CA2226621A1 - Detergent compositions - Google Patents

Abstract

There is provided a surfactant system comprising: (a) an anionic sulfate surfactant component; (b) a cationic ester surfactant; and (c) a hydrophilic alkoxylated nonionic surfactant having a HLB value of at least 9.1, wherein the weight ratio of anionic sulfate surfactant component to cationic ester surfactant is from 2.5:1 to 20:1 and the weight ratio of anionic sulfate surfactant component to hydrophilic alkoxylated nonionic surfactant is from 1:5 to 5:1. Alternatively, component (c) is a hydrophilic surfactant system comprising a plurality of nonionic surfactant components.

Description

W O 97/03164 PCTrUS96/11298 Detc~ composition~

Technical field The present invention relates to a three component surfactant system suitable for incorporation in de~ergellt compositions clesi~ned for use in laundry and dish washing methods.

Back~ u,ld 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 challenge faced by the form~ tor of detergent compositions for use in machine laundry and dishwashing methods. Surf~ct~n~ components have traditionally been employed in deter~ellt products to facilitate the removal of such greasy soils/stains. In particular, surfactant ~y~lellls comprising cationic esters have been described for use in greasy soil/stain removal.

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

~ US-A-4,228,042 discloses biodegradable cationic surfactants, including cationic ester surfactants for use in detergent compositions to provide greasy/oily soil removal. The combination of these cationic surfactants with nonionic surfactants in compositions designed for particulate soil W O 97/03164 PCTrUS96tll298 removal is also described. Anionic surfactants are disclosed as optional components of the compositions, but are present at Iow levels relative to the cationic surfactant component.

US-A-4,239,660 discloses laundry detergent compositions cont~ining cationic ester surfactant and nonionic surfactant at defined weight ratios.
Anionic surf~ct~nt~ are disclosed as optional components.

US-A-4,260,529 discloses laundry detergent compositions having a pH of no greater than 11 cont~inin~ cationic ester surfactant and nonionic surfactant at defined weight ratios. Anionic surfactants are disclosed as optional components of the compositions, but are present at low levels relative to the cationic ester surfactant component.

Anionic sulfate surfactants, particularly aL~yl sulfate and aL~cyl ethoxysulfate surfactants are also known to be useful components of deterge,lt compositions designed for greasy soil/stain removal. For example, WO 93/18124 discloses compositions cont~inin~ a mixed alkyl sulfate and alkyl ethoxysulfate surfactant ~yslelll.

It is desirable to combine the greasy soil/stain removal capability of anionic sulfate and cationic ester surfactants in a single surfactant system.
The Applicants have however, now found that a problem in combining cationic ester surfactants with anionic sulfate surfactants is the tendency for insoluble cationic:anionic sulfate complexes to form. This in fact, can lead to a marked reduction in greasy soil/stain removal ptlro~mance of the combined surfactant system.

Surprisingly, the Applicants have found that if hydrophilic nonionic surf~ct~nt, particularly hydrophilic alkoxylated nonionic surfactant is added to the combined surf~t~n~ syslelll the aforementioned problem may be ameliorated and significant greasy soil/stain removal performance benefits re~ e~l. By contrast, the addition of a hydrophobic alkoxylated surfactant does not ameliorate the problem.

All documents cited in the present description are, in relevant part, incorporated herein by reference.

CA 0222662l l998-0l-l2 W O 97/03164 PCTrUS96/11298 ~ Summ~ry of the Invention ~ According to the present invention there is provided a surfactant system comprising (a) an anionic sulfate surfactant component;

(b) a cationic ester surfactant; and (c) a hydrophilic alkoxylated nonionic surfactant having a HLB value of at least 9. 1 wherein the weight ratio of anionic sulfate surfactant component to cationic ester surf~ct~nt is from 2.5:1 to 20:1 and the weight ratio of anionic sulfate surfactant component to hydrophilic alkoxylated nonionic surfactant is from 1:5 to 5:1.

In one ~refel~ed aspect, the anionic sulfate component contains both alkyl sulfate and alkyl ethoxysulfate at a weight ratio of from 2:1 to 19:1.

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

IR5 - I +
Rl - C3 (CH)no (~u--(CH2)m--(Y)v--(CH2)t--N--R3 M

~4 wherein R1 is a Cs-C31 linear or branched alkyl, alkenyl or alkaryl chain or M-. N+(R6R7Rg)(CH2)S; X and Y, independently, are selected from the group consisting of COO, OCO, O, CO, OCOO, CONH,NHCO, OCONHNHCOO and CON(RgOR1o)Z, and CONR11Z wherein at least one of X or Y is a COO, OCO, OCOO, OCONH or NHCOO group; R2, R3, R4, R6, R7, R8 and R11 are independently selected from the group CA 0222662l l998-0l-l2 WO97/03164 PCTrUS96/11298 consisting of alkyl, alkenyl, hydroxyaL~yl, hydroxy-alkenyl and alkaryl groups having from 1 to 4 carbon atoms; Rg and R1o are independently selected from the group con.~i.ctin~ of linear or branched, saturated or ~1n~ rated carbon chains having from 1 to 8 carbon atoms; Z is a polyhydroxyhydrocarbyl moiety; and Rs is independently H or a C1-C3 alkyl group; wherein the values of m, n, s and t indepen~ent~y 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 and v is l; and wherein M is a counter anion.

In a further preferred aspect, the hydrophilic alkoxylated nonionic surfactant comprises ethoxylated alcohol surfactant having a degree of ethoxylation of at least 4.

According to another aspect of the present invention there is provided a surfactant system comprising (a) an anionic sulfate component;

(b) a cationic ester surfactant; and (c) a hydrophilic nonionic surfactant system comprising a plurality of nonionic surfactants having a HLB value of at least 9.1 wherein the weight ratio of anionic sulfate surf~ct~nt component to cationic ester surfactant is from 2.5:1 to 20:1 and the weight ratio of anionic sulfate surfactant component to hydrophilic nonionic surfactant sy~lelll is from 1:5 to 5:1.

In a preferred embodiment of this further aspect of the present invention the hydrophilic nonionic surfactant system preferably comprises aLkoxylated nonionic and polyhydroxy fatty acid amide surfactant.

W O 97/03164 PCTrUS96/11298 s Detailed description of the invention ~ The surfactant ~y~Lell-s of the invention are suitable for incorporation into various detergellt compositions, especially those designed for use in ~ laundry and m~chin~ dishwashing.

Anionic sulfate surfactant The first essenti~l element of the surfactant systems of the invention is a an anionic sulfate surf~c~nt.

Anionic sulfate surfactants suitable for use herein include the linear and branched primary and secondary alkyl sulfates, alkyl ethoxysulfates, fatty oleoyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, the C5-C17 acyl-N-(C1-C4 alkyl) and -N-(Cl-C2 hydroxyalkyl) gll-c~mine slllf~es, and sulfates of alkylpolysaccharides such as the slllf~tes of alkylpolyglucoside (the nonionic nons-llf~te-i compounds being described herein).

Alkyl sulfate surf~ct~nts are prefelred herein. These are preferably selected from the linear and branched primary Clo-C1g alkyl sulfates, more yrefel~bly the Cl1-Cls branched chain alkyl sulfates and the C12-Clg linear chain alkyl s~llf~tes.

One ~rererred aspect of the invention has Clo-Clg alkyl sulfate as the only anionic sulfate component.

Alkyl etho~cysulfate surf~t~ntc are also L,referred herein. These are preferably selected from the group con~is~in~ of the Clo-Clg alkyl sulfates which have been ethoxylated with from 0.5 to 20 moles of ethylene oxide per molecule. More preferably, the alkyl ethoxysulfate surfactant is a Cl1-C1g, most preferably C11-C1s alkyl sulfate which has been ethoxylated with from 0.5 to 7, preferably from 1 to 5, moles of ethylene oxide per molecule.

W O 97/03164 PCT~US96/11298 A particularly preferred aspect of the invention employs mixtures of allyl sulfate and alkyl ethoxysulfate surfactants at a weight ratio of from 2:1 to 19:1, preferably from 3:1 to 15:1, most ~lefe.ably from 4:1 to 10:1.
The anionic sulfate surfactant is typically present as a salt, such as a sodium, pot~ m, ammonium, or subst~ te-l ammonium salt such as the mono-, di- and triethanol~mine salts.

Cationic ester surfactant An essential component of the surfactant system is a cationic ester surfactant. That is, a compound having surfactant properties comprising at least one ester (ie -COO-) linkage and at least one cationically charged group.

The weight ratio of anionic sulfate surfactant component to cationic ester surfactant is from 2.5:1 to 20:1, preferably from 3:1 to 12:1, most preferably from 5:1 to 10:1.

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

Preferred water dispersible cationic ester surfactants are those having the formula:

Rl (}(CH)nO b (X~u (CH2)m (Y)v (C~H2)t N R3 M
- a wherein Rl is a Cs-C31 linear or branched alkyl, alkenyl or alkaryl chain or M-. N+(R6R7Rg)(CH2)S; X and Y, independently, are selected from the group concictin~ of COO, OCO, O, CO, OCOO, CONH, NHCO, OCONH NHCOO and CON(RgORlo)Z, and CONRllZ wherein at least W O 97/03164 PCTrUS96/11298 one of X or Y is a COO, OCO, OCOO, OCONH or NHCOO group; R2, R3~ R4~ R6, R7, R8 and Rll are independently selected from the group consisting of aLkyl, alkenyl, hydroxyalkyl, hydroxy-alkenyl and alkaryl groups having from 1 to 4 carbon atoms; Rg and Rlo are indepçntlçntly selected from the group con~icting of linear or br~ncherl, saturated or m~ rated carbon chains having from 1 to 8 carbon atoms; Z is a polyhydroxyhydrocarbyl moiety; and Rs is indepen-1ently H or a Cl-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 and v is l; and wherein M is a counter anion.

Preferably R2,R3 and R4 are independently selected from CH3 and -CH2CH20H.

Z is preferably derived from a reducing sugar in a reductive ~min~tion reaction, more preferably Z is glycityl moiety. Suitable reducing sugars include glucose, fructose, maitose, lactose, galactose, m~nn~se and xylose as well as glyceraldehyde. Z is most preferably selected from the group conci~tin~ of-CH2-(CHOH)n-CH2O-, -CH(CH2OH)-(CHOH)n l-CH2O-, -CH2-(CHOH)2(CHOR')(CHOH)-CH2O-, where n = 1-5 inclusive and R' is H or a cyclic mono- or polysaccharide and aLkoxylated derivatives thereof. Most ~lererred are glycityls wherein n = 4, particularly -CH2-(CHOH)4-CH2O-.

Preferably M is selected from the group con~i~tin~ of halide, methyl sulfate, sulfate, and nitrate, more L,lerelably methyl sulfate, chloride, bromide or iodide.

Prererled water dispersible cationic ester surf~ct~nt~ are the choline esters having the formula:

1~l CIH3 Rl--C--O--CH2CH2--I--CH3Mr wherein Rl is a Cll-Clg linear or branched alkyl chain.

CA 0222662l l998-0l-l2 W O97/03164 PCT~US96/11298 Particularly preferred choline esters of this type include the stearoylcholine ester quaternary methylammonium halides (Rl=C17 alkyl), palmitoyl choline ester quaternary methyl~mmonium halides (Rl=Cls alkyl), myristoyl choline ester quaternary methyl~mmonium h~licle~
(Rl=C13 aLkyl), lauroyl choline ester methylammonium halides (Rl=Cll alkyl), cocoyl choline ester quaternary methyl~mmonium halides (Rl=Cll C13 alkyl), tallowyl choline ester quaternary methylammonium halides (Rl=Cls C17 alkyl), and any mixtures thereof.

The particularly preferred choline esters, given above, may be preparedby the direct esterification of a fatty acid of the desired chain length with rlimethylaminoethanol~ in the presence of an acid catalyst. The reaction product is then quaternized with a methyl halide, forming 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 acid catalyst material. The reaction product is then quaternized with trimethyl~mine, forming the desired cationic material.

A particularly preferred gluc~mide betained ester has the formula:
O CH O
Il 1 3 ll R1--C--N--CH2--(CHOH)4--CH2--O--C--O--CH2N+(CH3)3- M-wherein Rl is a Cl l-Clg linear or branched alkyl chain.

Other suitable cationic ester surfactants have the structural formulas below, wherein d may be from 0 to 20.

W O 97/03164 PCT~US96/11298 Rl - O - C - ( CH2 )d C - O - CH2CH2- N -CH3 M

M CH3--~--CH2--CH2--O--C--~CH2)-- C--O--CH2--CH2--~--CH3M
CH3 ~H3 In a prefelred aspect the cationic ester surfactant is hydrolysable under the conditions of a laundry wash method.

Hydrophilic alkoxylated nonionic surfactant An essential component of the surfactant systems of the invention is a hydrophilic alkoxylated nonionic surfactant. For the purposes of the present invention hydrophilic is taken to mean having a HLB value of at least 9.1, prereldbly at least 10.0, more preferably at least 11Ø

A prefef~ed method of ev~ ting HLB value (hydrophilic-lipophilic balance value) herein is by use of the following formula:
MH

HLB value = 20 x MH + ML

where MH = formula weight of the hydrophilic portion of the molecule ML = formula weight of the lipophilic portion of the molecule Use of this formula is described in Surfactants and Interfacial Phenomena, M.J.Rosen, Wiley, 1978 at pages 241-245, particularly formula (8.13) of page 244.

For clarity, an example calculation using this formula for a C14-Cls alcohol (i.e. C14.s) ethoxylated with 7 moles of ethylene oxide would proceed as follows:

Hydrophilic portion = CH3(CH2)13.5- , MH = 204 CA 0222662l l998-0l-l2 W O 97/03164 PCTrUS96/11298 Lipophilic portion = -(C2H4O)7-OH , ML = 325 HLB value = 20 x = 12 3 204 + 325 The weight ratio of anionic sulfate surf~ct~nt component to hydrophilicaL~oxylated nonionic surf~ct~nt is from l:S to S:l, preferably from 1:4 to 4:1, most preferably from 1:3 to 3 :1.

Essentially any alkoxylated nonionic surfactants having a HLB
(hydrophilic-lipophilic balance) value of at least 9.1 are suitable. The ethoxylated and propoxylated nonionic surfactants are preferred.

The alkoxylated surfactants can be selected from the classes of the nonionic condensates of alkyl phenols, nonionic ethoxylated fatty alcohols, nonionic ethoxylated/propoxylated fatty alcohols, nonionic ethoxylate/propoxylate con-lenc~tes with propylene glycol, and the nonionic ethoxylate con~len~tion products with propylene oxide/ethylene minP adducts.

Nonionic alko~ylated alcohol surfactant The condensation products of aliphatic fatty alcohols with at least 4, preferably from 4 to 25 moles of alkylene oxide, particularly ethylene oxide and/or propylene oxide, are preferred hydrophilic alkoxylated nonionic surfactants herein. The alkyl chain of the aliphatic fatty alcohol can either be straight or branched, primary or secondary, and generally contains from 12 to 24 carbon atoms.

Prere.led are the ethoxylated aliphatic fatty alcohols having a degree of ethoxylation of at least 4. Particularly ~rere~.ed are the condensation products of fatty aliphatic alcohols having an alkyl group cont~inin~ from 12 to 20 carbon atoms, ~r~felably from 12 to 16 carbon atoms with from 4 to 10 moles, preferably from 4 to 7 moles of ethylene oxide per mole of alcohol.

CA 0222662l l998-0l-l2 Exemplary ethoxylated fatty alcohols herein include the condensation product of a C14-C1s alcohol with 7 moles of ethylene oxide (hlb =
12.3) and the condensation product of a fatty alcohol derived from coconut feedstock (typically C12-C14) with 7 moles of ethylene oxide (hlb = 12.8) Additional surfactant The surfactant systems of the invention may contain an additional surfactant selected from non-sulfate anionic, hydrophobic alkoxylated nonionic, non-aL~oxylated nonionic, non-ester cationic, ampholytic, amphoteric and zwitterionic surfactants and mixtures thereof.

The additional surfactant is preferably present only at low levels, typically of from 0% to 20%, more pr~fel~bly from 0% to 10% by weight of the surf~ct~nt ~y~lem. Most preferably the surfactant system contains no additional surfactant.

A typical listing of anionic, nonionic, ampholytic, and zwitterionic classes, and species of these surf~ct~nt~, is given in U.S.P. 3,929,678 issued to T ~ hlin and Heuring on December 30, 1975. Further examples are given in "Surface Active Agents and Detergents" (Vol. I and II by Schwartz, Perry and Berch). A list of suitable cationic surfactants is given in U.S.P. 4,259,217 issued to Murphy on March 31, 1981.

Where present, ampholytic, amphoteric and z~,vitteronic surfactants are generally used in combination with one or more anionic and/or nonionic surfactants.

Additional anionic surfactant The surf~ct~nt system may contain additional non-sulfate anionic surfactant. These can include salts (including, for example, sodium, pot~si~-m, ammonium, and substituted ammonium salts such as mono-, di- and triethanol~mine salts) of the anionic sulfonate, carboxylate and sarcosinate surfactants.

W O 97/03164 PCTrUS96/11298 Other non-sulfate anionic surfactants include the isethionates such as the acyl isethionates, N-acyl t~UldteS, fatty acid amides of methyl tauride, alkyl succinates and sulfosuccinates, monoesters of sulfosuccinate (especially salul~ted and lln~lrated C12-C18 monoesters) diesters of sulfosuccinate (especially saturated and lln~hlrated C6-C14 diesters), N-acyl sarcosinates. 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 sulfonate surfactant Anionic sulfonate surfactants suitable for use herein include the salts of Cs-C20 linear alkylbenzene sulfonates, alkyl ester sulfonates, C6-C22 primary or secondary aLkane sulfonates, C6-C24 olefin sulfonates, sulfonated polycarboxylic acids, alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfonates, and any mixtures thereof.

Anionic carboxylate surfactant Suitable anionic carboxylate surfactants include the alkyl ethoxy carboxylates, the alkyl polyethoxy polycarboxylate surf~et~ntc and the soaps ('alkyl carboxyls'), especially certain secondary soaps as described herein.

Suitable alkyl ethoxy carboxylates include those with the formula RO(CH2CH20)X CH2COO-M+ wherein R is a C6 to Clg alkyl group, x 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 cation. Suitable alkyl polyethoxy polycarboxylate surfactants include those having the formula RO-(CHRl-CHR2-O)-R3 wherein R is a C6 to Clg alkyl group"c is from 1 to 25, Rl and R2 are selected from the group con~i~tinr~ of hydrogen, methyl acid radical, succinic acid radical, hydroxysuccinic acid radical, and mixtures thereof, and R3 is selected from the group con~i~tin~ of hydrogen, substit--te~l or unsubstituted hydrocarbon having between 1 and 8 carbon atoms, and mixtures thereof.

CA 0222662l l998-0l-l2 W O 97/03164 PCT~US96/11298 Suitable soap surfactants include the secondary soap surfactants which - contain a carboxyl unit connected to a secondary carbon. Preferredsecondary soap surfactants for use herein are water-soluble members selected from the group con~i~ting of the water-soluble salts of 2-methyl-1-undecanoic acid, 2-ethyl-1-decanoic acid, 2-propyl-1-nonanoic acid, 2-butyl-l-octanoic acid and 2-pentyl-1-heptanoic acid. Certain soaps may also be included as suds suppressors.

Alkali metal sarcosinate surfactant Other suitable anionic surfactants are the alkali metal sarcosinates of formula R-CON (R1) CH2 COOM, wherein R is a Cs-C17 linear or branched alkyl or aLkenyl group, Rl is a Cl-C4 alkyl group and M is an aLkali metal ion. Preferred examples are the myristyl and oleoyl methyl sarcosinates in the form of their sodium salts.

Nonionic polyhydroxy fatty acid amide surfactant Polyhydroxy fatty acid amides suitable for use herein are those having the structural formula R2CONR1Z wherein: Rl is H, Cl-C4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl, ethoxy, propoxy, or a mixture thereof, plefeldble C1-C4 alkyl, more preferably C1 or C2 alkyl, most preferably Cl alkyl (i.e., methyl); and R2 is a Cs-C31 hydrocarbyl, preferably straight-chain Cs-Clg alkyl or aLkenyl, more preferably straight-chain Cg-C17 alkyl or aLkenyl, most preferably straight-chain Cl l-C17 alkyl or alkenyl, or mixture thereof; and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an aLkoxylated derivative (preferably ethoxylated 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 surf~ct~nt Suitable fatty acid amide surfactants include those having the formula:
R6CoN(R7)2 wherein R6 is an alkyl group cont~ining from 7 to 21, prefe~ably from 9 to 17 carbon atoms and each R7 is selected from the W O 97/03164 PCT~US96/11298 group consisting 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, Llenado, issued January 21, 1986, having a hydrophobic group cont~inin~ from 6 to 30 carbon atoms and a polysaccharide, e.g., a polyglycoside, hydrophilic group cont~inin~ from 1.3 to 10 saccharide units.

Preferred alkylpolyglycosides have the formula R20(CnH2nO)t(glYC~sYl)x wherein R2 is selected from the group con~isting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures 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 preferably derived from glucose.

Amphoteric surfactant Suitable amphoteric surf~ct~nt~ for use herein include the amine oxide surf~ct~nt~ and the alkyl amphocarboxylic acids.

Suitable amine oxides include those compounds having the formula R3(0R4)XNO(R5)2 wherein R3 is selected from an alkyl, hydroxyalkyl, acyl~midopropoyl and alkyl phenyl group, or mixtures thereof, cont~inin~
from 8 to 26 carbon atoms; R4 is an alkylene or hydroxyalkylene group cont~ining from 2 to 3 carbon atoms, or mixtures thereof; x is from O to 5, ~refel~Lbly from O to 3; and each RS is an alkyl or hydroxyalkyl group cont~inin~ from 1 to 3, or a polyethylene oxide group cont~inin~ from 1 to 3 ethylene oxide groups. Preferred are Clo-Clg alkyl dimethyl~min~
oxide, and C10 18 acyl~mi~lo aLkyl dimethyl~mine oxide.

W O 97/03164 PCTrUS96/11298 A suitable example of an alkyl aphodicarboxylic acid is Miranol(TM) C2M Conc. m~nllf~ctured by Miranol, Inc., Dayton, NJ.

CA 0222662l l998-0l-l2 W O 97/03164 PCTrUS96/11298 Zwitterionic surf~ct~nt Zwitterionic surf~ct~nt~ can also be incorporated into the deteLgellt compositions hereof. These surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or delivatives of quaternary ammonium, quaternary phosphonium or tertiary sulrulliulLI compounds. Betaine and slllt~ine surfactants are exemplary zwitterionic surfactants for use herein.

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 Cl-Cs hydrocarbyl group. Plerel~ed betaines are C12 18 dimethyl-ammonio hexanoate and the C10-l8 acylamidopropane (or ethane) dimethyl (or diethyl) betaines. Complex betaine surfactants are also suitable for use herein.

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

Delel~ellt compositions The surf~ct~nt ~y~le-lls of the present invention may be incorporated into detergent compositions. Typical levels of incorporation are from 1% to 95%, preferably from 2% to 50%, most preferably from 3% to 30%
surf~c~nt ~y~ by weight of the detergent composition.

The detergent compositions may also contain additional detergent components. The precise nature of these additional 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.

W O 97/03164 PCT~US96/11298 The detergent compositions preferably contain at least one additional ~ detergent component selected from bleaches, builders, organic polymeric compounds, enzymes, suds ~uyyreSSOrS, lime soap dispersants, soil suspension and anti-redeposition agents and corrosion inhibitors.

Water-soluble builder compound The delergellt compositions in accord with 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 preferably from 20~o to 60% by weight of the composition.

Suitable water-soluble builder compounds include 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 radicals separated from each other by not more that two carbon atoms, borates, phosphates, and mixt~lres of any of the foregoing.

The carboxylate or polycarboxylate builder can be momomeric or oligomeric in type although monomeric polycarboxylates are generally yrererred 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 cont~ining two carboxy groups include the water-soluble salts of succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid and fumaric acid, as well as the ether carboxylates and the sulfinyl carboxylates. Polycarboxylates co~ in~ three carboxy groups include, in particular, water-soluble citrates, aconitrates and citraconates as well as succinate derivatives such as the carboxymethyloxysuccinates described in British Patent No.
1,379,241, lactoxysuccinates described in British Patent No. 1,389,732, and aminosuccinates described in Netherlands Application 7205873, and the oxypolycarboxylate materials such as 2-oxa-1,1,3-propane tricarboxylates described in British Patent No. 1,387,447.

W O 97/03164 PCTrUS96/11298 Polycarboxylates cont~inin~ four carboxy groups include oxydisuccinates disclosed in British Patent No. 1,261,829, 1,1,2,2-ethane tetracarboxylates, 1,1,3,3-propane tetracarboxylates and 1,1,2,3-propane tetracarboxylates. Polycarboxylates cont~ining sulfo substituents include the sulfosuccinate derivatives disclosed in British Patent Nos. 1,398,421 and 1,398,422 and in U.S. Patent No. 3,936,448, and the sulfonated pyrolysed citrates described in British Patent No. 1,439,000. Preferred polycarboxylates are hydroxycarboxylates cont~inin~ up to three carboxy groups per molecule, more particularly citrates.

The parent acids of the monomeric or oligomeric polycarboxylate chçl~tin~: 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 con~inin~ borate-forming materials 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~si~lm and ammonium pyrophosphate, sodium and pot~ lm and ammonium pyrophosphate, sodium and potassium 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 deter~ellt compositions in accord with the present invention may contain a partially soluble or insoluble builder compound, typically present at a level of from 1 % to 80% by weight, ~lere.ably from 10% to 70% by weight, most preferably from 20% to 60% weight of the composition.
F~mples of largely water insoluble builders include the sodium ~l~lminosilicates .

, CA 0222662l l998-0l-l2 Suitable aluminosilicate zeolites have the unit cell formula Naz[(AlO2)z(SiO2)y]. xH2O wherein z and y are at least 6; the molar ratio of z to y is from 1.0 to 0.5 and x is at least 5, plefeldbly from 7.5 to 276, more preferably from 10 to 264. The ~ minosilicate material are in hydrated form and are preferably crystalline, cont~ining from 10% to 28%, more prefelably from 18% to 22% water in bound form.

The aluminosilicate zeolites can be naturally occurring materials, but are preferably synthetically derived. Synthetic crystalline ~ minosilicate ion exchange materials are available under the designations Zeolite A, Zeolite B, Zeolite P, Zeolite X, Zeolite HS and mixtures thereof. Zeolite A has the formula - -Na 12 [A102) 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.
~lk?,linity system The detergent compositions ~referably contain from 1.5 % to 95 %, prefefably from 5% to 60%, most prefe~ably from 10% to 40% by weight of the composition of an ~lk~linity system comprising components capable of providing ~ linity species in solution. By ~lk~linity species it is meant carbonate, bicarbonate, hydroxide and the various silicate anions.
Such ~lk~linity species can be formed for example, when ~lk~line salts selected from aLali metal or ~lk~lin~. earth carbonate, bicarbonate, hydroxide or silicate, including crystalline layered ~ilic~te, salts and any mixtures thereof are dissolved in water. ALkali metal percarbonate and persilicate salts are also suitable sources of ~lk~linity species.
F~mples of carbonates are the ~lk~lin~ earth and alkali metal carbonates, including sodium carbonate and sesqui-carbonate and any mixtures thereof with ultra-fine calcium carbonate such as are disclosed in German Patent Application No. 2,321,001 published on November 15, 1973.
ALkali metal percarbonate salts are also suitable sources of carbonate WO 97/03164 PCT~US96111298 species and are described in more detail in the section 'inorganic perhydrate salts' herein.

Suitable silicates include the water soluble sodium silicates with an Si02:
Na20 ratio of from 1.0 to 2.8, with ratios of from 1.6 to 2.0 being ereLled, and 2.0 ratio being most preferred. The silicates may be in the form of either the anhydrous salt or a hydrated salt. Sodium silicate with an SiO2: Na20 ratio of 2.0 is the most preferred silicate. Alkali metal persilicates are also suitable sources of silicate herein.

Piefe~red crystalline layered silicates for use herein have the generalformula NaMSix02x+ 1 ~YH20 wherein M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20. Crystalline layered sodium silicates of this type are disclosed in EP-A-0164514 and methods for their preparation are disclosed in DE-A-3417649 and DE-A-3742043. Herein, x in the general formula above piefelably has a value of 2, 3 or 4 and is preferably 2. The most preferred material is ~-Na2Si20s, available from Hoechst AG as NaSKS-6.

The crystalline layered silicate material is preferably present in granular deler~ ent compositions as a particulate in intim~t~ admixture with a solid, water-soluble ionisable material. The solid, water-soluble ionisable material is selected from organic acids, organic and inorganic acid salts and mixtures thereof.

Organic peroxyacid bleachin~ ~yslem A prere"ed feature of dele,gell~ compositions in accord with the invention is an organic peroxyacid bleaching system. In one prefel-ed execution the bleaching system 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. PreferLed sources of hydrogen peroxide include W O 97/03164 PCTrUS96/11298 inorganic perhydrate bleaches. In an alternative preferred execution a pLefolllled organic peroxyacid is incorporated directly into the ~ composition. Compositions cont~ininp mixtures of a hydrogen peroxide source and organic peroxyacid precursor in combination with a plefolllled organic pero~cyacid are also envisaged.

CA 0222662l l998-0l-l2 Inor~anic perhydrate bleaches Inorganic perhydrate salts are a prererled source of hydrogen peroxide.These salts are normally incorporated in the form of the alkali metal, preferably sodium salt at a level of from 1% to 40% by weight, more preferably from 2% to 30% by weight and most ~l-er~ bly from 5% to 2~ % by weight of the compositions.
Fx~mples of inorganic perhydrate salts include perborate, percarbonate,perphosphate, persulfate and persilicate salts. The inorganic perhydrate salts are normally the alkali metal salts. The inorganic perhydrate salt may be included as the crystalline solid without additional protection. For certain perhydrate salts however, the ~referred 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 coatings comprise inorganic salts such as alkali metal silicate, carbonate or borate salts or mixtures thereof, or organic materials such as waxes, oils, or fatty soaps.

Sodium perborate is a prer~,~ed perhydrate salt and can be in the form of the monohydrate of nominal formula NaB02H202 or the tetrahydrate NaB02H202-3H20-AL~cali metal percarbonates, particularly sodium percarbonate arepreferred perhydrates herein. Sodium percarbonate is an addition compound having a formula corresponding to 2Na2C03.3H202, and is available commercially as a crystalline solid.

Pot~si~lm peroxymonopersulfate is another inorganic perhydrate salt of use in the de~e~ellt compositions herein.

Peroxyacid bleach precursor Peroxyacid bleach precursors are compounds which react with hydrogen pe~oxide in a perhydrolysis reaction to produce a peroxyacid. Generally peroxyacid bleach precursors may be represented as W O 97/03164 PCTnUS96/11298 o 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 Il X-C-OOH

Peroxyacid bleach precursor compounds are preferably incorporated at a level of from 0.5 % to 20% by weight, more preferably from 1 % to 15 %
by weight, most preferably from 1.5% to 10% by weight of the detergent 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, imides, lactams and acylated derivatives of imi~ oles and oximes. Examples of useful materials within these classes are disclosed in GB-A-1586789.
Suitable esters are disclosed in GB-A-836988, 864798, 1147871, 2143231 and EP-A-0170386.

Leavln~ ~roups The leaving group, hereinafter L group, must be sufficiently reactive for the perhydrolysis reaction to occur within the optimum time frame (e.g., a wash cycle). However, if L is too reactive, this activator will be difficult to stabilize for use in a bleaching composition.

rlerelled L groups are selected from the group con~ictin~ of:

W O 97/03164 PCTnUS96/11298 ~Y ~3 ~R3Y

--N--C--R1 _N N --N--C--C H--R4 1 3 L~ ' i y IR3 r --O--C H=C--C H=C H2 --O--C H--C--C H=C H2 -~11--R1 & H7-C Y 11 O O

--O--C--CHR4 and N--S--CH--R4 and mixtures thereof, wherein Rl is an alkyl, aryl, or alkaryl group cont~inin~ from 1 to 14 carbon atoms, R3 is an alkyl chain cont~inin~
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 substituted by essentially any functional group including, for example alkyl, hydroxy, alkoxy, halogen, amine, nitrosyl, amide and ammonium or alkyl ~mmmonium groups The pr~feLl~d solubilizing groups are -S03-M +, -C02-M +, -S04-M ~, -N + (R3)~X- and O < --N(R3)3 and most preferably -S03-M + and -C~2 M wherein R is an alkyl chain cont~inin~ 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 activator.
Preferably, M is an aLkali metal, ammonium or substi~uted ammonium CA 0222662l l998-0l-l2 W O 97/03164 PCTrUS96/11298 cation, with sodium and pot~ m being most preferred, and X is a halide, hydroxide, methylsulfate or acetate anion.

Alkyl percarboxylic acid bleach precursors Alkyl percarboxylic acid bleach precursors form percarboxylic acids on perhydrolysis. Plerelled precursors of this type provide peracetic acid on perhydrolysis.

Pleferled allyl percarboxylic precursor compounds of the imide type include the N-,N,NlNl tetra acetylated alkylene rli~min~s wherein the alkylene group contains from 1 to 6 carbon atoms, particularly those compounds in which the alkylene group contains 1, 2 and 6 carbon atoms.
Tetraacetyl ethylene ~ mine (TAED) is particularly ~referled.

Other ~refelled alkyl percarboxylic acid precursors include sodium 3,5,5-tri-methyl hexanoyloxyben~ene sulfonate (iso-NOBS), sodium nonanoyloxybenzene sulfonate (NOBS), sodium acetoxybenzene sulfonate (ABS) and pent~cetyl glucose.

Amide substituted alkyl peroxyacid precursors Amide substit~lte~ alkyl peroxyacid precursor compounds are suitable herein, including those of the following general formulae:

Il l 11 1 11 11 O R5 0 or R5 0 0 wherein R1 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~ining 1 to 10 carbon atoms and L can be essentially any leaving group. Amide substit~lte~l bleach activator compounds of this type are described in EP-A-0170386.

W O 97/03164 PCT~US96/11298 Perbenzoic acid precursor Perbenzoic acid precursor compounds provide perbenzoic acid on perhydrolysis. Suitable O-acylated perbenzoic acid precursor compounds include the substituted and unsub~liLIl~e~1 benzoyl oxybenzene sulfonates, and the benzoylation products of sorbitol, glucose, and all saccharides with benzoylating agents, and those of the irnide type including N-benzoyl succinimide, tetrabenzoyl ethylene ~ min~ and the N-benzoyl substituted ureas. Suitable imitl~7ole type perbenzoic acid precursors include N-benzoyl imicl~7ole and N-benzoyl ben7imi~ ole. Other useful N-acyl group-cont~inin~ perbenzoic acid precursors include N-benzoyl pyrrolidone, dibenzoyl taurine and benzoyl pyro~lllt~mic acid.

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

Typically, cationic peroxyacid precursors are formed by substi~ltin~ the peroxyacid part of a suitable peroxyacid precursor compound with a positively charged functional group, such as an ammonium or alkyl ~mmmonium group, preferably an ethyl or methyl ammonium group.
Cationic peroxyacid precursors are typically present in the solid detergent compositions as a salt with a suitable anion, such as a halide ion.

The peroxyacid precursor compound to be so cationically substituted maybe a perbenzoic acid, or substit lte~l derivative thereof, precursor compound as described hereinbefore. .Altern~tively, the peroxyacid precursor compound may be an alkyl percarboxylic acid precursor compound or an amide substitll~e~l alkyl peroxyacid precursor as described hereinafter Cationic 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.

W O 97/03164 PCTnUS96/11298 Examples of ~rert;lLed cationic peroxyacid precursors are described in UK Patent Application No. 9407944.9 and US Patent Application Nos.
08/298903, 08/2986~0, 08/298904 and 08/298906.

- Suitable cationic peroxyacid precursors include any of the ammonium or alkyl ammonium substi~lte~ alkyl or benzoyl oxyben7ene sulfonates, N-acylated caprolactams, and monobenzoyltetraacetyl glucose benzoyl peroxides. Prefe~red cationic peroxyacid precursors of the N-acylated caprolactam class include the trialkyl ammonium methylene benzoyl caprol~ct~mc and the trialkyl ammonium methylene alkyl caprolactams.

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

[~N"C R~

wherein Rl is H, alkyl, alkaryl, aryl, or arylalkyl.

Preformed or anic peroxyacid The organic peroxyacid ble~ching system may contain, in addition 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 l,ref~,~bly from 1 % to 10% by weight of the composition.

A preferred class of organic peroxyacid compounds are the amide substituted compounds of the following general formulae:

W O 97/03164 PCT~US96/11298 Il l 11 1 11 11 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 alkyl, aryl, or alkaryl group cont~inin~ 1 to 10 carbon atoms. Amide substituted or~anic peroxyacid compounds of this type are described in EP-A-0170386.

Other organic peroxyacids include diacyl and tetraacylperoxides, especially diperoxydodecanedioc acid, diperoxytetr~(lec~nedioc acid and diperoxyhex~lec~ne-lioc acid. Mono- and diperazelaic acid, mono- and diperbrassylic acid and N-phthaloylaminoperoxicaproic acid are also suitable herein.

Bleach catalyst The detelgellt compositions optionally contain a transition metal cont~ininE~ bleach catalyst. One suitable type of bleach catalyst is a catalyst ~y~em comprising a heavy metal cation of defined bleach catalytic activity, such as copper, iron or m~n~nese cations, an auxiliary metal cation having little or no bleach catalytic activity, such as zinc or ahlmimlm cations, and a sequestrant having defined stability con~t~ntc for the catalytic and ~llxili~ry metal cations, particularly ethylenP~ min~tetraacetic 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~nese-based complexes disclosed in U.S. Pat. 5,246,621 and U.S. Pat. 5,244,594. Plerelred examples of these catalysts include MnIV2(u-o)3(l ,4,7-trimethyl-1,4,7-triazacyclononane)2-(PF6)2, MnLII2(u-O)l(u-OAc)2(1,4,7-trimethyl-1,4,7-triazacyclononane)2-(C104)2, MnIV4(u-O)6(1,4,7-triazacyclononane)4-(C104)2, MnIIIMnIV4(u-O)1(u-OAc)2 (1,4,7-trimethyl-1,4,7-triazacyclononane)2-(ClO4)3, and mixtures thereof.
Others are described in European patent application publication no.

W O 97103164 PCT~US96/11298 549,272. Other li~nfls suitable for use herein include 1,5,9-trimethyl-1,5,9-triazacyclododecane, 2-methyl-1,4,7-triazacyclononane, 2-methyl-1,4,7-triazacyclononane, 1,2,4,7-tetramethyl-1,4,7-triazacyclononane, and mixtures thereof.

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 teaches mononuclear m~nganp~se (IV) complexes such as Mn(1,4,7-trimethyl-1,4,7-triazacyclononane)(OCH3)3 (PF6). Still another type of bleach catalyst, as disclosed in U.S. Pat. 5,114,606, is a water-soluble complex of m~n~nese (III), and/or (IV) with a ligand which is a non-carboxylate polyhydroxy compound having at least three consecutive C-OH groups.
Other examples include binuclear Mn complexed with tetra-N-dentate and bi-N-dentate ligands, including N4MnIII(u-0)2MnIVN4)+and [13ipy2MnIII(u-0)2MnIVbipy2]-(clo4)3 .

Further suitable bleach catalysts are described, for example, in European patent application No. 408,131 (cobalt complex catalysts), European patent applications, publication nos. 384,503, and 306,089 (metallo-porphyrin catalysts), U.S. 4,728,455 (m~ng~nese/multiclent~te ligand catalyst), U.S. 4,711,748 and European patent application, publication no. 224,952, (absorbed m~n~nese on aluminosilicate catalyst), U.S.
4,601,845 (~lllminosilicate support with manganese and zinc or m~pnt~sium salt), U.S. 4,626,373 (m~ng~nese/ligand catalyst), U.S.
4,119,557 (ferric complex catalyst), German Pat. specification 2,054,019 (cobalt chelant catalyst) ~n~ n 866,191 (transition metal-cont~ining salts), U.S. 4,430,243 (chelants with m~n~nPse cations and non-catalytic metal cations), and U.S. 4,728,455 (m~n~n~se gluconate catalysts).

Heavy metal ion sequestrant The detergellt compositions in accord with the invention preferably contain as an optional component a heavy metal ion sequestrant. By heavy metal ion sequestrant it is meant herein components which act to sequester (chelate) heavy metal ions. These components may also have calcium and m~nPsium chelation capacity, but preferentially they show selectivity to binding heavy metal ions such as iron, m~n~~nese and copper.

CA 0222662l l998-0l-l2 W O 97/03164 PCT~US96/11298 Heavy metal ion sequestrants are generally present at a level of from 0.005 % to 20 ~, ~rerelably from 0.1 ~ to 10 %, more preferably from 0.25 ~ to 7.5 % and most prererably from 0.5% to 5~ by weight of the compositions.

Suitable heavy metal ion sequestrants for use herein include organic phosphonates, such as the amino alkylene poly (alkylene phosphonates), alkali metal ethane l-hydroAy disphosphonates and nitrilo trimethylene phosphonates.

Preferled among the above species are diethylene triamine penta (methylene phosphonate), ethylene ~ mine tri (methylene phosphon~te) hexamethylene ~ mine tetra (methylene phosphonate) and hydroxy-ethylene 1,1 diphosphonate.

Other suitable heavy metal ion sequestrant for use herein include nitrilotriacetic acid and polyaminocarboxylic acids such as ethylen~Ai~minotetracetic acid, ethylenetri~mine pent~cetic acid, ethylen~i~mine disuccinic acid, ethyl~n~ mine diglutaric acid, 2-hydroAy~ro~ylenP~ mine disuccinic acid or any salts thereof. Especially preferred is ethylene~ mine-N~N~-disuccinic acid (EDDS) or the alkali metal, ~lk~line earth metal, ~mmcmillm, or substituted ammonium salts thereof, or mixtures thereof.

Other suitable heavy metal ion sequestrants for use herein are iminodiacetic acid derivatives such as 2-hydroxyethyl diacetic acid or glyceryl imino rli~retic acid, described in EP-A-317,542 and EP-A-399,133. The imino~ cetic acid-N-2-hydroAyplo~yl sulfonic acid and aspartic acid N-carboAymethyl N-2-hydroAy~rupyl-3-sulfonic acid sequestrants described in EP-A-516,102 are also suitable herein. The ~3-~l~nine-N~Nl-diacetic acid, aspartic acid-N,N'-diacetic acid, aspartic acid-N-monoacetic acid and iminodisuccinic acid sequestrants described in EP-A-509,382 are also suitable.

EP-A476,257 describes suitable amino based sequestrants. EP-A-510,331 describes suitable sequestrants derived from collagen, keratin or W O 97/03164 PCTrUS96/11298 casein. EP-A-528,859 describes a suitable alkyl iminodiacetic acid sequestrant. Dipicolinic acid and 2-phosphonobutane-1,2,4-tricarboxylic acid are alos suitable. Glycin~mi~le-N,N'-disuccinic acid (GADS), ethylen~ mine-N-N'-~liElllt~ric acid (EDDG) and 2-- hydro~ypropylene li~minP--N-N'-disuccinic acid (HPDDS) are also suitable.

Enzyme Another preferred ingredient useful in the detergent compositions is one or more additional enzymes.

Preferred additional enzymatic materials include the commercially available lipases, cutinases, amylases, neutral and ~lk~line proteases, esterases, endogl~lc~n~es, cellulases, pectinases, l~ct~es and peroxidases conventionally incorporated into detergellt compositions. Suitable enzymes are discussed in US Patents 3,519,570 and 3,533,139.

rlerelled commercially available protease enzymes include those sold under the tr~clen~me~ Alcalase, Savinase, Primase, Durazym, and Esperase by Novo rnrlnstries A/S (Denmark), those sold under the tradename Maxatase, Maxacal and Maxapem by Gist-Brocades, those sold by Genencor International, and those sold under the tradename Opticlean 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.

Prer~rled amylases include, for example, a-amylases obtained from a special strain of B licheniformis, described in more detail in GB-1,269,839 (Novo). rrefelled commercially available amylases include for example, those sold under the tradename Rapidase by Gist-Brocades, and those sold under the tr~-len~me Termamyl and BAN by Novo Tn~ 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.

WO 97/03164 PCTrUS96/11298 Lipolytic enzyme may be present at levels of active lipolytic enzyme offrom 0.0001% to 2% by weight, preferably 0.001% to 1~ by weight, most ~rerel~bly from 0.001% to 0.5 % by weight of the compositions.

The lipase may be fungal or bacterial in origin being obtained, for example, from a lipase producing strain of Humicola sp., Thermomyces sp. or Pseudomonas sp. including Pseudomonas pseudoalcali~enes or Pseudomas fluorescens. Lipase from chemically or genetically modified mllt~nt~ of these strains are also useful herein. A preferred lipase is derived from Pseudomonas pseudoalcali~enes, which is described in Granted European Patent, EP-B-0218272.

Another preferred lipase herein is obtained by cloning the gene from Humicola l~ml~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 Industri A/S, Bagsvaerd, Denmark, under the trade name Lipolase. This lipase is also described in U.S.
Patent 4,810,414, Huge-Jensen et al, issued March 7, 1989.

Alcalase is a ~lereLled enzyme component of bleach-free detergent compositions ~iesignp~l for the washing of coloured or delicate fabrics, particularly in combination with a crystal growth inhibitor (e.g. HEDP) component Or~anic polymeric compound Organic polymeric compounds are preferred additional components of the deler~ellt compositions in accord with the invention, and are preferably 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 essçnti~lly any polymeric organic compound commonly used as dispersants, and anti-redeposition and soil suspension agents in detergent compositions, including any of the high molecular weight organic polymeric compounds described as clay flocc~ ting agents herein.

W O 97/03164 PCTrUS96/11298 Organic polymeric compound is typically incorporated in the detergent compositions of the invention at a level of from 0.1 % to 30%, l,refe~ably fromO.5% to 15%, most~refelablyfrom 1% to 10% byweightofthe compositions.
-Examples of organic polymeric compounds include the water solubleorganic homo- or co-polymeric polycarboxylic acids or their salts in which the polycarboxylic acid comprises at least two carboxyl radicals separated from each other by not more than two carbon atoms. Polymers of the latter type are disclosed in GB-A-1,596,756. Examples of such salts are polyacrylates of MWt 2000-5000 and their copolymers with 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 cont~ining 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 deler~ellt compositions herein include cellulose derivatives such as methylcellulose, carboxymethylcellulose, hydroxypropylmethylcellulose and hydroxyethylcellulose.

Further useful organic polymeric compounds are the polyethylene glycols, particularly those of molecular weight 1000-10000, more particularly 2000 to 8000 and most ~referably about 4000.

Suds ~uypressin~ ~y~lelll The delergellt compositions in accord with the invention, when formulated for use in machine washing compositions, preferably comprise a suds ~uppressing ~y~lem present at a level of from 0.01 % to 15 5~, preferably CA 0222662l l998-0l-l2 W O 97/03164 PCT~US96/11298 from 0.05% to 105~, most preferably from 0.1% to 5% by weight of the composition.

Suitable suds suppressing systems for use herein may comprise essentially any known antifoam compound, including, for example silicone antifoam compounds and 2-alkyl alcanol antifoam compounds.

By antifoam compound it is meant herein any compound or mixtures of compounds which act such as to depress the foaming or sn-l~ing produced by a solution of a detergent composition, particularly in the presence of agitation of that solution.

Particularly ~refelred antifoam compounds for use herein are silicone antifoam compounds defined herein as any antifoam compound including a silicone component. Such silicone antifoam compounds also typically contain a silica component. The term "silicone" as used herein, and in general throughout the in(i~ctry~ encompasses a variety of relatively high molecular weight polymers cont~ining siloxane units and hydrocarbyl group of various types. Preferred silicone antifoam compounds are the siloxanes, particularly the polydimethylsiloxanes having trimethylsilyl end blocking units.

Other suitable antifoam compounds include the monocarboxylic fatty acids and soluble salts thereof. These materials 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 suppressor typically have hydrocarbyl chains of 10 to 24 carbon atoms, preferably 12 to 18 carbon atoms. Suitable salts include the alkali metal salts such as sodium, potassium, and lithi~lm salts, and ammonium and aLkanol~mmonium salts.

Other suitable antifoam compounds include, for example, high molecular 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~min~s or di- to tetra alkylc1i~mine chlortri~7inPc formed as products of cyanuric chloride with two or three moles of a primary or secondary amine cont~ining 1 to W O 97/03164 PCT~US96/11298 24 carbon atoms, propylene oxide, bis stearic acid amide and monostearyl di-alkali metal (e.g. sodium, potassium, lithium) phosphates and phosphate esters.

- A ~rertr~d suds ~up~ressing system comprises (a) antifoam compound, ~refer~bly silicone antifoam compound, most preferably a silicone antifoam compound co~ ising in combination (i) polydimethyl siloxane, at a level of from 50% to 99%, preferably 75 % to 9S % by weight of the silicone antifoam compound; and (ii) silica, at a level of from 1% to 50%, yrefe~dbly 5% to 25%
by weight of the silicone/silica antifoam compound;

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

(b) a dispersant compound, most preferably comprising a silicone glycol rake copolymer with a polyoxyalkylene content 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%, preferably 1% to 10% by weight; a particularly ~referred silicone glycol rake copolymer of this type is DCOS44, commercially available from DOW Corning under the tr~len~me DCOS44;

(c) an inert carrier fluid compound, most preferably comprising a C16-Clg ethoxylated alcohol with a degree of ethoxylation of from S to 50, prefelably 8 to lS, at a level of from 5% to 80%, preferably 10% to 70%, by weight;

A highly ~re~elled particulate suds suppressing system is described in EP-A-0210731 and comprises a silicone antifoam compound and an organic carrier material having a melting point in the range 50~C to 85~C, wherein the organic carrier material comprises a monoester of glycerol CA 0222662l l998-0l-l2 W O97/03164 PCT~US96/11298 and a fatty acid having a carbon chain cont~ining from 12 to 20 carbon atoms. EP-A-0210721 discloses other preferred particulate suds suppressing systems wherein the organic carrier material is a fatty acid or alcohol having a carbon chain cont~ining from 12 to 20 carbon atoms, or a mixture thereof, with a melting point of from 45~C to 80~C.

CA 02226621 l998-0l-l2 W O 97/03164 PCTrUS96/11298 Clay softenin~ system The delergent compositions may contain a clay softening ~y~e comprising a clay mineral compound and optionally a clay flocc~ tin~
agent.

The clay mineral compound is preferably a smectite clay compound.
Smectite clays are disclosed 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 Company describe suitable organic polymeric clay flocc~ tin~ agents.

Polymeric dye transfer inhibitin~ a~ents The delergent compositions herein may also comprise from 0.01 % to 10 %, preferably from O.OS % to 0.5 % by weight of polymeric dye transfer in_ibiting agents.

The polymeric dye transfer inhibiting agents are preferably selècted from polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimicl~7ole, polyvinylpyrrolidonepolymers or combinations thereof.

It has been found that bleachfree delergent compositions cont~inin~
polymeric dye transfer inhibiting agents, crystal growth inhibitors (e.g.
HEDP) and high (>7.5%) levels of nonionic surfactant suprisingly provide excellent whiten~s m~in~eIl~nce, in addition to reduced tendency to fade coloured fabrics when used in the l~lln-lering of mixed fabric loads.

a) Polyamine N-oxide polymers Polyamine N-oxide polymers suitable for use herein contain units havingthe following structure formula:

CA 0222662l l998-0l-l2 W O 97/03164 PCTrUS96/11298 (I) I

wherein P is a polymerisable unit, and Il 11 11 A is NC, CO, C, -O-, -S-, -N-; x.is O or1;

R are aliphatic, ethoxylated aliphatics, aromatic, heterocyclic or alicyclic groups or any combination thereof whereto the nitrogen of the N-O group can be ~tt~chP-l or wherein the nitrogen of the N-O group is part of these groups.

The N-O group can be represented by the following general structures:

(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 attached or wherein the nitrogen of the N-O group forms part of these groups. The N-O group can be part of the polymerisable unit (P) or can be attached to the polymeric backbone or a combination of both.

Suitable polyamine N-oxides wherein the N-O group forms part of the polymerisable unit comprise polyamine N-oxides wherein R is selected from aliphatic, aromatic, alicyclic or heterocyclic groups. One class of said polyamine N-oxides comprises the group of polyamine N-oxides wherein the nitrogen of the N-O group forms part of the ~-group.

-W O 97/03164 PCTrUS96/11298 Preferred polyamine N-oxides are those wherein R is a heterocyclic group such as pyrridine, pyrrole, imirl~7ole, pyrrolidine, piperidine, quinoline, ~ acridine and derivatives thereof.

Other suitable polyamine N-oxides are the polyamine oxides whereto the N-O group is attached to the polymerisable unit. A prererl-ed 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 functional group is part of said R
group. Fx~m~les of these classes are polyamine oxides wherein R is a heterocyclic compound such as pyrridine, pyrrole, imi~ ole and derivatives thereof.

The polyamine N-oxides can be obtained in almost any degree of polymerisation. The degree of polymerisation is not critical provided the material has the desired water-solubility and dye-suspending power.
Typically, the average molecular weight is within the range of 500 to 1000,000.
b) Copolymers of N-vinylpyrrolidone and N-vinylimidazole Suitable herein are coploymers of N-vinylimitl~7ole and N-vinylpyrrolidone having an average molecular weight range of from 5,000 to 50,000. The prefe~red copolymers have a molar ratio of N-vinylimi~7ole 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 polyvinylpyrrolidones are commercially vailable from ISP
Corporation, New York, NY and Montreal, C~n~ under the product names PVP K-15 (viscosity molecular 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 CA 0222662l l998-0l-l2 W O97/03164 PCTrUS96/11298 suitable polyvinylpyrrolidones which are commercially available from BASF Cooperation include Sokalan HP 165 and Sokalan HP 12.

W O 97/03164 PCTnUS96/11298 d) Polyvinyloxazolidone - The detergent compositions herein may also utilize polyvinyloxazolidones as polymeric dye transfer inhibiting agents. Said polyvinyloxazolidones have an average molecular weight of from 2,500 to 400,000.

e) Polyvinylimidazole The detergellt compositions herein may also utilize polyvinylimicl~7ole as polymeric dye transfer inhibiting agent. Said polyvinylimid~7oles ~rererably have an average molecular weight of from 2,500 to 400,000.

Optical bri~htener The de~el~ellt compositions herein also optionally contain from about 0.005% to 5~o by weight of certain types of hydrophilic optical bri~hten~rs.

Hydrophilic optical briPhte-ners useful herein include those having the structural formula:

Rl R2 N~ ~ IH IH~NH~N(~N

R2 SO3M SO3M Rl wherein Rl is selected from ~nilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl; 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 potassium.

When in the above formula, Rl is ~nilino, R2 is N-2-bis-hydroxyethyl and M is a cation such as sodium, the brightener is 4,4',-bis[(4-anilino-6-(N-2-bis-hydroxyethyl)-s-triazine-2-yl)amino]-2,2'-stilbenedisulfonic acid and disodium salt. This particular brightener species is commercially CA 0222662l l998-0l-l2 W O 97/03164 PCTrUS96/11298 marketed under the tradename Tinopal-UNPA-GX by Ciba-Geigy Corporation. Tinopal-UNPA-GX is the preferred hydrophilic optical brigh~P-ner useful in the deterge~t compositions herein.

When in the above formula, Rl is anilino, R2 is N-2-hydroxyethyl-N-2-methyl~mino and M is a cation such as sodium, the brightener is 4,4'-bis[(4-anilino-~(N-2-hydroxyethyl-N-methyl~ mino)-s-triazine-2-yl)amino]2,2'-stilben~ llfonic acid disodium salt. This particular brightener species is commercially marketed under the tr~-len~me Tinopal SBM-GX by Ciba-Geigy Corporation.

When in the above formula, R1 is anilino, R2 is morphilino and M is a cation such as sodium, the bri~htener is 4,4'-bis[(4-anilino-6-morphilino-s-triazine-2-yl)amino]2,2'-stilbenedisulfonic acid, sodium salt. This particular briPhten~r species is commercially marketed under the tradename Tinopal AMS-GX by Ciba Geigy Corporation.

Cationic fabric softenin~ a~ents Cationic fabric softening agents can also be incorporated into compositions in accordance with the present invention. Suitable cationic fabric softening agents include the water insoluble tertiary amines or dilong chain amide m~teri~lc as disclosed in GB-A-1 514 276 and EP-B-0 011 340.

Cationic fabric softening agents are typically incorporated at total levels of from 0.5 % to 15 % by weight, normally from 1 % to 5 % by weight.

Other optional inPredients Other optional ingre~ients suitable for inclusion in the delerge~lt compositions in accord with the invention include perfumes, colours and filler salts, with sodium sulfate being a preferred filler salt.

pH of the compositions W O 97/03164 PCTnUS96/11298 The delergent compositions preferably have a pH measured as a 1%
solution in distilled water of at least 10.0, preferably from 10.0 to 12.5, - most pre~idbly from 10.5 to 12 Ø

Form of the compositions Solid detergent compositions in accordance with the invention can take a variety of physical forms including granular, bar and tablet forms. The detergent compositions can also be in liquid form. The compositions are particularly the so-called concentrated granular detergent compositions adapted to be added to a washing machine by means of a dispensing device placed in the machine drum with the soiled fabric load.

The mean particle size of the components of granular compositions in accordance with the invention should prefelably be such that no more that 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 ~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 detergent compositions in accordance with the present invention typically have a bulk density of at least 600 g/litre, more preferably from 650 g/litre to 1200 g/litre.BuLk density is measured by means of a simple funnel and cup device con~i~ting of a conical funnel moulded rigidly on a base and provided with a flap valve at its lower extremity to allow the contenl~ of the funnel to be emptied into an axially ~ligne-l cylindrical cup disposed below the funnel. The funnel is 130 mm high and has internal diameters of 130 mm and 40 mm at its respective ~ upper and lower extremities. It is mounted so that the lower extremity is 140 mm above the upper surface of the base. The cup has an overall height of 90 mm, an internal height of 87 mm and an internal diameter of 84 mm. Its nominal volume is 500 ml.

W O 97/03164 PCT~US96/11298 To carry out a me~ rement~ 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 implement 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 m~sllrements are made as required.

Surfactant a~glomerate particles The surfactant system herein is preferably present in granular compositions in the form of surf~ct~nt agglomerate particles, which may take the form of flakes, prills, marumes, noodles, ribbons, but ~>refel~bly take the form of granules. The most ~lefelled way to process the particles is by agglomerating powders (e.g. ~lllminosilicate~ 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 mixing an effective amount of powder with a high active surfactant paste in one or more agglomelatols such as a pan agglomerator, a Z-blade mixer or more preferably an in-line mixer such as those m~nllf~ctllred by Schugi (Holland) BV, 29 Chroomstraat 8211 AS, Lelystad, Netherlands, and Gebruder Lodige Maschinenbau GmbH, D4790 Paderborn 1, Elsenerstrasse 7-9, Postfach 2050, Germany. Most pLefelably 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, ~rer~ably 70% by weight to 85% by weight of surfactant 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 degradation of the anionic surfactants used. An operating temperature of the paste of 50~C to 80~C is typical.

Laundry w~hing method Machine laundry methods herein typically comprise treating soiled laundry with an aqueous wash solution in a washing machine having CA 0222662l l998-0l-l2 W O 97/03164 PCTrUS96/11298 dissolved or dispensed therein an effective amount of a machine laundry d~tel~ent composition in accord with the invention. By an effective - amount of the detergent composition it is meant from 40g to 300g ofproduct 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 conventional machine laundry methods.

In a ~referled use aspect a dispen~in~ device is employed in the washing method. The dispensing device is charged with the detergent product, and is used to introduce the product directly into the drum of the washing machine before the commencement of the wash cycle. Its volume capacity should be such as to be able to contain sufficient detergent product as would normally be used in the washing method.

Once the washing machine has been loaded with laundry the dispensing device cont~inin~ the deter~ellt product is placed inside the drum. At the commencement of the wash cycle of the washing machine water is introduced into the drum and the drum periodically rotates. The design of the dispensing device should be such that it permits cont~inment of the dry d~tel~ellt 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 delergent product during the wash the device may possess a number of openings through which the product may pass.
~ltern~tively, the device may be made of a material which is permeable to liquid but impermeable to the solid product, which will allow release of dissolved product. Preferably, the delerge-lt product will be rapidly released at the start of the wash cycle thereby providing tr~n~ient localised high concentrations of product in the drum of the washing machine at this stage of the wash cycle.

Prefelled dispensing devices are reusable and are designed in such a way that cont~iner integrity is m~int~inP~l in both the dry state and during the wash cycle. Especially prefeiied dispen~in~ devices for use with the composition of the invention have been described in the following patents;
GB-B-2, 157, 717, GB-B-2, 157, 718, EP-A-0201376, EP-A-0288345 WO 97/0316~ PCTrUS96/11298 46 and EP-A-0288346. An article by J.Bland published in ~nllf~cturing Chemist, November 1989, pages 4146 also describes especially ~rerelled dispensing devices for use with granular laundry products which are of a type commonly know as the "granulette". Another preferred dispensing device for use with the compositions of this invention is disclosed in PCT
Patent Application No. WO94/11562.

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 extending 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~lium. The support ring is provided with a m~kin~ arrangemnt to prevent egress of wetted, undissolved, product, this arrangement typically comprising radially ext.Qn~lin~ walls e~tPn~linE from a central boss in a spoked wheel configuration, or a ~imil~r structure in which the walls have a helical form.

Alternatively, 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 contents, 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 designed to rupture 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 sealing one edge of a pouch formed of a water impermeable polymeric film such as polyethylene or polypropylene.

Packa~ing for the compositions Commercially marketed executions of the bleaching compositions can be packaged in any suitable container including those constructed from -CA 0222662l l998-0l-l2 W O 97/03164 PCT~US96/11298 paper, cardboard, plastic materials and any suitable 1~min~tes. A
~refel~ed pacl~ in~ execution is described in European Application No.
- 94921505.7.

-PCTnUS96/11298 Abbreviations usçd in Examples In the detergellt compositions, the abbreviated component identifications have the following me~nin~.c:

LAS : Sodium linear C12 alkyl ben7ene sulfonate TAS : Sodium tallow alkyl sulfate C45AS : Sodium C14-Cls linear alkyl sulfate CxyEzS : Sodium Clx-Cly branched alkyl sulfate condensed with z moles of ethylene oxide C45E7 : A C14 15 predomin~ntly linear primary alcohol condensed with an average of 7 moles of ethylene oxide (HLB = 12.3) C25E3 : A C12 15 branched primary alcohol condensed with an average of 3 moles of ethylene oxide (HLB = 8.8) C25E5 : A C12 15 branched primary alcohol condensed with an average of 5 moles of ethylene oxide (HLB = 11.1) CEQ : RlCOOCH2CH2.N+(CH3)3 with Rl = Cll-l TCEQ : R2R3COOCH2CH2.N + (CH3)3 with R2 = C8 and R3 = C6 QAS : R2.N+(CH3)2(C2H4OH) with R2 = C12 ~ C14 Soap : Sodium linear alkyl carboxylate derived from an 80/20 mixture of tallow and coconut oils.
TFAA : C16-Clg alkyl N-methyl ~lllc~mide TFAA2 : Hydrophilic C12-C14 alkyl N-methyl gl~lc~mi~le.
TPKFA : C12-C14 topped whole cut fatty acids STPP : Anhydrous sodium tripolyphosphate Zeolite A : Hydrated Sodium Aluminosilicate of formula Nal2(A1~2Si~2)12. 27H20 having a primary 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 -W O 97/03164 PCTnUS96/11298 Carbonate : Anhydrous sodium carbonate with a particle size between 200~1m and 900)1m Bicarbonate : Anhydrous sodium bicarbonate with a particle size distribution betvveen 400~m and 1200~Lm Silicate : Amorphous Sodium Silicate (SiO2:Na2O; 2.0 ratio) Sodium sulfate: Anhydrous sodium sulfate Citrate : Tri-sodium citrate dihydrate of activity 86.4%
with a particle size distribution between 425~m and 850 llm MA/AA : Copolymer of 1:4 maleic/acrylic acid, average molecular weight about 70,000.
CMC : Sodium carboxymethyl cellulose Protease : Proteolytic enzyme of activity 4KNPU/g sold by NOVOTn~netries A/S under the tradename Savinase Alcalase : Proteolytic enzyme of activity 3AU/g sold by NOVOTn~lstries A/S
Cellulase : Cellulytic enzyme of activity 1000 CEVU/g sold by NOVOTn~stries A/S under the tr~en~m~
Carezyme Amylase : Amylolytic enzyme of activity 60KNU/g sold by NOVOTn~lletries A/S under the tradename Termamyl 60T
Lipase : Lipolytic enzyme of activity 100kLU/g sold by NOVO Tn~l~l.stries A/S under the tr~-len~me Lipolase Endolase : Endogllln~.~e enzyme of activity 3000 CEVU/g sold by NOVOTn~llstries A/S
PB4 : Sodium perborate tetrahydrate of nominal formula NaBO2.3H2O-H2o2 PBl : Anhydrous sodium perborate monohydrate bleach of nominal formula NaBO2.H2O2 Percarbonate : Sodium Pelcarl~onate of nominal formula 2Na2C03.3H202 NOBS : Nonanoyloxybenzene sulfonate in the form of the sodium salt.

TAED : Tetraacetylethylenefli~mine DTPMP : Diethylene tri~mine penta (methylene phosphonate), marketed by Monsanto under the Trade name Dequest 2060 Photoactivated: Sulfonated Zinc Phthlocyanine encapsulated in bleach dextrin soluble polymer Brightener 1 : Disodium 4,4'-bis(2-sulphostyryl)biphenyl Brightener 2 : Disodium 4,4'-bis(4-anilino-6-morpholino-1.3.5-triazin-2-yl)amino) stilbene-2: 2 ' -disulfonate .
HEDP : 1, l-hydroxyethane diphosphonic acid PVNO : Polyvinylpyridine N-oxide PVPVI : Copolymer of polyvinylpyrolidone and vinylimicl~ole SRP 1 : Sulfobenzoyl end capped esters with oxyethylene oxy and terephtaloyl backbone SRP 2 : Diethoxylated poly (1, 2 propylene terepht~l~te) short block polymer Silicone antifoam: Polydimethylsiloxane foam controller with siloxane-oxyalkylene copolymer as dispersing agent with a ratio of said foam controller to said dispersing agent of 10:1 to 100:1.
In the following F~mrles all levels are quoted as % by weight of the composition:

Example 1 Comparative performance test protocol - stain removal Two white polyester cotton sheets were prewashed in a non-biological bleach-free heavy duty detergent. Two sets of eight test swatches of size 6cm x 6cm were cut from each sheet. SBK sebum stains were then evenly applied using a paint brush to one set of swatches, and lipstick stains to the second set.

Each of the eight swatches of each swatch set was subjected to one washcycle in an Atlas (tr~-len~me) launderometer. The swatches were then W O 97/03164 PCTrUS96/11298 assessed for removal of the various fatty stains by a four person grading panel using the well-known four-point Scheffé scale.

In more detail, an Atlas ~ n~lerometer was employed, and a 60~C, 45 mimlte wash cycle employed. Water of 10~ Clark hardness ( = 1.5 mmol Ca2+/litre) was used. Defined levels of deler~ellt base powder and surfactant system were employed in the wash solutions.

The detergent base powder was made up with the following composition:

Base powder Zeolite A 13.0 Na SKS-6/citric acid (79:21) 13.5 Carbonate 9.6 TAED 6.6 Percarbonate 29.0 DETPMP 1. 1 Protease 0.8 Lipase 0.18 Cellulase 0.32 Amylase 0.30 MA/AA 3.7 CMC 0.5 Granular suds ~u~ )ressor 1.9 Misctmoisture to 100%
-W O 97/03164 PCT~US96tll298 Comparative testin~ 1 - wash solutions The above stain removal test protocol was followed in comparing the efficiency of four dirrerent wash solutions A to D in removing fatty soils.
Wash solution B was derived by a~r~liate dissolution of a surf~ct~nt sy~le~ in accord with the invention, in combination with the deter~;ellt base powder. Wash solutions A, C and D are comparative solutions.

The composition of each of the wash solutions was as follows:

A B C D
C45AS 280 ppm 280 ppm 400 ppm 400 ppm C35AE3S 100 ppm 100 ppm 100 ppm 100 ppm C45E7 - 400 ppm - 400 ppm C25E3 400 ppm - 400 ppm CEQ 120 ppm 120 ppm Base powder5000 ppm 5000 ppm 5000 ppm 5000 ppm Comparative testin~ 1 - results B vs A B vs D A vs C
Sebum removal (PSU) +1.3s +0.9s -0.1 Lipstick removal +1.5s +2.3s -0.5 (PSU) s = significant at 95% confi~lence level The comparisons show that:

1. When the hydrophobic C25E3 nonionic of A is replaced by the hydrophilic C45E7 nonionic of B stain removal performance is enhanced.

2. When a portion of the C45AS of D is replaced by CEQ in the presence of hydrophilic C45E7 stain removal pelrolmance is enh~nced.

W O 97/03164 PCTrUS96/11298 3. When a portion of the C45AS of C is replaced by CEQ in the presence of hydrophobic C25E3 stain removal pelrc,llllance, by contrast is reduced.

Comparative testin~ 2 - wash solutions The above stain removal test protocol was followed, with two adjustments namely that the wash temperature was 30~C and the sebum soil was replaced by a dirty motor oil soil, in comparing the efficiency of two further wash solutions E and F in removing fatty soils. Wash solution F
was derived by ~ropliate dissolution of a surfactant system in accord with the invention. Wash solution E is comparative.

The composition of each of the wash solutions was as follows:

E F
C45AS 360 ppm 360 ppm C35AE3S 90 ppm 90 ppm C45E7 - 340 ppm C25E3 340 ppm TTCEQ 140 ppm 140 ppm Base powder 5000 ppm 5000 ppm Comparative testin~ 2 - results F vs E
Dirty motor oil removal (PSU) +0.9s Lipstick removal (PSU) + 1.5s s = si~nificant at 95% confi-le.nce level W O 97/03164 PCTrUS96/11298 The comparison shows that:

1. When the hydrophobic C25E3 nonionic of E is replaced by the hydrophilic C45E7 nonionic of F stain removal performance is enhanced.

W O 97/03164 PCTnUS96111298 Example 2 - The following laundry detel-gellt compositions A to F were prepared in accord with the invention:

A B C D E F
C45AS 8.0 8.0 8.0 8.0 8.0 8.0 C45E7 3.4 4.4 5 0 3 0 7 0 3 0 CEQ 1.0 0.8 1.2 1.0 0.8 0.6 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 0.25 0.25 0.250.25 0.250.25 HEDP 0.3 0.3 0.3 0.3 0.3 0-3 Protease 0.26 0.26 0.260.26 0.260.26 Amylase 0.1 0.1 0.1 0.1 0.1 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 W O 97/03164 PCTrUS96/11298 Photoactivated 15 15 15 15 15 15 bleach (ppm) ppm ppm ppm ppm ppmppm Brightener 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 antifoam 0.5 0.5 0.5 0.5 0.5 0.5 Misc/minors to 100%

Density in g/litre 630 670 670 500 670 670 ~lk~linity 6.8 6.8 6.8 18.5 18.5 18.5 W O 97/03164 PCTrUS96/11298 Ex~mple 3 The following granular laundry detergellt compositions G to I of buLk density 750 g/litre were prepared in accord with the invention:

G H
TAS 1.2 1.8 1.6 C45AS 5.2 7.0 8.0 C25AE3S - 0.8 1.2 C45E7 3.25 5.5 5.0 CEQ 0.8 1.0 2.0 STPP 10.7 Zeolite A - 19.5 19.5 NaSKS-6/citric acid - 10.6 10.6 (79:21) Carbonate 16.1 21.4 21.4 Bicarbonate - 2.0 2.0 Silicate 6.8 Sodium sulfate 39.8 - 14.3 PB4 5.0 12.7 TAED 0.5 3.1 DETPMP 0.25 0.2 0.2 HEDP - 0.3 0.3 Protease 0.26 0.85 0.85 Lipase 0.15 0.15 0.15 - Cellulase 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~htçner 1 0.08 0.19 0.19 Bri ~htçner 2 - 0.04 0.04 Perfume 0.3 0.3 0.3 Silicone antifoam 0.5 2.4 2.4 Minors/misc to 100%

W O 97/03164 PCT~US96/11298 Example 4 The following delergent formulations, according to the present invention were ~r~ared, where J is a phosphorus-cont~inin~ deterge,lt composition, K is a zeolite-cont~inin~ detelgent composition and L is a compact deleLgelll composition:
J K L
Blown Powder STPP 14.0 - 14.0 Zeolite A - 20.0 C45AS 9.0 12.0 8.0 MA/AA 2.0 4.0 2.0 LAS 6.0 - 9.0 TAS 2.0 CEQ 1.5 3.0 1.5 Silicate 7.0 8.0 8.0 CMC 1.0 1.0 0.5 Bri~htener 2 0.2 0.2 0.2 Soap 1.0 1.0 1.0 DTPMP 0.4 0.4 0.2 Spray On C45E7 5.0 5.0 4.0 Silicone antifoam 0.3 0.3 0.3 Perfume 0.3 0.3 0-3 Dry additives Carbonate 26.0 23.0 25.0 PB4 18.0 18.0 10 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 Amylase 0.25 0.30 0.15 Dry mixed sodium 3.0 3.0 5.0 sulfate Balance (Moisture & 100.0 100.0 100.0 Miscellaneous) Density (g/litre) 630 670 670 CA 0222662l l998-0l-l2 W O 97/03164 ~CT~US96/11298 Example ~;

The following nil bleach-cont~ining delergellt formulations of particular use in the washing of colored clothing, according to the present invention were prepared:

M N O P
Blown Powder ZeoliteA 15.0 15.0 - 15.0 Sodium sulfate 0.0 5.0 - 0.0 CEQ 2.0 1.5 1.3 2.0 DTPMP 0.4 0.5 - 0.4 CMC 0.4 0.4 - 0.4 MA/AA 4.0 4.0 - 4.0 LAS - - - 3.0 Agglomerates LAS - - - 6.0 C45AS 8.0 7.0 11.0 TAS 3.0 2.0 - 3.0 Silicate 4.0 4.0 - 4.0 Zeolite A 10.0 15.0 13.0 10.0 CMC - - 0.5 MA/AA - - 2.0 Carbonate 9.0 7.0 7.0 9.0 Spray On Perfume 0.3 0.3 0.5 0.3 C45E7 4.0 6.0 4.0 6.0 C25E3 2.0 - 2.0 3.0 Dry additives HEDP - - - 0.5 MA/AA - - 3.0 NaSKS-6 - - 12.0 Citrate 10.0 - 8.0 10.0 Bicarbonate 7.0 3.0 5.0 6.0 Carbonate 8.0 5.0 7.0 6.0 PVPVI/PVNO 0.5 0.5 0.5 0.5 Alcalase 0.5 0.3 0.9 0.5 ~ ir~e 0.4 0.4 0.4 0.4 W O 97/03164 PCT~US96/11298 Amylase 0.6 0.6 0.6 0.6 Cellulase 0.6 0.6 0.6 0.6 Silicone alltifoam 5.0 5.0 5.0 5.0 Dry additives Sodium sulfate 0.0 9.0 0.0 0.0 R~l~nce (Moisture and 100.0 100.0 100.0 100.0 Miscellaneous) Density (g/litre) 700 700 700 700 W O 97/03164 PCTrUS96/11298 Example 6 ~ The following detergent formulations, according to the present invention were prepared:
Q R S T
C45AS 12.0 12.0 12.0 10.0 - QAS 0.7 1.0 - 0.7 TFAA - 1.0 - -C25E5 4.0 5.0 5.0 5 0 C45E3S - 2.5 CEQ 2.0 1.5 1.0 1.0 STPP 30.0 18.0 15.0 Silicate 9.0 7.0 10.0 Carbonate 15.0 10.5 15.0 25.0 Bicarbonate - 10.5 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 ~ .ir~e 0.2 0. 1 0.2 0. 1 Cellulase 0.15 0.05 Photoactivated70ppm 45ppm - 10ppm bleach (ppm) Brightener 1 0.2 0.2 0.08 0.2 PBl 6.0 2.0 NOBS 2.0 1.0 R~l~nce 100 100 100 100 (Moisture and Miscellaneous) = ~

W O97/03164 PCT~US96/11298 Example 7 The following deterg~l1t formulations, according to the present invention were prepared:
U V W
Blown Powder Zeolite A10.0 15.0 6.0 Sodium sulfate 19.0 5.0 7.0 MA/AA 3.0 3.0 6.0 C45AS 14.0 13.0 14.0 C E Q 2.0 2.0 2.0 Silicate - 1.0 7.0 Soap - - 2.0 Bri~ht~nPr 1 0.2 0.2 0.2 Carbonate 28.0 26.0 20.0 DTPMP - 0.4 0.4 Spray On C45E7 3.0 3.0 3.0 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 0.1 0.1 Cell~ 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 Miscellaneous) -W O 97/03164 PCTrUS96/11298 Example 8 The following high density and bleach-cont~inin~ detergent formulations, according to the present invention were prepared:

X Y Z
Blown Powder Zeolite A 15.0 15.0 15.0 Sodim sulfate 0.0 5.0 0.0 45AS 4.0 4.0 4.0 QAS - 1.5 1.5 CEQ 1.0 1.0 0.5 DTPMP 0.4 0.4 0.4 CMC 0.4 0.4 0-4 MA/AA 4.0 2.0 2.0 Agglomerates LAS 4.0 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 6.0 Spray On Perfume 0.3 0.3 0.3 C45E7 4.0 4.0 4.0 Dry additives Citrate 5.0 - 2.0 Bicarbonate - 3.0 Carbonate 8.0 15.0 10.0 TAED 6.0 2.0 5.0 PB1 14.0 7.0 10.0 Polyethylene oxide of MW - - 0.2 5,000,000 Bento.~ile clay - - 10.0 Protease 1.0 1.0 1.0 Lipase 0.4 0.4 0.4 Amylase 0.6 0.6 0.6 Cellulase 0.6 0.6 0.6 CA 0222662l l998-0l-l2 4 PCTrUS96/11298 Silicone antifoam5.0 5.0 5.0 Dry additives Sodium sulfate 0.0 3.0 0.0 Balance (Moisture and 100.0 100.0 100.0 Miscellaneous) Density (g/litre) 850 850 850 W O 97/03164 PCTrUS96/11298 Example 9 The following _igh density detergellt formulations, according to the present invention were ~r~ared:
AA AB AC

Agglomerate C45AS 11.0 14.0 12.0 CEQ 3.0 3.5 3.5 Zeolite A 15.0 6.0 6.0 Carbonate 4.0 8.0 8.0 MA/AA 4.0 2.0 2.0 CMC 0.5 0.5 0.5 DTPMP 0.4 0.4 0.4 Spray On C25E5 5.0 5.0 C25E3 - 5 o TFAA2 - - 1.0 Perfume 0.5 0.5 Dry Adds HEDP 0.5 0.3 0.3 SKS 6 13.0 10.0 10.0 Citrate 3.0 1.0 1.0 TAED 5.0 7.0 7.0 Percarl,onate 20.0 20.0 20.0 SRP 1 0.3 0.3 0.3 Protease 1.4 1.4 1.4 Lipase 0.4 0.4 0.4 Cellulase 0.6 0.6 0.6 Amylase 0.6 0.6 0.6 Silicone antifoam 5.0 5.0 5.0 Bri~htenPr 1 0.2 0.2 0.2 Bri~htenPr 2 0.2 R~l~nce (Moisture and 100 100 100 Miscellaneous) Density (g/litre) 850 850 850 W O 97/03164 P ~ rUS96/11298 Example 10 The following liquid dele~e,l~ formulations, according to the present invention were prepared:
AD AE AF AG AH AI AJ AK
C45AS 10.11.0 9.0 - 13.0 - - -C25AS 4.0 1.0 2.0 10. - 11.0 15.0 15.0 O
C25E3S 1.0 - - 3.0 - - 2.0 4.0 C25E7 6.0 8.0 11. 2.5 10.0 2.0 4.0 4.0 o TFAA - - - 4.5 - 6.0 8.0 8.0 C12-14 ally1 - - - - 3 ~lim~thylhydroxy ethyl ammonium chloride CEQ 0.5 1.5 1.0 0.7 2.0 1.5 1.8 2.0 TPKFA 2.0 - 11. 2.0 - 13.0 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 Fth~nnl 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 8.0 13.0 Mono Ethanol Amine - - - 5.0 - - 9.0 9.0 Tri Ethanol Amine - - 8.0 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 pen~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 CA 0222662l l998-0l-l2 W O 97/03164 PCT~US96/11298 Protease 0.5 0.5 0.4 0.2 - 0.5 0.3 0.6 Alcalase - - - - 1.5 Lipase - 0.10 - 0.0 - - 0.15 0.15 Amylase 0.2 0.25 0.6 0.5 0.25 0.9 0.6 0.6 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 B~l~nce (water and 100 100 100 100 100 100 100 100 Miscellaneous)

Claims (14)

WHAT IS CLAIMED IS:

1. A surfactant system comprising:

(a) an anionic sulfate surfactant component;

(b) a cationic ester surfactant; and (c) a hydrophilic alkoxylated nonionic surfactant having a HLB
value of at least 9.1 wherein the weight ratio of anionic sulfate surfactant component to cationic ester surfactant is from 2.5:1 to 20:1 and the weight ratio of anionic sulfate surfactant component to hydrophilic alkoxylated nonionic surfactant is from 1:5 to 5:1.

2. A surfactant system according to Claim 1 wherein the anionic sulfate component contains both alkyl sulfate and alkyl ethoxysulfate surfactant at a weight ratio of from 2:1 to 19:1.

3. A surfactant system according to Claim 1 wherein the anionic sulfate component contains only C10-C18 alkyl sulfate.

4. A surfactant system 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 NHCOO and CON(R9OR10)Z, and CONR11Z wherein at least one of X or Y is a COO, OCO, OCOO, OCONH or NHCOO group; R2, R3, R4, R6, R7, R8 and R11 are independently selected from the group consisting of alkyl, alkenyl, hydroxyalkyl, hydroxy-alkenyl and alkaryl groups having from 1 to 4 carbon atoms; R9 and R10 are independently selected from the group consisting of linear or branched, saturated or unsaturated carbon chains having from 1 to 8 carbon atoms; Z is a polyhydroxyhydrocarbyl moiety; 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 and v is 1; and wherein M is a counter anion.

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

6. A surfactant system according to Claim 4 wherein the cationic ester is selected from the choline esters having the formula:

wherein R1 is a C11-C19 linear or branched alkyl chain.

7. A surfactant system according to any of Claims 1 to 6 wherein the hydrophilic alkoxylated nonionic surfactant comprises ethoxylated aliphatic fatty alcohol surfactant having a degree of ethoxylation of at least 4.

8. A surfactant system according to Claim 7 wherein the ethoxylated aliphatic fatty aliphatic alcohol has an alkyl group containing from 12 to 20 carbon atoms and the degree of ethoxylation is from 4 to 10.

9. A surfactant system according to any of Claims 1 to 8 wherein the weight ratio of anionic sulfate surfactant component to cationic ester surfactant is from 5:1 to 10:1 and the weight ratio of anionic sulfate surfactant component to hydrophilic alkoxylated nonionic surfactant is from 1:3 to 3:1.

10. A surfactant system according to any of Claims 1 to 9 containing additional surfactant selected from non-sulfate anionic, hydrophobic alkoxylated nonionic, non-alkoxylated nonionic, non-ester cationic, ampholytic, amphoteric and zwitterionic surfactants and mixtures thereof.

11. A surfactant system comprising:

(a) an anionic sulfate surfactant component;

(b) A cationic ester surfactant; and (c) a hydrophilic nonionic surfactant system comprising a plurality of nonionic surfactants having a HLB value of at least 9.1 wherein the weight ratio of anionic sulfate surfactant component to cationic ester surfactant is from 2.5:1 to 20:1 and the weight ratio of anionic sulfate surfactant component to hydrophilic nonionic surfactant system is from 1:5 to 5:1.

12. A surfactant system according to Claim 11 wherein said hydrophilic nonionic surfactant system comprises alkoxylated nonionic and polyhydroxy fatty acid amide surfactant.

13. A detergent composition comprising:

(a) from 1% to 95% by weight of the composition of a surfactant system according to any of Claims 1 to 12; and (b) at least one detergent component selected from bleaches, builders, organic polymeric compounds, enzymes, suds suppressors, lime soap dispersants, soil suspension and anti-redeposition agents and corrosion inhibitors.

14. 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 Claim 13 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.