboxylate and sarco~in~te surfactants. Anionic sulfate surf~ct~nt~ are ~refelled.

Other ~nionic surfactants include the isethionates such as the acyl i~ethion~te~, N-acyl taurates, fatty acid ~mit1es of methyl tauride, alkyl succinates and sulfosuccinates, monoesters of sulfosuccinate (especially saturated and lln~ lrated C12-C18 monoesters) diesters of slllfosllccinate (especially saturated and lln~tllrated C6-C14 ~liesters), N-acyl sarco.cin~tes. Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tallow oil.
Anionic sulfate surfactant Anionic sulfate surf~ct~nts suitable for use herein include the linear and br~n~.he~l primary and secondary all~yl slllf~tes, alkyl etho~yslllf~tes, fatty oleoyl glycerol slllf~tes, aLkyl phenol ethylene oxide ether snlf~tes~ the CS-C17 acyl-N-(cl-c4 alkyl) and -N-(Cl-C2 hydro~yalkyl) ~ C~min~
slllf~tes, and sulfates of aLkylpolysacch~ri/1e~ such as the sl-lf~t~s of aLkylpolyglucoside (the nonionic non~llf~te!l compounds being described herein).

Alkyl slllf~te surf~ct~nts are preferably selected from the linear and br~n~he~l primary Clo-Clg alkyl ~lllf~tes, more preferably the Cll-Cls br~nch~ chain alkyl sslf~tes and the C12-C14 linear chain alkyl slllf~tes.

Alkyl ethoxyslllf~te surf~ct~nts are preferably selected from the group con~istin~ of the Clo-Clg alkyl slllf~te~ which have been ethoxylated with from 0.5 to 20 moles of ethylene oxide per molecule. More ~refer~bly, the alkyl ethoxys~lf~te surf~ct~nt is a Cll-Clg, most preferably Cll-Cls alkyl sulfate which has been ethoxylated with from 0.5 to 7, ~refeidbly from 1 to 5, moles of ethylene oxide per molecule.

A particlll~rly preferred aspect of the invention employs mixtures of the plefelred aLkyl slllf~te and alkyl ethoxysulfate surf~ct~nt~. Such m~ lres have been disclosed in PCT Patent Applic~tion No. WO 93/18124.

Anionic sulfonate surfactant Anionic s~lfon~te snrf~ct~nt~ s--it~kle for use herein include the salts of Cs-C20 linear alkylben7lo-ne sulfonates, alkyl ester sulfonates, C6-C22 pAmary or secon~ry alkane sulfonates, C6-C24 olefin sulfonates, sulfonated polycarbo~cylic acids, alkyl glycerol sulfonates, fatty acyl glycerol slltfon~tes~ fatty oleyl glycerol sulfonates, and any ~ luies thereof.

Anionic carbo~cylate surfactant Suitable anionic carbo~cylate surf~ct~nts incl~cle tlle alkyl etho~cy carbo~cylates, the alkyl polyetho~y polycarboxylate surf~ct~nt~ and the soaps ('alkyl carboxyls'), especially certain secondary soaps as described herein.

CA 02226620 l998-0l-l2 W O 97/03160 PCT~US96/11105 Suitable alkyl ethoxy carboxylates include those with the formula RO(CH2CH20)X CH2COO-M+ wherein R is a C6 to Clg alkyl group, ~c ranges from O to 10, and the ethoxylate distribution is such that, on a weight basis, the amount of material where x is 0 is less than 20 % and M
is a c~ti ?n Suitable alkyl polyethoxy polycarboxylate surf~ct~nt~ inrl~ e those having the formula RO-(CHRl-CHR2-O)-R3 wherein R is a C6 to Clg alkyl group, x is from 1 to 25, Rl and R2 are selected from the group con~istinP of hydrogen, methyl acid r~lic~l, succinic acid r~lic~l, hydroxysuccinic acid radical, and mixtures thereof, and R3 is selected from the group conci~tin~ of hydrogen, substit~lte-l or nn~llbs~ e~l hydrocarbon having between 1 and 8 carbon atoms, and m~ lres thereof.

Suitable soap surfactants incllltle the secondary soap surf~ct~nts which contain a carboxyl unit connected to a secondary carbon. P~erelled secondary soap surf~ct~nts for use herein are water-soluble members selecte~l from the group con~i~ting of the water-soluble salts of 2-methyl-l-undecanoic acid, 2-ethyl-1-decanoic acid, 2-~ro~yl-1-nonanoic acid, 2-butyl-l-octanoic acid and 2-pentyl-1-heptanoic acid. Certain soaps may also be incl~ etl as suds ~u~ressors.
Alkali metal sarcosinate surfactant Other suitable ~nionic surf~ct~ntc are the alkali metal sarco~in~tes of formula R-CON (Rl) CH2 COOM, wherein R is a Cs-C17 linear or br~nche-l alkyl or alkenyl group, Rl is a Cl-C4 alkyl group and M is an alkali metal ion. Prererred e~camples are the myristyl and oleoyl methyl sarcosin~tes in the form of their sodium salts.

Alkoxylated nonionic surfactant Fssenti~lly any aLko~cylated nonionic surfactants are suitable herein. The ethoxylated and propoxylated nonionic surfactants are preferred.
rrerer~ed alko~cylated surf~ct~nts can be selected from the çl~ses of the nonionic conrl~n~tes of alkyl phenols, nonionic etho~cylated alcohols, WO97/03160 PCT~US96/11105 nonionic ethoxylated/propoxylated fatty alcohols, nonionic ethoxylate/propoxylate con~len~tee with propylene glycol, and the nonionic ethoxylate con~len~tion products with propylene oxide/ethylene mine ~ Uctc.

Nonionic alkoxylated alcohol surfactant The con~lene~tion products of ~lirh~tic alcohols with from 1 to 25 moles of alkylene oxide, particularly ethylene oxide and/or propylene oxide, are suitable for use herein. The alkyl chain of the aliphatic alcohol can either be straight or branched, primary or secondary, and generally cont~in.~
from 6 to 22 carbon atoms. Particularly preferred are the con~len~tion products of alcohols having an alkyl group cont~inin from 8 to 20 carbon atoms with from 2 to 10 moles of ethylene oxide per mole of alcohol.
Nonionic polyhydroxy fatty acid amide surf~ct~nt Polyhydroxy fatty acid ~mi~le~ suitable for use herein are those having the structural formula R2CONRlZ wherein: Rl is H, Cl-C4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl, ethoxy, propo~cy, or a mixture thereof, prer~lable Cl-C4 alkyl, more preferably Cl or C2 alkyl, most yrefelably Cl alkyl (i.e., methyl); and R2 is a Cs-C31 hydrocarbyl, preferably straight-chain Cs-Clg alkyl or alkenyl, more ~rerelably str~i~ht-chain Cg-C17 all~yl or alkenyl, most ylcr~;lably straight-chain Cll-C17 alkyl or alkenyl, or mixture thereof; and Z is a polyhydro~yhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connecte~ to the chain, or an alkoxylated derivative (preferably etho~ylated or propoxylated) thereof. Z preferably will be derived from a reducing sugar in a reductive ~min~tion reaction; more preferably Z is a glycityl.

Nonionic fatty acid amide surfactant Suitable fatty acid amide surf~ct~ntc include those having the formula:R6CoN(R7)2 wherein R6 is an alkyl group cont~inin from 7 to 21, preferably from 9 to 17 carbon atoms and each R7 is selecte~l from the W O 97/03160 PCT~US96/11105 group coneietin~ of hydrogen, Cl-C4 alkyl, Cl-C4 hydroxyalkyl, and -(C2H40)XH, where x is in the range of from 1 to 3.

Nonionic alkylpolysaccharide surfactant Suitable aLkylpolysaccharides for use herein are disclosed in U.S. Patent 4,565,647, ~ len~-lo, issued January 21, 1986, having a hydrophobic group cont~ining from 6 to 30 carbon atoms and a polys~cch~ri~le, e.g., a polyglycoside, hydrophilic group cont~ining from 1.3 to 10 saccharide units.

Plefelled aLkylpolyglycosides have the formula R20(CnH2nO)t(glycosyl)~c wherein R2 is selected from the group coneietinP of alkyl, alkylphenyl, hydroxyaLkyl, hydroxyaLkylphenyl, and mi~ res thereof in which the 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 ~lefelably derived from glucose.
Amphoteric surfactant Suitable amphoteric surf~ct~nte for use herein include the amine oxide sllrf~ct~nte and the alkyl amphocarboxylic acids.

Suitable amine oxides inclllde those compounds having the formula R3(0R4)XNO(R5)2 wherein R3 is selected from an alkyl, hydro~cyalkyl, acyl~mi~lQpropoyl and alkyl phenyl group, or m~ res thereof, cont~inin from 8 to 26 carbon atoms; R4 is an alkylene or hydro~cyalkylene group cont~ininE from 2 to 3 carbon atoms, or mixtllres thereof; ~ is from O to 5, ~rereldbly 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. Plerel~ed are Clo-Clg alkyl ~imethyl~min~
oxide, and Cl~lg acyl~mi~lo alkyl dimethyl~minto oxide.

CA 02226620 l998-0l-l2 -W O 97/03160 PCT~US96/11105 A suitable example of an aLkyl aphodicarboxylic acid is Miranol(TM) C2M Conc. m~nllf~ctllred by Miranol, Inc., Dayton, NJ.

Zwitterionic surfactant ZwitteriQnic surf~ct~nts can also be incorporated into the detergent compositions hereof. These surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary ~min~-s, or derivatives of qu~te~ - y ~mmonillm~
qu~tern~ry phosphonium or tertiary sulfonium compounds. Betaine and slllt~ine surf~ct~nts are exemplary zwitterionic surfactants for use herein.

Suitable bet~in~s are those compounds having the formula R(R')2N+R2COO- wherein R is a C6-C1g hydrocarbyl group, each R1 is typically Cl-C3 alkyl, and R2 is a C1-Cs hydrocarbyl group. Preferred bet~ines are C12 18 flim~thyl-ammonio hexanoate and the C1~1g acyl~mi~lopropane (or ethane) ~limethyl (or diethyl) bet~inf~s. Comple~
betaine surf~ct~nt~ are also suitable for use herein.

Cationic surfactants Additional cationic surf~ct~nts can also be used in the detergent compositions herein. Suitable cationic surfactants include the quaternary ammonium surf~ct~nt~ selected from mono C6-C16~ preferably C6-C10 N-alkyl or aLenyl ~mmonillm surfactants wherein the rem~inin~ N
positions are substit-~te~l by methyl, hydroxyethyl or hydro~yplo~yl groups.

~lk~linity In the detergent compositions of the present invention pre~erably a ~lk~linity ~iy:i~em is present to achieve optimal cationic ester surf~ct~nt performance. The ~lk~linity ~y~leLu comprises components capable of providing ~lk~linity species in solution. By ~lk~linity species it is meant herein: carbonate, bicarbonate, hydroxide, the various ~ilic~te anions, percarbonate, perborates, perphosphates, persulf~te and persilicate.

W O 97/03160 PCTrUS96/lllO5 Such ~lk~1inity species can be formed for example, when ~lk~lin~. salts selected from aLkali metal or ~lk~line earth carbonate, bicarbonate, hydro~cide or silicate, including crystalline layered silicate, salts and any mixhlres thereof are dissolved in water.
Fx~mples of carbonates are the ~lk~line earth and alkali metal carbonates, including sodium carbonate and sesqui-carbonate and any mi~tures thereof with ultra-fine calcium carbonate such as are disclosed in Cc~ma~
Patent Applic~tion No. 2,321,001 published on November 15, 1973.

Suitable silicates include the water soluble sodium .~ilic~tes with an SiO2:
Na20 ratio of from 1.0 to 2.8, with ratios of from 1.6 to 2.0 being preferred, and 2.0 ratio being most prefelred. The ~ilic~tes may be in the form of either the anhydrous salt or a hydrated salt. Sodium ~ilic~te with an SiO2: Na20 ratio of 2.0 is the most yrert;l~ed silis~te.

erell~d cryst~llinto layered ~ilic~tes for use herein have the general formula NaMSix02x+ 1 ~YH20 wherein M is sor~ m or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20. Cryst~lline layered sodium silicates of this type are disclosed in EP-A-0164514 and methods for their preparation are ~lisclose l in DE-A-3417649 and DE-A-3742043. Herein, ~ in the general formula above prereiably has a value of 2, 3 or 4 and is ~lere~ably 2. The most preferred m~teri~l is ~-Na2Si20s, available from Hoechst AG as NaSKS-6.

Water-soluble builder compound The delergent compositions of the present invention preferably contain a water-soluble builder compound, typically present at a level of from 1 %
to 80% by weight, preferably from 10% to 70% by weight, most ~rere~ably from 20% to 60% by weight of the composition.

W O97/03160 PCT~US96/11105 Suitable water-soluble builder compounds inCl~ld~ the water soluble monomeric polycarboxylates, or their acid forms, homo or copolymeric polycarboxylic acids or their salts in which the polycarboxylic acid comprises at least two carboxylic r~ic~lc separated from each other by not more that two carbon atoms, borates, phosphates, and mixtllres of any of the foregoing.

The carboxylate or polycarboxylate builder can be momomeric or oligomeric in type although monomeric polycarboxylates are generally preferred for reasons of cost and performance.

Suitable carboxylates cont~inin~ one carboxy group include the water soluble salts of lactic acid, glycolic acid and ether derivatives thereof.
Polycarboxylates cC nt~inin~ two carboxy groups include the water-soluble salts of succinic acid, malonic acid, (ethy1en~ioxy) rli~cetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid and fum~ric acid, as well as the ether carbo~cylates and the sulfinyl carboxylates. Polycarboxylates containing three carboxy groups include, in particular, water-soluble citrates, aconitrates and citraconates as well as succinate deliv~lives such as the carboxymethyloxysuccinates described in British Patent No.
1,379,241, lactoxysuccin~tes described in British Patent No. 1,389,732, and an~inosuccinates described in Netherlands Application 7205873, and the oxypolycarboxylate m~teri~l~ such as 2-oxa-1,1,3-~1~alle tricarboxylates described in British Patent No. 1,387,447.
Polycarboxylates cont~inin~ four carboxy groups include o~cydisuccinates disclosed in British Patent No. 1,261,829, 1,1,2,2-ethane tetracarbo~cylates, 1,1,3,3ylo~a~e tetracarboxylates and 1,1,2,3-~ro~ane tetracarboxylates. Polycarboxylates cont~ining sulfo sllbstiblente inclll~e the sulfosucci~ate derivatives disclosed in British Patent Nos. 1,398,421 and 1,398,422 and in U.S. Patent No. 3,936,448, and the snlfon~tetl pyrolysed citrates described in British Patent No. 1,439,000. Pie~elled polycarboxylates are hydroxycarboxylates cont~inin~ up to three carbo~cy groups per molecule, more particularly citrates.

W O 97/03160 PCTrUS96/11105 The parent acids of the monomeric or oligomeric polycarbo~cylate chelating agents or mixtures thereof with their salts, e.g. citric acid or citrate/citric acid mixtures are also contemplated as useful builder components.

Borate builders, as well as builders cont~inin~ borate-~oll,~g m~te.ri~
that can produce borate under detergent storage or wash conditions are useful water-soluble builders herein.

Suitable examples of water-soluble phosphate builders are the alkali metal tripolyphosphates, sodium, pot~sillm and ammonium pyrophosphate, sodium and pot~cillm and ammonium pyrophosphate, sodium and pot~i-lm orthophosphate, sodium polymeta/phosphate in which the degree of polymerization ranges from about 6 to 21, and salts of phytic acid.

Partially soluble or insoluble builder compound The detergent compositions of the present invention may contain a partially soluble or insoluble builder compound, typically present at a level of from 1% to 80% by weight, preferably from 10% to 70% by weight, most preferably from 20% to 60% weight of the composition.
F.x~mples of largely water insoluble builders include the sodium minosilicates.

Suitable ~hlminosilic~te zeolites have the unit cell formula Nazt(Alo2)z(sio2)y]. ~cH2O wherein z and y are at least 6; the molar ratio of z to y is from 1.0 to 0.5 and x is at least 5, l,refe~bly from 7.5 to 276, more yrefeiably from 10 to 264. The ~hlminosilicate material are in hydrated form and are preferably cryst~lline, cont~inin~ from 10% to 28%, more ~refeidbly from 18% to 22% water in bound form.

The ~hlminQsilicate zeolites can be naturally occurring m~teri~l~, but are preferably synth~tic~lly derived. Synthetic cryst~lline ~hlmino~ c~t~ ion e~rh~n~e materials are available under the de~i~n~tion~ Zeolite A, Zeolite W O 97/03160 PCT~US96/lllOS

B, Zeolite P, Zeolite X, Zeolite HS and mixtures thereof. Zeolite A has the formula Na 12 tAlO2) 12 (sio2)l2]~ xH2O
wherein x is from 20 to 30, especially 27. Zeolite X has the formula Na86 [(Alo2)86(sio2)lo6] 276 H2O.
Or~anic peroxyacid bleachin~ system A preferred feature of detergent compositions of the invention is an organic peroxyacid ble~chin~ ~yslem. In one preferred execution the ble~chin~ ~y~leu~ contains a hydrogen peroxide source and an organic peroxyacid bleach precursor compound. The production of the organic peroxyacid occurs by an in situ reaction of the precursor with a source of hydrogen peroxide. Preferred sources of hydrogen peroxide incl~l~le inorganic pelLy-llate bleaches. In an ~ltern~tive preferred exec~tion a yrefolllled organic peroxyacid is incorporated directly into the composition. Compositions cont~inin~ mixtures of a hydrogen pero~cide source and organic peroxyacid precursor in combination with a preformed organic peroxyacid are also envisaged.

CA 02226620 l998-0l-l2 W O 97/03160 PCTrUS96/11105 Inor~anic perhydrate bleaches Inorganic perhydrate salts are a preferred source of hydrogen peroxide.
These salts are normally incorporated in the form of the alkali metal, ~rcre~ably sodium salt at a level of from 1% to 40% by weight, more preferably from 2% to 30% by weight and most preferably from 5% to 25 % by weight of the compositions.
F~mples of inorganic perhydrate salts include perborate, percarbonate, perphosphate, persulfate and persilicate salts. The inorganic perhydrate salts are normally the aL~ali metal salts. The inorganic perhydrate salt may be included as the cryst~llin~ solid without ~1dition~l protection. For certain perhydrate salts however, the preferred executions of such granular compositions utilize a coated form of the material which provides better storage stability for the perhydrate salt in the granular product. Suitable co~tin~c comprise inorganic salts such as alkali metal silicate, carbonate or borate salts or mixtures thereof, or organic materials such as waxes, oils, or fatty soaps.

Sodium perborate is a preferred perhydrate salt and can be in the form of the monohydrate of nominal formula NaB02H202 or the tetraLyd~ate NaB02H202 3H20 Alkali metal percarbonates, particularly sodium percarbonate are p~e~elled pelllydr~Lles herein. Sodium percarbonate is an ~lclition compound having a formula corresponding to 2Na2C03.3H202, and is available commercially as a cryst~lline solid.

Pot~s~inm peroxymonopersulfate is another inorganic perhydrate salt of use in the detergent compositions herein.
Peroxyacid bleach precursor Peroxyacid bleach precursors are compounds which react with hydrogen peroxide in a perhydrolysis reaction to produce a peroxyacid. Generally peroxyacid bleach precursors may be represented as W O97/03160 PCTrUS96/11105 X-C--L

where L is a leaving group and X is essentially any functionality, such that on perhydroloysis the structure of the peroxyacid produced is o X--C--OOH

Peroxyacid bleach precursor compounds are ~lefelably incorporated at a level of from 0.5% to 20% by weight, more yrefelably from 1% to 15%
by weight, most preferably from 1.5% to 10% by weight of the delergent compositions.

Suitable peroxyacid bleach precursor compounds typically contain one ormore N- or O-acyl groups, which precursors can be selected from a wide range of classes. Suitable classes include anhydrides, esters, imi~les, l~ct~m~ and acylated derivatives of imi~ oles and o~imes. F~mples of useful materials within these c~ ses are disclosed in GB-A-1586789.
Suitable esters are disclosed in GB-A-836988, 864798, 1147871, 2143231 and EP-A-0170386.

Leaving ~roups The leaving group, hereinafter L group, must be sufficiently reactive for the perhydrolysis re~ction to occur within the optimum time frame (e.g., a wash cycle). However, if L is too reactive, this activator will be difficult to stabilize for use in a bleaching composition Preferred L groups are selected from the group con~isting of: -CA 02226620 l998-0l-l2 W O97/03160 PCT~US96/11105 --0~, O~Y , and --0 --I--C--R1 _N N 1~l R3 r --O--CH=C--CH=CH2 --O--CH=C--CH=CH2 1~l Y~ 1~l -O--C--R1 _N~ NR4 --N ~NR4 Il 11 O O

--O--C=CHR4 , and I 1l--CH--R4 R3 o and mi~t~lres thereof, wherein Rl is an alkyl, aryl, or alkaryl group cs~nt~inin~ from 1 to 14 carbon atoms, R3 is an alkyl chain cont~ining from 1 to 8 carbon atoms, R4 is H or R3, and Y is H or a solubilizing group. Any of Rl, R3 and R4 may be substitlltecl by essenti~lly any functional group including, for example alkyl, hydro~cy, alkoxy, halogen, amine, nitrosyl, amide and ammonium or alkyl ~mmmonium groups The L,re3reL,ed solubilizing g3oups are -S03-M +, -C02-M +, -S04-M +, -N+(R )4X- and O< N(R )3 and most pLefel~bly -S03-M+ and -C~2 M wherein R3 is an alkyl chain cont~ining from 1 to 4 carbon atoms, M is a cation which provides solubility to the bleach activator and X is an anion which provides solubility to the bleach acliv~tor.
Preferably, M is an alkali metal, ammonium or sub~ 3 ammonium c~tion~ with sodium and pot~si~lm being most preferred, and X is a halide, hydroxide, methylc-llf~te or acetate anion.
Alkyl percarboxylic acid bleach precursors Alkyl percarboxylic acid bleach precursors form percarboxylic acids on perhydrolysis. Preferred precursors of this type provide peracetic acid on perhydrolysis.

Preferred alkyl percarboxylic precursor compounds of the iide type include the N-,N,NlNl tetra acetylated aLkylene ~i~minec wherein the alkylene group cont~in~ from 1 to 6 carbon atoms, particularly those compounds in which the alkylene group contains 1, 2 and 6 carbon atoms.
Tetraacetyl ethylene rli~mine (TAED) is particularly preferred.

Other ~referfed allyl percarboxylic acid precursors include so~ m 3,5,5-tri-methyl hP~noyloxyben7Pne sulfonate (iso-NOBS), sodium non~nQylo~cyben7P,ne sulfonate (NOBS), sodium aceto~ybP-n7enP, sulfonate (ABS) and p~nt~cetyl glucose.

Amide substituted alkyl peroxyacid precursors Amide snbstit~ltp~ alkyl peroxyacid precursor compounds are suitable herein, including those of the following general formlll~P:

11 1 11 ~1 O R5 O or R5 O O

wherein Rl is an alkyl group with from 1 to 14 carbon atoms, R2 is an alkylene group cont~inin~ 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 essçnti~lly any leaving group. Amide substitllte~l bleach activator compounds of this type are described in EP-A-0170386.

W O 97103160 PCT~US96/11105 Perbenzoic acid precursor Perbenzoic acid precursor compounds provide perbenzoic acid on perhydrolysis. Suitable O-acylated perbenzoic acid precursor compounds include the substit~lte~l and unsubstitllte~ benzoyl oxyben7en~o- slllfon~tes, and the benzoylation products of sorbitol, glucose, and all saccharides with benzoylating agents, and those of the imide type including N-benzoyl succinimi-le, tetrabenzoyl ethylene cli~mine and the N-benzoyl substiblter ureas. Suitable imirl~701e type perbenzoic acid precursors inclllde N-benzoyl imi~1~7Ole and N-ben_oyl ben7imicl~7Ole. Other useful N-acyl group-cont~inin~ perbenzoic acid precursors include N-benzoyl pyrrolidone, dibenzoyl t~llrin-o and benzoyl pyro~ t~mic acid.

Cationic peroxyacid precursors Cationic peroxyacid precursor compounds produce cationic peroxyacids on perhydrolysis.

Typically, c~tionic pero~cyacid precursors are formed by s~lbs~ the pero~yacid part of a suitable pero~yacid precursor compound with a positively charged functional group, such as an ammonium or alkyl ~mmmonium group, plefelably an ethyl or methyl ammonium group.
Cationic peroxyacid precursors are typically present in the solid deLelgent compositions as a salt with a suitable anion, such as a halide ion.
The peroxyacid precursor compound to be so cationically substitllte~ may be a perbenzoic acid, or substibltecl derivative thereof, precursor compound as ~escribed hereinbefore. Alternatively, the peroxyacid precursor compound may be an aL~yl percarboxylic acid precursor compound or an amide substit~lte~l aL~yl peroxyacid precursor as described herein~fter ~3tioniC peroxyacid precursors are described in U.S. Patents 4,904,406;
4,751,015; 4,988,451; 4,397,757; 5,269,962; 5,127,852; 5,093,022;
5,106,528; U.K. 1,382,594; EP 475,512, 458,396 and 284,292; and in JP 87-318,332.

CA 02226620 l998-0l-l2 W O 97/03160 PCT~US96/11105 2~

Fr~mrles of prefelled cationic peroxyacid precursors are described in UK Patent Application No. 9407944.9 and US Patent Application Nos.
08/298903, 08/298650, 08/298904 and 08/298906.

Suitable cationic peroxyacid precursors include any of the ammonium or alkyl ammonium substit~lte~ alkyl or benzoyl oxyben7~ne sulfonates, N-acylated caprol~ct~me, and monobenzoyltetraacetyl glucose benzoyl peroxides. rreferred c~tinnic peroxyacid precursors of the N-acylated caprol~ct~m class include the trialkyl ammonium methylene benzoyl caprol~ct~me and the trialkyl ammonium methylene alkyl caprol~ct~m~.

Benzoxazin or~anic peroxyacid precursors Also suitable are precursor compounds of the benzox~7in-type, as disclosed for example in EP-A-332,294 and EP-A~82,807, particularly those having the formula:

~N"C R1 wherein Rl is H, alkyl, alkaryl, aryl, or arylalkyl.

Preformed orPanic peroxyacid The organic pero~yacid ble~rhing ~ysLe~ may contain, in ~ lition to, or as an alternative to, an organic peroxyacid bleach precursor compound, a preformed organic peroxyacid, typically at a level of from 1 % to 15% by weight, more prefe.ably from 1 % to 10% by weight of the composition.

A preferred class of organic peroxyacid compounds are the amide sl~bstitntefl compounds of the following general formlll~e:

CA 02226620 1998-01-12 ,.
W O 97/03160 PCT~US96/11105 O R5 0 or R5 0 0 wherein Rl is an alkyl, aryl or alkaryl group with from 1 to 14 carbon atoms, R2 is an alkylene, arylene, and alkarylene group cont~inin~ from 1 to 14 carbon atoms, and R5 is H or an aL~yl, aryl, or alkaryl group cont~inin~ 1 to 10 carbon atoms. Amide substituted organic peroxyacid compounds of this type are described in EP-A-0170386.

Other organic peroxyacids include diacyl and tetraacylperoxides, especially diperoxydodec~nP~1ioc acid, diperoxytetradec~nP-lioc acid and diperoxyh~x~lec~ne~liQc acid. Mono- and diper~7~1~ic acid, mono- and diperbrassylic acid and N-phthaloyl~minoperoxicaproic acid are also suitable herein.

Bleach catalyst The compositions optionally contain a transition metal cont~inin~ bleach catalyst. One suitable type of bleach catalyst is a catalyst ~y~lel~l comprising a heavy metal cation of defined bleach catalytic activity, such as copper, iron or m~n~nese c~tione~ an ~llxili~ry metal cation having little or no bleach catalytic activity, such as zinc or ~hlmimlm cations, and a sequestrant having defined stability conet~nts for the catalytic and ry metal c~tione~ particlll~rly ethylene~ min~tetr~cetic acid, ethylen~ minetetra(methylenephosphonic acid) and water-soluble salts thereof. Such catalysts are disclosed in U.S. Pat. 4,430,243.

Other types of bleach catalysts include the m~n~n~se-based complexes disclosed in U.S. Pat. 5,246,621 and U.S. Pat. 5,244,594. P~efelled e~amples of these catalysts include MnIV2(u-o)3(l ,4,7-trimethyl-1,4,7 triazacyclononane)2-(PF6)2, MnIII2(u-O) 1 (u-OAc)2(1,4,7-trimethyl-1~4~7-triazacyclonons~n~o)2-(clo4)2~ MnIV4(u-0)6(1,4,7-triazacyclonon~ne)4-(C104)2, MnIIIMnIV4(u-0)1(u-OAc)2 (1,4,7-trimlothyl-l~4~7-triazacyclonon~ne)2-(clo4)3~ and mix~lres thereof.
Others are described in European patent application publication no.
549,272. Other li~~n-ls suitable for use herein include 1~s~9-~rim~th =
CA 02226620 l998-0l-l2 WO97/03160 PCT~US96/lllOS

1,5,9-tri~cyclododecane, 2-methyl-1,4,7-triazacyclononane, 2-methyl-l ,4,7-tria7~cyclonon~ne, 1,2,4,7-tetramethyl-1,4,7-triazacyclonon~n~o, and mixtures 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~r-h~s mononuclear m~ng~nese (rV) complexes such as Mn(1,4,7-tAmethyl-1,4,7-tri~7~cyclononane)(OCH3)3 (PF6). Still another type of bleach catalyst, as disclosed in U.S. Pat. 5,114,606, is a water-soluble comple~c of m~ng~n~se (III), and/or (IV) with a ligand which is a non-carboxylate polyhydroxy compound having at least three consecutive C-OH groups.
Other examples incl~ e binuclear Mn complexed with tetra-N~ent~te and bi-N~lent~te lig~n-le, including N4MnIII(u-0)2MnIVN4)+and [Bipy2MnIII(u-0)2MnIVbipy2]-(C104)3 .

Further suitable bleach catalysts are described, for example, in European patent application No. 408,131 (cobalt complex catalysts), Eu~opean patent applic~tion~ public~tion nos. 384,503, and 306,089 (met~11~
porphyrin catalysts), U.S. 4,728,455 (m~n~nese/mlllti(1~nt~te ligand catalyst), U.S. 4,711,748 and European patent application, publication no. 224,952, (absorbed m~ng~nese on ~hlminosilic~te catalyst), U.S.
4,601,845 (~hlminosilicate support with m~n~nese and zinc or m~n~Sillm salt), U.S. 4,626,373 (m~ng~nese/ligand catalyst), U.S.
4,119,557 (ferric complex catalyst), German Pat. specific~tion 2,054,019 (cobalt çhel~nt catalyst) C~n~ n 866,191 (transition metal-co..~
salts), U.S. 4,430,243 (chel~nt~ with m~ng~nPse c~tion~ and non-catalytic metal cations), and U.S. 4,728,455 (m~ng~nese gluconate catalysts).

Heavy metal ion se~uestrant The deLer~c~t compositions of the invention plefelably contain as an optional component a heavy metal ion sequestrant. By heavy metal ion sequestrant it is meant herein components which act to sequester (ch~l~te) heavy metal ions. These components may also have calcium and m~s~nesillm chelation capacity, but ~rerele~tially they show selectivity to binding heavy metal ions such as iron, m~ng~n~se and copper.
-W O 97/03160 PCT~US96/11105 Heavy metal ion sequestrants are generally present at a level of from 0.005% to 20%, preferably from 0.1% to 10%, more ~,eferably from 0.25 % to 7.5 % and most preferably from 0.5 % to 5 % by weight of the compositions.

Suitable heavy metal ion sequestrants for use herein include organic phosphonates~ such as the amino alkylene poly (alkylene phosphQn~e~), alkali metal ethane 1-hydroxy disphosphon~tes and nitrilo trimethylene phosphonates.

Preferred among the above species are diethylene tri~mine penta (methylene phosphon~te), ethylene ~ mine tri (methylene phosphon~te) he~methylene ~ mine tetra (methylene phosphonate) and hydro~y-ethylene 1,1 diphosphon~te.

Other suitable heavy metal ion sequestrant for use herein in~ de nitrilotri~cetic acid and polyaminocarboxylic acids such as ethylenP,~ minotetracetic acid, ethylenetri~mine pent~cetic acid, ethyl~-nP~ minP disuccinic acid, ethylenP~ minP, ~lighlt~ric acid, 2-hydro~yL,ropylP-nP~i~minP disuccinic acid or any salts thereof. Especially preferred is ethyhPnp~ minp~-N~Nl-disuccinic acid (EDDS) or the alkali metal, ~lk~linP, earth metal, ammonium, or s~bsti~ltefl ~mmnninm salts thereof, or mixtures thereof.

Other suitable heavy metal ion sequestrants for use herein are imino~ cetic acid derivatives such as 2-hydroxyethyl ~i~cetic acid or glyceryl i~no diacetic acid, described in EP-A-317,542 and EP-A-399,133. The iminoAi~cetic acid-N-2-hydro,~y~r~yl sulfonic acid and aspartic acid N-carboxymethyl N-2-hydroxypropyl-3-sulfonic acid sequestrants ~1escrihed in EP-A-516,102 are also suitable herein. The ,B-~l~nine-N,N'-diacetic acid, aspartic acid-N,N'-~ cetir. acid, aspartic acid-N-mono~cetic acid and imino~ ccinic acid sequestrants described in EP-A-509,382 are also suitable.

CA 02226620 1998-01-12 ,..

W O 97/03160 PCT~US96/lllO5 EP-A~76,257 describes suitable amino based sequestrants. EP-A-510,331 describes suitable sequestrants derived from collagen, keratin or casein. EP-A-528,859 describes a suitable alkyl iminodiacetic acid sequestrant. Dipicolinic acid and 2-phosphonobutane-1,2,~tricarboxylic acid are alos suitable. Glycin~mi~le-N,N'-disuccinic acid (GADS), ethylene~ minP-N-N~iElllt~tic acid (EDDG) and 2-hydroAypr~ylçr e~ mine-N-N'-disuccinic acid (HPDDS) are also suitable.

Enzyme Another preferred ingredient useful in the detergent compositions is one or more ~ ition~l enzymes.

Prer~lled additional enzymatic m~teri~l~ include the commercially available lip~es, c~ltin~ces~ cellulases, neutral and ~lk~lin~ proteases, esterases, pectin~es, l~ct~ses and pero~ci~ es conventionally incorporated into detergent compositions. Suitable enzymes are discussed in US Patents 3,519,570 and 3,533,139.

Plefelled commercially available protease enzymes include those sold under the tr~-len~mes Alcalase, Savinase, Primase, Durazym, and Esperase by Novo ~n~ tries A/S (Denm~rk), those sold under the tr~len~m~ M~t~e, ~c~l and Maxapem by Gist-Broc~-les, those sold by Genencor Intern~tion~l, and those sold under the tr~dçn~m~
Opticle~n and Optimase by Solvay Enzymes. Protease enzyme may be incorporated into the compositions in accordance with the invention at a level of from 0.0001% to 4% active enzyme by weight of the composition.

Lipolytic enzyme may be present at levels of active lipolytic enzyme of from 0.0001% to 2% by weight, preferably 0.001% to 1% by weight, most ~lefeldbly from 0.001% to 0.5 % by weight of the compositions.

The lipase may be fungal or bacterial in origin being obt~in~l, for e~cample, from a lipase producing strain of Humicola sp., Thermomyces W O 97/03160 PCTrUS96/lllO5 sp. or Pseudomonas sp. including Pseudomonas pseudoalcaligenes or Pseudomas fluorescens. Lipase from chemically or genetically modified mllt~nt~ of these strains are also useful herein. A ~rerelred lipase is derived from Pseudomonas pseudoalcaligenes, which is described in Granted European Patent, EP-B-0218272.

Another preferred lipase herein is obtained by cloning the gene from Humicola l~nll~inosa and expressing the gene in Aspergillus orvza, as host, as described in European Patent Application, EP-A-0258 068, which is commercially available from Novo ~n~ ctri A/S, Bagsvaerd, Denm~rk, under the trade name Lipolase. This lipase is also described in U.S.
Patent 4,810,414, Huge-Jensen et al, issued March 7, 1989.

Organic polymeric compound Organic polymeric compounds are preferred ~ ition~l components of the dete~ent composition~ in accord with the inVpntion~ and are ~refe~ably present as components of any particulate components where they may act such as to bind the particulate component together. By organic polymeric compound it is meant herein essenti~lly any polymeric organic compound commonly used as dispersants, and anti-redeposition and soil suspension agents in delergent compositions, including any of the high molec~ r weight organic polymeric compounds described as clay flocc~ ting agents herein.
Organic polymeric compound is typically incorporated in the deterge~t compositions of the invention at a level of from 0.1% to 30%, preîelably from 0.5% to 15%, most prerelably from 1% to 10% by weight of the compositions.
F~mples of organic polymeric compounds include the water soluble organic homo- or co-polymeric polycarboxylic acids or their salts in which the polycarbo~cylic acid comprises at least two carbo~cyl rs~di~
separated from each other by not more than two carbon atoms. Polymers of the latter type are disclosed in GB-A-1,596,756. Fx~mples of such salts are polyacrylates of MWt 2000-5000 and their copolymers with = ~

W O97/03160 PCT~US96/11105 maleic anhydride, such copolymers having a molecular weight of from 20,000 to 100,000, especially 40,000 to 80,000.
The polyamino compounds are useful herein including those derived from aspartic acid such as those disclosed in EP-A-305282, EP-A-305283 and EP-A-351629.

Terpolymers co~ ..in~ monomer units selected from maleic acid, acrylic acid, polyaspartic acid and vinyl alcohol, particularly those having an average molecular weight of from 5,000 to 10,000, are also suitable herein.

Other organic polymeric compounds suitable for incorporation in the deLe,gellt compositions herein include cellulose derivatives such as methylcelllllose, carboxymethylcellulose, hydro~y~lu~ylmethylcellulose and hydro~yelhyicellulose.
Further useful organic polymeric compounds are the polyethylene glycols, particularly those of molec~ r weight 1000-10000, more particularly 2000 to 8000 and most ~rereldbly about 4000.
Suds ~u~ ssinv ~y~

The dete,ge~t compositions of the invention, when formlll~te~l for use in m~chine washing compositions, ~refe,ably comprise a suds ~u~pressi~g ~y~ present at a level of from 0.01 % to 15 %, preferably from 0.05 %
to 10%, most ~l~refably from 0.1 % to 5% by weight of the composition-Suitable suds ~u~plessing ~y~le~s for use herein may com~rise essenti~llyany known ~ntifo~m compound, including, for example .~ one ~ ;
compounds and 2-alkyl alcanol antifoam compounds.
By ~ntifo~m compound it is meant herein any compound or mi~ctures of compounds which act such as to depress the fo~min or s~ in~ pro~lllce i by a solution of a deterge~t composition~ particularly in the presence of ~it~tion of that solution.

W O 97/03160 PCT~US96/11105 Particularly preferred antifoam compounds for use herein are silicone antifoam compounds defined herein as any ~ntifo~m compound inchl-lin~
a silicone component. Such silicone antifoam compounds also typically cont~in a silica component. The term "silicone" as used herein, and in general throughout the in-lllstry, encompasses a variety of relatively high molecular weight polymers cont~inin~ siloxane units and hydrocarbyl group of various types. Preferred silicone antifoam compounds are the siloxanes, particularly the polydimethylsilo~canes having trim.othylsilyl end blocking units.

Other suitable antifoam compounds incl~l-le the monocarbo~cylic fatty acids and soluble salts thereof. These m~teri~1s are described in US
Patent 2,954,347, issued September 27, 1960 to Wayne St. John. The monocarboxylic fatty acids, and salts thereof, for use as suds ~u~ressor typically have hydrocarbyl chains of 10 to 24 carbon atoms, ~re~eiably 12 to 18 carbon atoms. Suitable salts include the alkali metal salts such as sodium, pot~sillm, and lithillm salts, and ~mmonillm and alkanol~mmonillm salts.
Other suitable ~ .ro~m compounds include, for example, high moleclll~3r weight fatty esters (e.g. fatty acid triglycerides), fatty acid esters of monovalent alcohols, aliphatic Clg-C40 ketones (e.g. stearone) N-alkylated amino tri~7in~s such as tri- to hexa-alkylmel~mines or di- to tetra alkykli~mine chlortri~7ines formed as products of cyanuric 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 monoste~
di-alkali metal (e.g. sodium, pot~illm, lithillm) phosphates and phosphate esters.
A yrefelred suds ~u~ressing system comprises (a) antifoam compound, plefel~Lbly silicone antifoam compound, most ple~rably a silicone antifoam compound co~ ising in combination CA 02226620 l998-0l-l2 W O 97/03160 PCT~US96/11105 (i) poly limetllyl siloxane, at a level of from 50~ to 99%, preferably 75 % to 95 % by weight of the silicone antifoam compound; and (ii) silica, at a level of from 1% to 50%, preferably ~ % to 25 %
by weight of the silicone/silica antifoam compound;

wherein said silica/.~ilicone antifoam compound is incorporated at a level of from 5% to 50%, l,fefe~dbly 10% to 40% by weight;

(b) a di~elsant compound, most preferably comprising a silicone glycol rake copolymer with a polyoxyalkylene contt~nt of 72-78 %
and an ethylene oxide to propylene oxide ratio of from 1:0.9 to 1:1.1, at a level of from 0.5% to 10%, ~referably 1% to 10% by weight; a particularly ~lefelred silicone glycol rake copolymer of this type is DCO544, commercially available from DOW Corning under the tr~ -n~mlo. DCO544;

(c) an inert carrier fluid compound, most preferably com~-ising a C16-Clg ethoxylated alcohol with a degree of etho~ylation of from 5 to 50, ~rerelably 8 to lS, at a level of from 5% to 80%, prGfeldbly 10% to 70%, by weight;

A highly l,lG~erf~d particulate suds suppressing ~y~le~ is described in EP-A~210731 and com~lises a silicone antifoam compound and an organic carrier m~t~.ri~l having a melting point in the range 50~C to 85~C, wherein the organic carrier m~teri~l CO~p- ;ses a monoester of ~lycerol and a fatty acid having a carbon chain cont~ining from 12 to 20 carbon atoms. EP-A ~210721 discloses other prerel,ed particulate suds ~u~lessing ~y~lems wherein the organic carrier m~t~-.ri~l iS a fatty acid or alcohol having a carbon chain cont~inin~ from 12 to 20 carbon atoms, or a ~i~lure tbereof, with a mPltin~ point of from 45~C to 80~C.

Clay softening ~y:ileul CA 02226620 l998-0l-l2 W O 97/03160 PCTrUS96/11105 The d~tergellt compositions may contain a clay softening ~ysle~
comprising a clay mineral compound and optionally a clay flocc~ tin agent.

The clay mineral compound is prereidbly a smectite clay compound.
Smectite clays are ~ close-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 Co~ ally describe suitable organic polymeric clay flocc~ tin~ agents.

CA 02226620 l998-0l-l2 W O97/03160 rcTrus96/lllos Polymeric dye transfer inhibitin~ a~ents The detelgent compositions herein may also comprise from 0.01% to 10 %, ~le~l~bly from 0.05% to 05% by weight of polymeric dye transfer inhibiting agents.
The polymeric dye transfer inhibiting agents are preferably selected from polya~ine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vi~yli~ olto, polyvillyl~yll~olidonepolymers or comb;n~tion~ thereof.

a) Polyamine N-oxide polymers Polyamine N-oxide polymers suitable for use herein cont~in units having the following structure formula:
p I

(I) I

wherein P is a polymeri~hle unit, and A is NC, CO, C, -O-, -S-, -N-; x is Q or 1;

R are ~lirh~tic~ ethoxylated ~lirh~tics, aromatic, heterocyclic or alicyclic glOU~S or any comhin~tion thereof whereto the nitrogen of the N-O group can be ~tt~r~h~d or wherein the nitrogen of the N-O group is part of these groups.

The N-O group can be represent~l by the following general structures:

CA 02226620 l998-0l-l2 W O 97/03160 PCT~US96/11105 (R1 ) X - I -(R2)Y

(R3)z or N-(R1 )x wherein Rl, R2, and R3 are aliphatic groups, aromatic, heterocyclic or alicyclic groups or combinations thereof, x or/and y or/and z is 0 or 1 and wherein the nitrogen of the N-O group can be ~tt~ch~ or wherein the nitrogen of the N-O group forms part of these groups. The N-O group can be part of the polymPric~hle unit (P) or can be ~tt~che-l to the polymeric backbone or a combin~tion of both.

Suitable polyamine N-oxides wherein the N-O group forms part of the polymeric~hle unit co...l . ;ce polyal"ine N-oxides wherein R is selecte~l from ~lirh~tic, aromatic, alicyclic or heterocyclic groups. One class of said polyamine N-oxides com~lises the group of polyamine N-oxides 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 pyrrit1ine, pyrrole, imitl~ole, pyrrolidine, piperi~line, quinoline, ~crif1in~ and derivatives thereof.

Other suitable poly~ e N-oxides are the polyamine oxides whereto the N-O group is ~tt~h~ to the polymerisable unit. A ~le~red class of these poly~i~e N-oxides co~rises 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 function~l group is part of said R
group. F.~mples of these cl~cses are polyamine oxides wherein R is a heterocyclic compound such as pyrridine, pyrrole, imi-l~701e and derivatives thereof.
The polyamine N-oxides can be obtained in almost any degree of polymeric~tiQn The degree of polymerisation is not critical provided the m~teri~l has the desired water-solubility and dye-suspPn-ling power.
Typically, the average molec~ r weight is within the range of 500 to 1000,000.

CA 02226620 l998-0l-l2 WO 97/03160 PCT~US96/11105 b) Copolymers of N-vinylpyrrolidone and N-vinylimidazole Suitable herein are coploymers of N-vinylimi~ ole and N-vi~yl~yllolidone having an average molecular weight range of from 5,000 to 50,000. The preferred copolymers have a molar ratio of N-vinylimi~ ole to N-vinylpyrrolidone from 1 to 0.2.
c) Polyvinylpyrrolidone The detergent compositions herein may also utilize polyvinylpyrrolidone("PVP") having an average molecular weight of from 2,500 to 400,000.
Suitable polyvinyl~ylroli~lQnes are commercially vailable from ISP
Corporation, New York, NY and Montreal, ('~n~ under the product names PVP K-15 (viscosity molec~ r weight of 10,000), PVP K-30 (average molecular weight of 40,000), PVP K-60 (average molecular weight of 160,000), and PVP K-90 (average molecular weight of 360,000). PVP K-15 is also available from ISP Corporation. Other suitable polyv~yl~ylroli~lon~s which are commercially available from BASF Cooperation in-lu-le Sok~l~n HP 165 and Sok~l~n HP 12.
d) Polyvi"yloxazolidone The deler~ent compositions herein may also utilize polyvinylo~cazolidones as polymeric dye transfer inhibiting agents. Said polyvinyloxazolidones have an average molecnl~r weight of from 2,500 to 400,000.

ç) Polyvinylimid~ole The delel~e~t compositions herein may also utilize polyvil~ylimi~l~7Ole as polymeric dye transfer inhibiting agent. Said polyvinylimi~l~7oles preferably have an average molecular weight of from 2,500 to 400,000.

Optical brightener CA 02226620 l998-0l-l2 The deter~ellt compositions herein also optionally contain from about 0.005% to 5% by weight of certai~ types of hydrophilic optical bri~hten~rs.

Hydrophilic optical bri~htçn~rs useful herein include those having the structural formula:
~ON~ I ~ IH Hl ~NI ~NNO~N

wherein Rl is selected from ~nilino, N-2-bis-hydroxyethyl and NH-2-hydro~yet~yl; R2 is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methyl~mino, morphilino, chloro and amino; and M is a salt-forming cation such as sodium or pot~sinm.

When in the above formula, Rl is anilino, R2 is N-2-bis-hydro,~ye~yl and M is a cation such as sodium, the brightener is 4,4' ,-bis[(4-~ni1ino-~(N-2-bis-hydro~y~l~yl)-s-tri~7-in~-2-yl)amino]-2,2'-stilbenç~ llfonic acid and disodium salt. This particular bri~htener species is commercially marketed under the tr~en~mP Tinopal-UNPA-GX by Ciba-Geigy Corporation. Tinopal-UNPA-GX is the yreferred hydrophilic optical bri~ht~n~or useful in the detelgellt 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 bright~ner is 4,4'-bis[(4-~nilino-~(N-2-hydroxyethyl-N-methyl~mino)-s-tri~7ine-2-yl)amino]2,2'-stilbenecli~lllfonic acid disodium salt. This particular bri~htener species is commercially marketed under the tr~e-n~me Tinopal SBM-GX by Ciba-Geigy Corporation.

When in the above formula, Rl is ~nilino, R2 is morphilino and M is a cation such as sodium, the bri~htener is 4,4'-bist(4-~nilino-~morphilino-s-tria_ine-2-yl)a_ino]2,2'-stilben~islllfonic acid, sodium salt. This WO97/03160 PCT~US96/11105 particular bri~htener species is co~ercially m~rk~te~l under the tr~le.n~m~ Tinopal AMS-GX by Ciba Geigy Corporation.

W O 97/03160 PCT~US96/11105 Cationic fabric softenin~ a~ents Cationic fabric softening agents can also be incorporated into compositions in accordance with the present invention. Suitable cationic fabric softe-nin~ agents include the water insoluble tertiary ~min.o.~ or dilong chain amide m~teri~l~ as disclosed in GB-A-l 514 276 and EP-B~
011 340.

Cationic fabric softenin~ agents 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~lipnts suitable for inclusion in the compositions of the invention incl~l~le perfumes, colours and filler salts, with sodium snlf~te being a L,refelled filler salt.

pH of the compositions The present compo.~ition~ ~rer~lably have a pH me~ red as a 1%
solution in ~listille~l water of at least 8.5.0, ~lefelably from 9.0 to 12.5, most ~re~bly from 9.5 to 11Ø

Form of the compositions The compositions in accordance with the invention can take a variety of physical forms including granular, tablet, bar and liquid forms. The compo.~ition.~ are particularly the so-called concentrated granular detergen~ compositions adapted to be added to a washing m~c.hine by means of a dispen~in~ device placed in the m~chin~ drum with the soiled fabric load.

In general, granular detergent compositions in accordance with the present invention can be made via a variety of methods including dry mi~cing, spray drying, agglomeration and gr~m-l~tion.

W O 97/03160 PCT~US96/11105 ~4 The mean particle size of ~e components of granular compositions in accordance with the invention should preferably be such that no more that 5 5~ of particles are greater than 1 .7mm in diameter and not more than 5 %
of particles are less than 0.15mm in diameter.

The term mean particle size as defined herein is calculated by sieving a sample of the composition into a number of fractions (typically 5 fractions) on a series of Tyler sieves. The weight fractions thereby obtained are plotted ~.~pin~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 detergent compositions in accordance with the present invention typically have a bulk density of at least 600 g/litre, more ~rert;lably from 650 g/litre to 1200 g/litre. Bulk density is m~s~lred by means of a simple funnel and cup device con~icting of a conic~l funnel moulded rigidly on a base and provided with a flap valve at its lower extremity to allow the conte-nt~ of the funnel to be emptied into an axially ~lignPA cylindrical cup disposed below the funnel. The funnel is 130 mm high and has intern~ meters of 130 mm and 40 mm at its respective upper and lower extremities. It is mounted so that the lower e~tremity is 140 mm above the upper surface of the base. The cup has an overall height of 90 ~, an intern~l height of 87 mm and an intçrn~ m~ter of 84 mm. Its nominal volume is 500 ml.

To carry out a m~ rem~nt, the fur~el is filled with powder by hand pouring, the flap valve is ope~ed 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 obtained for the weight of powder doubled to provide a bulk density in g/litre. Replicate me~ remf~ntS are made as required.

Surfactant agglomerate particles W O97103160 PCT~US96111105 The cationic ester surf~ct~nt herein, plefelably with ~ tional surf~ct~nte, is preferably present in granular compositions in the form of surfactant 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 agglomerating powders (e.g. ~ mino.cilic~te, carbonate) with high active surf~ct~nt pastes and to control the particle size of the resultant agglomerates within specified limits. Such a process involves mi~cinp an effective amount of powder with a high active surfactant paste in one or more agglomerators such as a pan agglomerator, a Z-blade mixer or more yrefelably an in-line mixer such as those m~nllf~ct~lred by Schugi (Holland) BV, 29 Chroomstraat 8211 AS, Lelystad, Netherlands, and Gebruder Lodige ~echinenh~ll GmbH, D4790 Paderborn 1, Flsen~rstraSSe 7-9, Postf~ch 2050, Germany. Most ~lere~bly a high shear mixer is used, such as a Lodige CB (Trade Name).

A high active surf~ct~nt paste comprising from 50% by weight to 95% by weight, preferably 70% by weight to 85% by weight of surf~ct~nt is typically used. The paste may be pumped into the agglomerator at a temperature high enough to m~int~in a pumpable 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.

T ~mdry washin~ method ~chine laundry methods herein typically comprise treating soiled laundry with an aqueous wash solution in a washing m~chine having dissolved or dispensed therein an effective amount of a m~chin.o laundry delerge~t compo~ition in accord with the invention. By an effective amount of the detergenl composition it is meant from 40g to 300g of product dissolved or dispersed in a wash solution of volume from 5 to 65 litres, as are typical product dosages and wash solution volumes commonly employed in conv~ntion~l machine laundry methods.

W O97/03160 PCT~US96/11105 In a preferred use aspect a dispensing device is employed in the washing method. The dispensing device is charged with the deter~e~t product, and is used to introduce the product directly into the drum of the washing m~chine before the commpncement of the wash cycle. Its volume capacity should be such as to be able to contain s lfficient dt;Le~gellt product as would normally be used in the w~hin~ method.

Once the washing m~chine has been loaded with laundry the dispen~in~
device cont~ining the detergent product is placed inside the drum. At the commencem~ont of the wash cycle of the w~hin~ m~chine water is introduced into the drum and the drum periodically rotates. The design of the dispensing device should be such that it permits cont~inmtont of the dry detergellt product but then allows release of this product during the wash cycle in response to its agitation as the drum rotates and also as a result of its contact with the wash water.

To allow for release of the detergent product during the wash the device may possess a number of openings through which the product may pass.
Altern~tively, the device may be made of a m~t~ri~l which is permP~ble to liquid but impermeable to the solid product, which will allow release of dissolved product. PlG~lably, the delelgellt product will be rapidly rele~se~l at the start of the wash cycle thereby providing tr~nsi~-nt loc~ l high concentrations of product in the drum of the washing m~chine at t_is stage of the wash cycle.

P~ert;lled dispen~in~ devices are reusable and are de~ ne~ in such a way that cont~intor integrity is m~int~in~-l in both the dry state and during the wash cycle. Especially yrer~lled dispensing devices for use with the composition of the invention have been described in the following p~t~ntc;
GB-B-2, 157, 717, GB-B-2, 157, 718, EP-A-0201376, EP-A~288345 and EP-A-0288346. An article by J.Bland published in M~n~lf~ctllrin~
Ch~mist, November 1989, pages 4146 also describes especially prefe~led dispensing devices for use with granular laundry products which are of a type commonly know as the "gr~mllette". Another preferred dispen~inE~
device for use with the compositions of this invention is disclosed in PCT
Patent Application No. WO94/11562.

CA 02226620 l998-0l-l2 W O 97/03160 PCTrUS96/lllOS

Especially preferred dispensing devices are disclosed in European Patent Application Publication Nos. 0343069 & 0343070. The latter Application discloses a device comprising a flexible sheath in the form of a bag exte.n~lin~ from a support ring defining an orifice, the orifice being adapted to admit to the bag sufficient product for one washing cycle in a washing process. A portion of the washing medium flows through the orifice into the bag, dissolves the product, and the solution then passes outwardly through the orifice into the washing me~illmt The support ring is provided with a m~king arrangemnt to prevent egress of wetted, ~n~li.c~olved, product, this arrangement typically comprising radially e~te.n~lin~ walls e~t~n~ing from a central boss in a spoked wheel configuration, or a ~imil~r structure in which the walls have a heliC~
form.
,~lte.rn~tively, the dispensing device may be a flexible container, such as a bag or pouch. The bag may be of fibrous construction coated with a water impermeable protective material so as to retain the co..te..ls, such as is disclosed in European published Patent Application No. 0018678.
Alternatively it may be formed of a water-insoluble synthetic polymeric material provided with an edge seal or closure ~1eSi~n~ to l~tule in aqueous media as disclosed in European published Patent Application Nos.0011500,0011501,0011502, and 0011968. A convenient form of water frangible closure comprises a water soluble adhesive disposed along and s~lin~ one edge of a pouch formed of a water impermeable polymeAc film such as polyethylene or poly~lo~ylene.
Packa~ing for the compositions Commercially marketed executions of the bleaching composition.s can be packaged in any suitable container including those constructed from paper, cardboard, plastic materials a~d any suitable l~min~t~s. A
~referred p~k~inf~ e~cecution is described in European Application No.
94921505.7.

WO97/03160 PCTrUS96tlllO5 Abbreviations used in Examples ID the detel~ent compositions, the abbreviated component i~le.n~ific~tion.c have the following me~nin LAS : Sodium linear C12 alkyl ben7:~n~, sulfonate TAS : Sodium tallow alkyl sulfate C45AS : Sodium C14-C1s linear alkyl sulfate CxyEzS : Sodium Clx-C1y br~nch~rl alkyl slllf~te con~len.~ed with z moles of ethylene o~cide C45E7 : A C14 15 predomin~ntly linear primary alcohol con~en.~e~l with an average of 7 moles of ethylene oxide C25E3 : A C12 15 br~nche-l ~ri~al~ alcohol con(l~n~e~l with an average of 3 moles of ethylene o~cide C25E5 : A C12 15 br~n~h~tl primary alcohol con~en~e~
with an average of S moles of ethylene o~ide CEQ I : R1COOCH2CH2.N+(CH3)3 with R1 = C11-CEQ II : RlCOOCH2CH2CH2N+(CH3)3 with Rl--Cll-cl3 CEQ III RlCOO CH2 CH2 N~(CH3)2(CH2CH20H) with Rl=cll-cl3 CEQ IV : Rl COOCH2CH2 N+ (CH3CH2)2(CH3) with Rl =cll-cl3 QAS : R2.N + (CH3)2(C2H4OH) with R2 = C 12 - C 14 Soap : Sodium linear aLkyl carboxylate derived from an 80/20 mixture of tallow and COCO~lU~ oils.
TFAA : C16-C18 alkyl N-methyl gl~lc~mi~le TPKFA : C12-C14 topped whole cut fatty acids STPP : Anhydrous sodium tripolyphosphate Zeolite A : Hydrated Sodium ~ minnsilic~te of formula Nal2(A102SiO2)12. 27H20 having a primary particle size in the range from 0.1 to 10 micrometers CA 02226620 l998-0l-l2 W O 97/03160 PCTrUS96/11105 NaSKS-6 : Crystalline layered silicate of formula ~ -Na2Si20s Citric acid : Anhydrous citric acid Carbonate : Anhydrous sodium carbonate with a particle size between 20011m and 90011m Bicarbonate : Anhydrous sodium bicarbonate with a particle size distribution between 400~m and 1200~m Silicate : Amorphous Sodium Silicate (SiO2:Na2O; 2.0 ratio) Sodium sulfate: Anhydrous sodium slllf~te Citrate : Tri-sodium citrate dihydrate of activity 86.4~
with a particle size distribution between 425,um and 850 ,um MA/AA : Copolymer of 1:4 maleic/acrylic acid, average molecular weight about 70,000.
CMC : Sodium carbo~ymethyl celllllose Protease : Proteolytic enzyme of activity 4KNPU/g sold by NOVO ~n~ etrie~e A/S under ~che tr~n~me Savinase Alcalase : Proteolytic enzyme of activity 3AU/g sold by NOVO ~n~lstries A/S
Cellnl~ee : Cellulytic enzyme of activity 1000 CEVU/g sold by NOVO Tn~llstries A/S under the tr~1en~me Carezyme Amylase : Amylolytic enzyme of activity 120KNU/g sold by NOVO Tn-l~lstries A/S under the tr~lçn~m~
Termamyl 120T
.ip~e : Lipolytic enzyme of activity 100kLU/g sold by NOVO Tn~lllstries A/S under the tr~-len~m~
Lipolase Erldolase : Endo~ll-n~e enzyme of activity 3000 CEVU/g sold by NOVO ~n~lllstries A/S
PB4 : Sodium perborate tetrahydrate of nominal formula NaBO2.3H2O-H2o2 PBl : Anhydrous sodium perborate bleach of nominal formula NaBo2.H2o2 W O 97/03160 PCTrUS96/11105 Percarbonate : Sodium Percarbonate of nominal formula 2Na2C03.3H202 NOBS : Nonanoyloxyben7~o.nt-. sulfonate in the form of the sodium salt.
TAED : Tetraacetylethylene~ minf-DTPMP : Diethylene tri~mine penta (methylene phosphonate), marketed by Monsanto under the Trade name Dequest 2060 Photoactivated : Sulfonated Zinc Phthlocyanine enc~rs~ tç~l in bleach ~lextrin soluble polymer Bri~ht~.ner 1 : Disodium 4,4'-bis(2-sulphostyryl)biphenyl Bri~ht~.ner 2 : Disodium 4,4'-bis(~nilino-6-morpholino-1.3.5-tria7in-2-yl)a_ino) stilbene-2:2'~i.~nl~onate.
HEDP : 1,1-hydroxyethane diphosphonic acid PVNO : Polyvinyl~yridine N-oxide PVPVI : Copolymer of polyvinylpyrolidone and vinylimi-l~7Ole SRP 1 : Sulfobenzoyl end capped esters with o~yet~ylene o~cy and terephtaloyl backbone SRP 2 :Diet_oxylated poly (1, 2 propylene terepht~l~te) short block polymer Silicone all~iroal-~ : Polyrlim~.thylsiloxane foam controller with .~ilo~ne-o~cyalkylene copolymer as dispersing agent with a ratio of said foam controller to said dispersing agent of 10:1 to 100:1.

CA 02226620 l998-0l-l2 W O 97/03160 PCT~US96/11105 In the following Examples all levels are quoted as % by weight of the composition:

Example 1 The following laundry detergellt compositions A to F were prepared in accord with the invention:

A B C D E F
LAS 8.0 8.0 8.0 8.0 8.0 8.0 C25E3 3.4 3.4 3.4 3.4 3.4 3.4 CEQ I - 0.8 4.5 2.0 - 0.7 CEQ II 6.0 0.5 - 0.7 2.0 0.8 QAS - - 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 Silicate 1.4 1.4 1.4 3.0 3.0 3.0 Sodium sulfate 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 TAED 1.5 1.5. 1.5 1.5 1.5 1.5 DETPMP 0.250.25 0.25 0.25 0.250.25 HEDP 0.3 0.3 0.3 0.3 0.3 0 3 Protease 0.260.26 0.26 0.26 0.260.26 CA 02226620 l998-0l-l2 WO 97tO3160 PCTrUS96/11105 Amylase 0.4 0.1 0.15 0.2 0.25 0.1 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~htPn~.r 1 O.Q9 0.09 0 09 0.09 0.09 o.og Perfume 0.3 0.3 0.3 0.3 0.3 0.3 Silicone antifoam 0.5 0.5 0.5 0.5 0.5 0.5 Misc/minors to 100%

Density in ~/litre 850 850 850 850 850 850 CA 02226620 l998-0l-l2 W O 97/03160 PCTnUS96/11105 Example 2 The following granular laundry detergent compositions G to I of bulk density 750 g/litre were prepared in accord with the invention 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 - 2.0 CEQ III 8.4 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 Silicate 6.8 W O 97/03160 PCTrUS96111105 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 e 0.15 0.15 0.15 Cell~ se 0.28 0.28 0.28 Amylase 0.1 0.1 0.1 MA/AA 0.8 1.6 1.6 CMC 0.2 0.4 0.4 Photoactivated bleach 15 ppm 27 ppm 27 ppm ~pm) Bri~ht~nçr 1 0.08 0.19 0.19 Bri~htt-.ner 2 - 0.04 0.04 Perfume 0.3 0.3 0.3 Silicone ~ntifo~m o.~ 2.4 2.4 Minors/misc to 100%

CA 02226620 l998-0l-l2 ..

Example 3 The following detel~ ent form~ tions, according to the present invention were prepared, where J is a phosphorus-cont~inin~ deter~ellt composition, K is a zeolite-cont~inin~ detergent composition and L is a compact detergent 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 ~I 2.0 Silicate 7.0 3.0 3.0 CMC 1.0 1.0 0.5 Bri~htenPr 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 antifoam 0.3 0.3 0 3 Perfume 0.3 0.3 0.3 Dry additives Carbonate 6.0 13.0 15.0 PB4 18.0 18.0 10.0 PBl 4.0 4.0 0 TAED 3.0 3.0 1.0 Photoactivated bleach 0.02 0.02 0.02 Protease 1.0 1.0 1.0 Lipase 0.4 0.4 0.4 CA 02226620 l998-0l-l2 W O97/03160 PCT~US96/11105 Amylase 0.25 0.30 0.15 Dry mixed sodium 3.0 3.0 5.0 sulfate R~l~nce (Moisture & 100.0 100.0 100.0 Miscellaneous) Density (~/litre) 630 670 670 , W O 97/03160 PCTrUS96/lllOS

Example 4 The following nil bleach-cont~inin~ detergent formulations of particular use in the washing of colored clothing, according to the present 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 0.5 CEQ 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 Zeolite A 10.0 15.0 13.0 CMC - o 5 MA/AA - - 2.0 Carbonate 9.0 7.0 7.0 Spray On Perfume 0.3 0.3 0 5 C45E7 4.0 4.0 4.0 C25E3 2.0 2.0 2.0 Dry additives MA/AA - 3.0 NaSKS-6 - - 12.0 Citrate 10.0 - 8 .0 Bicarbonate 7.0 3.0 5 0 Carbonate 8.0 5.0 7.0 PVPVI/PVNO 0.5 0.5 0.5 SUBSTITUTE SHEET ~RULE 2B) , CA 02226620 l998-0l-l2 W O 97/03160 PCT~US96/11105 Alcalase 0.5 0.3 0 g Lipase 0.4 0.4 0.4 Amylase 0.6 0.2 0.7 Cellulase 0.6 0.6 0.6 Silicone antifoam 5.0 5.0 5 0 Dry additives Sodium sulfate 0.0 9.0 0 0 Balance (Moisture and 100.0 100.0 100.0 Miscellaneous) Density (g/litre) 700 700 700 SUBSTITUTE SHEET (RULE 26) W O 97/03160 PCT~US96/11105 Example 5 I

The following deter~,ent form~ tions, according to the present invention 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 III 0.4 - 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 ir~e 0.2 0.1 0.2 0.1 Cellulase 0.15 0.05 Photoactivated70ppm 45ppm - 10ppm bleach (ppm) Bri~hte.n~.r 1 0.2 0.2 0.08 0.2 PB 1 6.0 2.0 NOBS 2.0 1.0 R~l~nce 100 100 100 100 (Moisture and Miscellaneous) W O97/03160 PCT~US96/11105 Example 6 The following detergent form~ tion~, according to the present inventionwere prepared:
T U V
Blown Powder Zeolite A 30.0 22.0 6.0 Sodium sulfate 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 C E Q II - 0.4 2.5 C E Q IV 1.5 l.S O.S
Silicate - 1.0 5.0 Soap - - 2.0 Brighte.ner 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 Lipase 0.4 0.4 0.4 Amylase 0.1 0.3 0.6 C~ e 0.1 0.1 0.1 NOBS - 6.1 4.5 PB1 1.0 5.0 6.0 Sodium sulfate - 6.0 R~l~nce (Moisture 100 100 100 and ~i~cçll~neous) W O 97/03160 PCTrUS96/11105 Example 7 The following high density and bleach-cont~inin~ dete~e,~t form~ tion~,according to the present invention were prepared:
W X Y

Blown Powder Zeolite A 15.0 15.0 15.0 Sodim sulfate 0.0 5.0 0.0 LAS 3.0 3.0 3.0 QAS - 1.5 1.5 CEQ II 0.5 0.5 CEQ III 0.9 1.2 2.5 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 Perfume 0.3 0.3 0.3 C45E7 2.0 2.0 2.0 C25E3 2.0 - -Dry additives Citrate 5.0 - 2.0 Bicarbonate - 3.0 Carbonate 8.0 15.0 10.0 TAED 6.0 2.0 5.0 PB 1 14.0 7.0 10.0 Polyethylene o~cide of MW - - 0.2 5,000,000 Bentonite clay - - 10.0 Protease 1.0 1.0 1.0 CA 02226620 1998-01-12 .-W O97/03160 PCT~US96/11105 Lipase 0.4 0.4 0 4Amylase 0.6 1.0 0.8 Cellulase 0.6 0.6 0.6 Silicone antifoam 5.0 5.0 5.0 Dry additives Sodium sulfate 0.0 3.0 0.0 R~l~nr.e (Moisture and 100.0 100.0 100.0 Miscellaneous) Density (~/litre) 850 850 850 W O 97/03160 PCT~US96/11105 Example 8 The following high density detergent form~ tions, according to the present invention were prepared:

Z AA

Agglomerate C45AS 11.0 14.0 CEQ IV 3.8 2.2 Zeolite A 15.0 6.0 Carbonate 4.0 8.0 MA/AA 4.0 2.0 CMC 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 Percarbonate 20.0 20.0 SRP 1 0.3 0.3 Protease 1.4 1.4 Lipase 0.4 0.4 Cellulase 0.6 0.6 Amylase 0.6 0.2 Silicone antiroam 5.0 5.0 Bri~htener 1 0.2 0.2 Bri~hten~r 2 0.2 R~l~nce (Moisture and 100 100 Miscellaneous) Density (g/litre) 850 850 CA 02226620 l998-0l-l2 ~,Y~mrle 9 The following liquid detergent formulations, according to the present invention were prepared:
AB AC AD AE AF AG AH AI
CEQ I 0.4 1.0 0.8 0.4 2.6 1.5 1.0 2.5 CEQ II 0.6 1.2 0.7 0. 1.2 0.5 2.5 1.5 LAS 10. 13.0 9.0 - 25.0 o C25AS 4.0 1.0 2.0 10. - 13.0 18.0 15.0 o 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 QAS - - - - 3.0 1.0 TPKFA 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/tetradecenyl 12. 10.0 - - 15.0 succinic acid 0 Oleic acid 4.0 2.0 1.0 - 1.0 Ethanol 4.0 4.0 7.0 2.0 7.0 2.0 3.0 2.0 1,2 Propanediol 4.0 4.0 2.0 7.0 6.0 8.0 10.0 13.-Mono Ethanol Amine - - - 5.0 - - 9.0 9.0 Tri Ethanol Amine - - 8 - - - - -NaOHup topH 8.0 8.0 7.6 7.7 8.0 7.5 8.0 8.2 Ethoxylated 0.5 - 0.5 0.2 - - 0.4 0.3 tetraethylene pent~mine DTPMP 1.0 1.0 0.5 1.0 2.0 1.2 1.0 SRP 2 0.3 - 0.3 0.1 - - 0.2 0.1 PVNO - - - - - - - 0.10 Protease 0.5 0.5 0.4 0.2 - 0.5 0.3 0.6 s SUBSTITUTE SHEET ~RULE 26) CA 02226620 l998-0l-l2 W O 97/03160 PCTrUS96/11105 Alcalase - - - - 1.5 Lipase - 0.10 - 0.0 - - 0.15 0.15 Amylase 0.2 0.3 0.6 0.5 0.1 0.9 0.6 0.8 S
Cellulase - - - 0.0 - - 0.15 0.15 s 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 Bentonite clay - - - - 4.0 4.0 Suspending clay SD3 - - - - 0.6 0.3 Balance (Moisture and 100 100 100 100 100 100 100 100 Miscellaneous) SUBS~n SEEr (~E ~6)

Claims (11)

WHAT IS CLAIMED IS:

1. A detergent composition comprising (a) a cationic ester surfactant; and (b) an amylolytic enzyme present at a level of from 0.05% to 5.0%
by weight of said detergent composition, on a 120 KNU/g activity 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 amylolytic enzyme is present at a level from 0.1% to 3.0% by weight of the detergent composition, on a 120 KNU/g activity 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.

8. A detergent composition according to any of Claims 1 to 7, wherein the amylolytic enzyme is an .alpha.-amylase.

9. A detergent composition according to any of Claims 1 to 8 wherein an cellulase or endolase enzyme is present, or mixtures thereof.

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

11. 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 10 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.