CA2247829A1 - Cationic detergent compounds - Google Patents

Abstract

There is provided a cationic ester surfactant comprising at least one ester linkage and at least one cationically charged group characterized in that said cationically charged group is an ammonium group substituted by at least one hydroxyalkyl group. Surfactant systems and detergent compositions suitable for use in laundry and dishwashing methods containing the cationic ester surfactants are also provided.

Description

W O 97/32955 PCTnJS97/03111 Cationic deter~ent compounds Technical field The present invention relates to selected cationic ester surfactants which are suitable for use in laundry and dish w~hing methods.

Back~round to the invention The satisfactory removal of greasy soils/stains, that is soils/stains having a high proportion of triglycerides or fatty acids, is a challenge faced by the formlll~tQr of detergent compositions for use in machine laundry and dishw~.~hing methods. Surfactant components have traditionally been employed in detelgellt products to facilitate the removal of such greasy soils/stains.

In particular, surf~ct~nt systems comprising cationic ester surf~ct~ntc have been described for use in greasy soil/stain removal. By cationic ester surfactants it is meant those compounds having surf~ct~nt properties which comprise at least one ester (i.e. -COO-) linkage and at least one cationically charged group. The cationically charged group is often an ammonium or substituted ammonium group.

For example, EP-B-21,491 discloses delel~,elll compositions cont~ining a nonionic/cationic surfactant mixture and a builder mixture comprising aluminosilicate and polycarboxylate buildler. The cationic surfactant may be a cationic ester. Improved particulate and greasy/oily soil removal is described.

US-A-4,228,042 discloses biodegradable cationic surf~ct~nt~, including cationic ester surfactants for use in detergent compositions to provide greasy/oily soil removal. The combination of these cationic surfactants with nonionic surf~ct~nt~ in compositions de~ign~l for particulate soil removal is CA 02247829 l998-08-3l W O 97/32955 PCT~US97/03111 also described. Anionic sur~actants are disclosed as optional components of the compositions, but are present at low levels relative to the cationic surfactant component.

US-A-4,239,660 discloses laundry detergent compositions cont~inin~
cationic ester surfactant and nonionic surfactant at defined weight ratios and an ~lk~linity source. The ~lk~linity source enables a wash solution having a pH of from 8 to 10 to be formed within 3 minlltes of dissolution of the composition in water at 100~F (37~C) at a solution concentration of 0.15%.

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 surf~et~nt component.

The Applicants have now found that certain cationic ester surf~t~nt~, in which the cationically charged group is an amrnonium group substi~lte~l by at least one hydroxyalkyl group, demonstrate enhanced stain removal performance under the wash conditions of a typical laundry method, particularly at low wash temperatures. The enh~n~e~l low wash temperature performance is believed to be related to the good cold water solubility of these cationic esters. Additionally, the cationic ester surf~ct~nt~
demonstrate enh~nce ;l perfume robustness, that is to say that fabrics washed in perfume-cont~ining detergellls cont~inin~ these surfactants have an improved perfume profile.

The prior art documents cited above include a general description of cationic ester surf~ct~nts in which it is envisaged that the cationically charged group is an ammonium substituted optionally by various substitutuent groups. Choline ester surf~ct~nt.~ having methyl substituerlts are however, exclusively exemplified. None of the documents provides any teaching of the enhanced stain removal capability or perfume robustness exhibited by the present cationic ester surfactants in which the cationically W O 97/32955 PCTrUS97/03111 charged group is an ammonium group substituted by at least one hydroxyalkyl group.

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

S~-mm~ of the Invention According to the present invention there is provided a cationic ester surfactant comprising at least one ester (i.e. -COO-) linkage and at least one cationically charged group characterized in that said cationically charged group is an ammonium group substi~lte~l by at least one hydroxyalkyl group.

In a preferred aspect, the cationic ester surfactant is selected from those having the forrnula:

Rs +
R~ (CH)nO b (X)U (C~2)m-(~v-(CH2)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 consisting of COO, OCO, O, CO, OCOO, CONH,NHCO, OCONH and NHCOO wherein at least one of X or Y is a COO, OCO, OCOO, OCONH or NHCOO group; R2 is a hydroxyalkyl group having from 1 to 4 carbon atoms; R3, R4, R6, R7, and R8 are independently selected from the group consisting of alkyl, alkenyl, hydroxyalkyl, hydroxy-alkenyl and alkaryl groups having from 1 to 4 carbon atoms; and Rs 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 W O 97/32955 PC~rUS97/03111 the range from 0 to 20, and the values of a, u and v independently are either 0 or 1 with the proviso that at least one of u or v must be 1; and wherein M is a counter anion.

l;)etailed description of the invention Cationic ester surfactant The sur~actant of the present invention 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 cationically charged group is an amrnonium group substituted by at least one, preferably only one, hydroxyalkyl group. The hydroxyallyl preferably has from 1 to 4 carbon atoms, more preferably 2 or 3 carbon atoms, most preferably 2 carbon atoms.

Preferred cationic ester surfactants are those having the formula:

~l-- R5 ~X)u ( C H2 )m (Y)v--(C H2 )t--N--R3 M
b 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 con~i~tin~ of COO, OCO, O, CO, OCOO, CONH, NHCO, OCONH and NHCOO wherein at least one of X or ~ is a COO, OCO, OCOO, OCONH or NHCOO group; R2 is a hydroxyalkyl group having from 1 to 4 carbon atoms; R3, R4, R6, R7, and R8 are independently selected from the group consisting of alkyl, alkenyl, hydroxyalkyl, hydroxy-alkenyl and alkaryl groups having from 1 to 4 carbon atoms; and Rs is independently H or a Cl-C3 alkyl group; wherein the values of m, n, CA 02247829 l998-08-3l W O 97/32955 PCTrUS97/03111 s and t independently lie in the range of from O to 8, the value of b lies in ~ the range from O to 20, and the values of a, u and v independently are either O or 1 with the proviso that at least one of u or v must be 1; and ~ wherein M is a counter anion.

Preferably R2 is a -CH2CH20H group and R3 and R4 are both CH3 groups.

Preferably M is selected from the group consisting of halide, methyl sulfate, sulfate, and nitrate, more preferably methyl sulfate, chloride, bromide or iodide.

Preferred water dispersible cationic ester surfactants are the hydroxyethyl choline esters having the formula:

R1 C ~--CH2CH2--N~--CH3 M-wherein Rl is a Cll-Clg linear or branched alkyl chain.

Particularly preferred choline esters of this type include the stearoyl choline ester quaternary dime~yl(hydroxyethyl)ammonium halides (Rl=C17 alkyl), p~lmitoyl choline ester quaternary dimethyl(hydroxyethyl~ammonium halides (Rl =Cls alkyl), myristoyl choline ester quaternary dimethyl(hydro~cyethyl)ammonium halides (Rl = C 13 alkyl), lauroyl choline ester dimethyl(hydroxyethyl)ammonium halides (Rl =Cl l alkyl), cocoyl choline ester quaternary dimethyl(hydroxyethyl)ammonium halides (Rl =Cl l C13 alkyl), tallowyl choline ester quaternary dimethyl(hydroxyethyl)ammonium halides (Rl=Cls C17 alkyl), and any mixtures thereof.

The particularly preferred cationic esters, given above, may be synthesized by the direct ~mid~tion of a fatty acid (RlCOOH), fatty acid ester W O 97/32955 PCT~US97/03111 (RlCOORn) or fatty acid halide (R1COOHal) of the desired chain length with diethanol~mine (a secondary amino alcohol) to form diethanolamide, preferably in the presence of a catalyst, such as an acid catalyst methanesulfonic or sulfuric acid or a basic catalyst, such as sodium methoxide. The reaction product is heated, preferably under acid conditions, to force the rearrangement of the ethanolamide to the ester amine, which is then quaternized with a 'quaternizing agent' such as methyl halide, methyltosylate or dimethylsulfate forming the desired cationic ester.

The quaternization step in the above synthetic route is preferably carried out in the presence of a solvent such as ethanol, toluene, propylene glycol or preferably a fatty alcohol ethoxylate such as C1o-C1g fatty alcohol ethoxylate having a degree of ethoxylation of from 3 to 50 ethoxy groups per mole. It can be useful to have an anionic surfactant, such as linear alkyl benzene sulfonate present during the ~uaternization step to disrupt the formation of any aqueous gel phases.

Analogous synthetic routes may be employed to make other cationic esters in accord with the invention.

Thus a route involving esterification of an, optionally substi~-te~l, secondary amino alcohol with a fatty acid, fatty acid ester or fatty acid halide to form an alkanol~mirle, followed by rearrangement of the amide to form an ester amine, followed by quaternization of the amine group with an, optionally substitl~te~l~ alkyl halide to obtain the cationic ester product is generally envisaged.

Surfactant systems Surfactant systems herein comprise the cationic ester surfactant in accord with the present invention in combination with an additional surfactant selected from nonionic, non-ester cationic, ampholytic, amphoteric and zwitterionic surf~ct~nt~ and mixtures thereof.

-W O 97/32955 PCTrUS97/03111 A typical listing of anionic, nonionic, ampholytic, and zwitterionic classes, and species of these surfactants, is given in U.S.P. 3,929,678 issued to l_aughlin and EIeuring 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.

Surfactant sytems comprising anionic and/or nonionic surfactants in combination with the cationic ester surfactants of the invention are preferred herein. Most preferably the surfactant systems comprise both anionic and nonionic surfactants in combination with the cationic ester surfactants of the invention.

The weight ratio of anionic surfactant to cationic ester surfactant in the surfactant system is preferably from 3:1 to 50:1, more preferably from 4:1 to 40:1, most preferably from 5:1 to 20:1.

The weight ratio of nonionic surfactant to cationic ester surf~l~t~nt in the surfactant system is preferably from 3:1 to 50:1, more preferably from 4:1 to 40:1, most preferably from 5:1 to 20:1.

Anionic surfactant Essentially any anionic surfactants useful for detersive purposes are suitable. These can include salts (including, for example, sodium, potassium, ammonium, and substih-te-l ammonium salts such as mono-, di-and triethano!~min~ salts) of the anionic sul~ate, sulfonate, carboxylate and sarcosinate surfactants. Anionic sulfate surfactants are preferred.

Other anionic surf~ct~nte include the isethionates such as the acyl isethionates, N-acyl taurates, fatty acid amides of methyl tauride, alkyl succinates and sulfosuccinates, monoesters of sulfosuccinate (especially saturated and lln.e~t~lrated C12-C18 monoesters) diesters of sulfosuccinate (especially saturated and llne~1~lrated C6-C14 diesters), N-acyl sarcosinates.

CA 02247829 l998-08-3l W O 97/32955 PCT~US97/03111 Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tallow oil.

Anionic sulfate surfactant Anionic sulfate 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 Cs-C17 acyl-N-(Cl-C4 alkyl) and -N-(C1-C2 hydroxyalkyl) glucamine sulfates, and sulfates of alkylpolysaccharides such as the sulfates of alkylpolyglucoside (the nonionic nonsulfated compounds being described herein).

Alkyl sulfate surfactants are preferably selected from the linear and branched primary Clo-Clg alkyl sulfates, more preferably the C11-C1s branched chain alkyl sulfates and the C12-C14 linear chain alkyl sulfates.

Alkyl ethoxysulfate surfactants are preferably selected from the group consisting of the C1o-C1g 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 C11-Clg, 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.

A particularly preferred aspect of the invention employs mixtures of the preferred alkyl sulfate and alkyl ethoxysulfate surfactants. Such mixtures have been disclosed in PCT Patent Application No. WO 93/18124.

Anionic sulfonate surfactant Anionic sulfonate surf~ct~nt~ suitable for use herein include the salts of Cs-C20 linear alkylbenzene sulfonates, alkyl ester sulfonates, C6-Cz primary or secondary alkane sulfonates, C6-C24 olefin sulfonates, sulfonated polycarboxylic acids, alkyl glycerol sulfonates, fatty acyl W O 97132955 PCTrUS97/03111 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 sur~actants 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 ~ 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, x is from 1 to 25, Rl and R2 are selected from the group consisting o~ hydrogen, methyl acid radical, succinic acid radical, hydroxysuccinic acid radical, and mixtures thereof, and R3 is selected from the group consisting of hydrogen, substihlte~l or unsubstituted hydrocarbon having between 1 and 8 carbon atoms, and mixtures thereof.

Suita~le soap surf~ct~nts include the secondary soap surf~t~nt~ which contain a carboxyl uI~it conn~cteA to a secondary carbon. Preferred secondary soap sur~ct~n~ for use herein are water-soluble members selected from the group consisting of the water-soluble salts of 2-methyl-1-~lnrl~c~noic 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 (Rl) CH2 COOM, wherein R is a Cs-C17 linear or branched alkyl or alkenyl group, Rl is a Cl-4 alkyl group and M is an W O 97/32955 PCT~US97103111 alkali metal ion. Preferred examples are the myristyl and oleoyl methyl sarcosinates in the form of their sodium salts.

Alkoxylated nonionic surfactant Essentially any alkoxylated nonionic surfactants are suitable herein. The ethoxylated and propoxylated nonionic surfactants are preferred.

Preferred alkoxylated surfactants can be selected from the classes of the nonionic condensates o~ alkyl phenols, nonionic ethoxylated alcohols, nonionic ethoxylated/propo~cylated fatty alcohols, nonionic ethoxylatelpropoxylate condensates with propylene glycol, and the nonionic ethoxylate condensation products with propylene oxide/ethylene dt~mine adducts.

Nonionic alkoxylated alcohol surfactant The condensation products of aliphatic alcohols with from 1 to 25 moles of alkylene oxide, particularly ethylene oxide and/or propylene oxide, are suitable for use herein. The alkyl chain of the aliphatic alcohol can either be straight or branched, primary or secondary, and generally contains from ~ to 22 carbon atoms. Particularly preferred are the condensation products of alcohols having an alkyl group cont~inin~ from 8 to 20 carbon atoms with from 2 to 10 moles of ethylene oxide per mole of alcohol.

Nonionic polyhydroxy fatty acid amide surfactant Polyhydroxy fatty acid amides suitable for use herein are those having the structural formula R2CONRlZ wherein: R1 is H, C1-C4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl, ethoxy, propoxy, or a mixture thereof, preferable C1-C4 alkyl, more preferably Cl or C2 alkyl, most preferably Cl alkyl (i.e., methyl); and R2 is a Cs-C31 hydrocarbyl, preferably straight-chain Cs-C1g 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 ;s a polyhydroxyhydrocarbyl having a CA 02247829 l998-08-3l W O 97/32955 PCTAJS97/~3111 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 reduc;ng sugar in a reductive ~min~tion reaction; more preferably Z is a glycityl.

Nonionic fatty acid amide surfactant Suitable fatty acid amide surfactants include those having the formula:R6CoN(R7)2 wherein R6 is an alkyl group cont~inin~ from 7 to 21, preferably from 9 to 17 carbon atoms and each R7 is selected from the group consisting of hydrogen, Cl-C4 allcyl, C l-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 con~ining from 6 to 30 carbon atoms a~d 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 consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the allyl 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.c for use herein include the amine oxidesurfactants and the alkyl amphocarboxylic acids.

W O 97132955 PCTrUS97/03111 Suitable amine oxides include those compounds having the formula R3(oR4)XNO(R5)2 wherein R3 is selected from an alkyl, hydroxyalkyl, acylamidopropoyl and alkyl phenyl group, or mixtures thereof, cont~ining from 8 to 26 carbon atoms; R4 is an alkylene or hydroxyalkylene group cont~inin~ from 2 to 3 carbon atoms, or mixtures thereof; x is from O to 5, preferably from O to 3; and each R5 is an alkyl or hydroxyalkyl group cont~inin~ from ~ to 3, or a polyethylene oxide group cont~inin~ from 1 to 3 ethylene oxide groups. Preferred are Clo-C1g alkyl dimethyl~min~
oxide, and C10 18 acylamido alkyl dimethyl~mint? oxide.

A suitable example of an alkyl aphodicarboxylic acid is Miranol(TM) C2MConc. manufactured by Miranol, Inc., Dayton, NJ.

Zwitterionic surfactant Zwitterionic surfactants can also be incorporated into the detergent compositions hereof. These surf~ct~nt~ can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. Betaine and sultaine surfactants are exemplary zwitterionic surfactants for use herein.

Suitable betaines are those compounds having the formula R(R')2N~R2COO- wherein R is a C6-C1g hydrocarbyl group, each Rl is typically C l-C3 alkyl, and R2 is a C 1-Cs hydrocarbyl group. Preferred betaines are C12 18 dimethyl-ammonio hexanoate and the C10-l8 acylamido~ro~alle (or ethane) ~limet~yl (or diethyl) betaines. Complex betaine surf~t~nt~ are also suitable for use herein.

Gationic surfactants Additional cationic surfactants can also be used in the detefgen~
compositions herein. Suitable cationic surfactants include the quaternary ammonium surf~ct~nt~ selected from mono C6-C16, preferably C6-Clo N-, CA 02247829 l998-08-3l W O 97/32955 PCT~US97/03111 alkyl or alkenyl ammonium surfactants wherein the rem~ining N positions are substituted by methyl, hydroxyethyl or hydroxypropyl groups.

I:)etergent compositions Detergent compositions may be form~ te-l cont~ining the cationic esters of the present invention, and the above me~tioned cationic ester cont~inin~
surfactant systems, in combination with additional detergent components.
Perfume-cont~inin~ d~tel~,ellL compositions are particularly favoured.

Preferably, the level of incorporation of the surfactant system is from 1%
to 95 %, more preferably from 3 % to 60 %, most preferably from 5 % to 40% by weight of the deLel~el,L composi~ion. The level of incorporation of the cationic ester surfactant is preferably from 0.1% to 50%, more preferably from 0.5% to 30%, most preferably from 1.0% to 10% by weight of the detel~;ellL composition.

Detergent compositions cont~ining one or more additional deterg,ellt components selected from the group consisting of an ~lk~linity system, bleaches, builders, organic polymeric co;mpounds, enzymes, suds suppressors, lime soap dispersants, soil suspension and anti-redeposition agents and corrosion inhibitors are thus envisaged. 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 w~hin~ operation for which it is to be used.

Alk~linity system Detergent compositions herein may contain from 1.5% to 95%, preferably from 5% to 605~, most preferably from 10% to 40% by weight of the composition of an ~lk~linity system comprising components capable of providing ~lk~linity species in solution. By ~lk~lini~y species it is meant herein: carbonate, bicarbonate, hydroxide and the various silicate anions.

Such ~lk~linity species can be formed for example, when ~lk~line salts selected from aLkali metal or ~lk~line earth carbonate, bicarbonate, hydroxide or silicate, including crystalline layered silicate, salts and any mixtures thereof are dissolved in water. Alkali metal percarbonate and persilicate salts are also suitable sources of ~lk~linity species.

Examples of carbonates are the ~lk~line 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 species and are described in more detail in the section ~inorganic perhydrate salts' herein.

Suitable silicates include the water soluble sodium silicates with an SiO2:
Na20 ratio of from 1.0 to 2.8, with ratios of from 1.6 to 2.0 being preferred, and 2.0 ratio being most 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.

Preferred cryst~llin~ 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 ~e general formula above preferably has a value of 2, 3 or 4 and is pre~erably 2. The most preferred material is ~-Na2Si20s, available from Hoechst AG as NaSKS-6.

The crystalline layered silicate material is preferably present in granular detergent compositions as a particulate in intim~te admixture with a solid, water-soluble ionisable material. The solid, water-soluble ionisable CA 02247829 l998-08-3l W O 97/3295~ PCTrUS97/03111 material is selected from organic acids, organic and inorganic acid salts and ~ mixtures thereof.

A preferred detergent composition herein comprises (a) from 1 % to 90 % by weight of the composition of a surfactant system comprising an anionic surfactant and a cationic ester surfactant in accord with the present invention at a weight ratio of anionic to cationic ester surfactant of from 3:1 to 15:1; and (b) from 1.5 % to 95 ~ by weight of the composition of an ~lk~l~nity system comprising ~lk~line salts selected from the group consisting of alkali metal or ~lk~line earth carbonate, bicarbonate, hydroxide or silicate, including crystalline layered silicate, salts and any mixtures thereof.

Water-soluble builder compound The detergent compositions herein 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%
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 se~al~ted from each other by not more that two carbon atoms, borates, phosphates, and mixtures of any of the foregoing.

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

W O 97/32955 PCTrUS97/03111 Suitable carboxylates cont~ining one carboxy group include the water soluble salts of lactic acid, glycolic acid and ether derivatives thereof.
Polycarboxylates cont~inin~ 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 cont~inin~ 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.

Polycarboxylates cont~inin~ four carboxy groups include oxydisuccinatesdisclosed in British Patent No. 1,261,829, 1,1,2,2-ethane tetracarboxylates, l,1,3,3-propane tetracarboxylates and 1,1,2,3-propane tetracarboxylates.
Polycarboxylates cont~ininp: 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 chelating agents or mixtures thereof with their salts, e.g. citric acid or citrate/citric acid rnixtures are also co~ nl~lated as useful builder components.

Borate builders, as well as builders cont~ininp: 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, potassium and ammonium pyrophosphate, sodium and potassium and ammonium pyrophosphate, sodium and CA 02247829 l998-08-3l W O 97/32955 PCTrUS97/03111 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 detergent compositions herein may contain a partially soluble or insoluble builder compound, typically present at a level of from 1% to 80 by weight, preferably from 10% to 70% by weight, most preferably from 20% to 60% weight of the composition.

Examples of largely water insoluble builders include the sodium aluminosilicates .

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

The aluminosilicate zeolites can be naturally occurring materials, but are preferably synthetically derived. Synthetic crystalline aluminosilicate 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 [Al~2) 12 (sio2)l2]. xH2O
wherein x is from 20 to 30, especially 27. Zeolite ~ has the formula Na86 [(Alo2)86(sio2)lo6~. 276 H2O.
Organic peroxyacid bleaching system A preferred feature of deteLgent compositions herein is an organic peroxyacid bleaching system. In one preferred execution the bleaching W O 97/3295~ PCT~US97/~3111 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. Preferred sources of hydrogen peroxide include inorganic perhydrate bleaches. In an alternative preferred execution a preformed organic peroxyacid is incorporated directly into the composition.
Compositions cont~inin~ mixtures of a hydrogen peroxide source and organic peroxyacid precursor in combination with a preformed organic peroxyacid are also envisaged.

Inorganic perhydrate bleaches Inorganic perhydrate salts are a preferred 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 preferably from 5% to 25 ~ by weight of the compositions.

Examples of inorganic perhydrate salts include perborate, percarbonate,perphosphate, persulfate and persilicate salts. The inorganic perhydrate salts 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 preferred executions of such granular compositions utilize a coated form of the material which provides better stora~e 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 preferred perhydrate salt and can be in ~e form of the monohydrate of nominal formula NaB02H202 or the tetrahydrate NaB02H202 3H20- .

Alkali metal percarbonates, particularly sodium percarbonate are preferred perhydrates herein. Sodium percarbonate is an addition compound having a W O 97/32955 PCTrUS97/03111 form~lla corresponding to 2Na2~O3.3H202, and is available commercially as a crystalline solid.

Potassium peroxymonopersulfate is another inorganic perhydrate salt of use in the detergent compositions herein.

Peroxyacid bleach precursor Peroxyacid bleach precursors are compounds which react with hydrogen peroxide in a perhydrolysis reaction to produce a peroxyacid. Generally peroxyacid bleach precursors may be represented as 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 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 imidazoles 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.

Leaving ~roups W O 97/3295~ PCT~US97/03111 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 dif~lcult to stabilize for use in a bleaching composition.

Pre~erred L groups are selected from the group consisting of:

_0~ o~Y and --~~

~ --N N --N--C--CH--R4 1 3 L~ R3 Y
y IR3 r --O--C H=C--C H=C H2 --O--C H=C--C H=C H2 Il Y ~
-~11--R1 ~CH2-C\ --N C/

O O
F~3 0 Y
--~C--CHR4 , and I S--CH--R4 R3 o and mixtures thereof, wherein R1 is an alkyl, aryl, or alkaryl group cont~ininp; from 1 to 14 carbon atoms, R3 is an alkyl chain cont~ining from 1 to 8 carbon atoms, R4 is H or R3, and Y is H or a solubilizing group.
Any of Rl, R3 and R4 may be substituted by essentially any functional W O 97/32955 PCT~US97/03111 group including, for example alkyl, hydroxy, alkoxy, halogen, amine, ~ nitrosyl, amide and ammonium or alkyl ~mmmonium groups ~ The preferred solubilizing groups are -SO3-M+, -CO2-M+, -SO4-M+, -N + (R3)~X- and O < --N(R3)3 and most preferably -SO3-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 substituted ammonium cation, with sodium and potassium 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. Preferred precursors of this type provide peracetic acid on perhydrolysis.

Preferred alkyl percall,oxylic precursor compounds of the imide type include the N-,N,NlNl tetra acetylated alkylene fli~mines wherein the alkylene group contains from 1 to 6 carbon atoms, particularly those compounds in which the allylene group contains 1, 2 and 6 carbon atoms.
Tetraacetyl ethylene ~ mine (TAED) is particularly pl~felled.

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

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

CA 02247829 l998-08-3l W O 97/32955 PCT~US97/03111 R1----C----N----R2---C--L R1 --N -C ~ 2~C L
O R5 O or R5 O O

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 substituted bleach activator compounds of this type are described in EP-A-0170386.

Perbenzoic acid precursor Perbenzoic acid precursor compounds provide perbenzoic acid on perhydrolysis. Suitable O-acylated perbenzoic acid precursor compounds include the substih-te~l and unsubstituted benzoyl oxybenzene sulfonates, and the benzoylation products of sorbitol, glucose, and all saccharides with benzoylating agents, and those of the imide type including N-benzoyl succinimide, tetrabenzoyl ethylene ~ mine and the N-benzoyl substituted ureas. Suitable imidazole type perbenzoic acid precursors include N-benzoyl imi~1~7O1e and N-benzoyl benzimidazole. Other useful N-acyl group-cont~ining perbenzoic acid precursors include N-benzoyl pyrrolidone, dibenzoyl taurine and benzoyl pyroglutamic acid.

Cationic peroxyacid precursors Cationic peroxyacid precursor compounds produce cationic peroxyacids onperhydrolysis.

Typically, cationic peroxyacid precursors are formed by substitlltin~ 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.

, W O 97/32955 PCT~US97/03111 The peroxyacid precursor compound to be so cationically substihlte~ maybe a perbenzoic acid, or substituted derivative thereof, precursor compound as described hereinbefore. Alternatively, the peroxyacid precursor compound may be an alkyl percarboxylic acid precursor compound or an amide subst;tuted 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.

Examples of preferred cationic peroxyacid precursors are described in UK
Patent Application No. 9407944.9 and US Patent Application Nos.
08/298903, 08/298650, 08/298904 and 08/298906.

Suitable cationic peroxyacid precursors include any of the ammonium or alkyl ammonium substitl-teA alkyl or benzoyl oxybenzene sulfonates, N-acylated caprolactams, and monobenw,yltetraacetyl glucose benzoyl peroxides. Preferred cationic peroxyacid precursors of the N-acylated caprol~ct~m class include the trialkyl ammonium methylene benzoyl caprol~st~m~ and the trialkyl ammonium methylene alkyl caprol~çt~m~.

Benzoxazin organic peroxyacid precursors Also suitable are precursor compounds of the benzoxazin-type, as disclosed for example in EP-A-332,294 and EP-A-482,807, particularly those having the formula:

~ NoC R1 wherein R1 is H, alkyl, alkaryl, aryl, or arylalkyl.

W O 97132955 PCTrUS97/03111 Preformed organic peroxyacid The organic peroxyacid bleaching system may contain, in addition to, oras 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 preferably from 1 % to 10 5~ by weight of the composition.

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

R1 C N ~ pC2--C OOH R1 N C R2 C--OOH
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 RS is H or an alkyl, aryl, or alkaryl group cont~inin~ 1 to 10 carbon atoms. Amide substituted orgar~ic peroxyacid compounds of this type are described in EP-A-0170386.

Other organic peroxyacids include diacyl and tetraacylperoxides, especially diperoxydorlec~n~-lioc acid, diperoxytetr~lec~nedioc acid and diperoxyhe~ lec~n~-lioc acid. Mono- and diperazelaic acid, mono- and diperbrassylic acid and N-phthaloyl~minoperoxicaproic acid are also suitable herein.

Bleach catalyst The detergent compositions optionally contain a transition metal cont~inin~;
bleach catalyst. One suitable type of bleach catalyst is a catalyst system 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 all~mim-m cations, and a sequestrant having defined stability con~t~nt~ for the catalytic and auxiliary metal cations, particularly ethylene~i~minetetraacetic acid, W O 97/329S~ PCTrUS97/03111 ethylene~ 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. Preferred examples of these catalysts include MnIV2(u-O)3(1,4,7-trimethyl-1,4,7-triazacyclononane)2-(PF6)2, MnIII2(u-O)l(u-OAc)2(1,4,7-trimethyl-1,4,7-triazacyclononane)2-(C104)2, MnIV4(u-C))6(1,4,7-triazacyclononane)4-(ClO4)2, MnIIIMnIV4(u-o)l(u-oAc)2-(l ,4,7-trimethyl-1,4,7-triazacyclononane)2-(C104)3, and mixtures thereof. Others are described in European patent application publication no. 549,272. Other ligands suitable for use herein include l,5,9-trimethyl-1,5,9-triazacyclodorlec~n~, 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 manganese (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~np;~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 n~ls, including N4MnIII(u-O)2MnIVN4) +and [Bipy2MnII~(u-0)2MnIVbipy23 -(C104)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~n~se/multidentate ligand catalyst), U.S.
4,711,748 and European patent application, publication no. 224,952, (absorbed m~n~nese on aluminosilicate ratalyst)~ U.S. 4,601,845 (aluminosilicate support with m~n~nese and zinc or m~gnesium salt), U.S.
4,626,373 (m~nf~nese/ligand catalyst), U.S. 4,119,557 (ferric complex catalyst), German Pat. specification 2,054,019 (cobalt chelant catalyst) CA 02247829 l998-08-3l W O 97/32955 PCT~US97/03111 ~n~ n 866,191 (transition metal-cont~inin~ salts), U.S. 4,430,243 (chelants with m~n~nese cations and non-catalytic metal cations), and U.S.
4,728,455 (m~n~nese gluconate catalysts).

Heavy metal ion sequestrant The detergent compositions herein 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 magnesium chelation capacity, but preferentially they show selectivity to binding heavy metal ions such as iron, m~n~nese and copper.

Heavy metal ion sequestrants are generally present at a level of from 0.005% to 20%, preferably from 0.1% to ~0%, more preferably from 0.25 % to 7.5 % and most preferably from 0.5 ~ to 5 ~ by weight of the compositions.

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

Preferred among ~e above species are diethylene tri~mine penta (methylene phosphonate), ethylene tli~min~ tri (methylene phosphonate) 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 ethylene~ minotetracetic acid, ethylenetri~mine pentacetic acid, ethyle~ mine disuccinic acid, ethylen~ mine diglutaric acid, 2-hydroxypropylen~ mine disuccinic acid or any salts thereof. Especially preferred is ethylene~ min~-N,N'-disuccinic acid (EDDS) or the alkali CA 02247829 l998-08-3l W O 97/32955 PCTrUS97/03111 metal, ~lk~line earth metal, ammonium, or substinlted ammonium salts thereof, or mixtures thereof.

~ Other suitable heavy metal ion sequestrants for use herein are iminodiacetic acid derivatives such as 2-hydroxyethyl ~ cetic acid or glyceryl imino diacetic acid, described in EP-A-317,542 and EP-A-399,133. The iminodiacetic acid-N-2-hydroxypropyl sulfonic acid and aspartic acid N-carboxymethyl N-2-hydroxypropyl-3-sulfonic acid sequestrants described in EP-A-516,102 are also suitable herein. The ,B-~l~nine-N,N'-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.

~P-A-476,257 describes suitable amino based sequestrants. EP-A-510,331 describes suitable sequestrants derived from collagen, keratin or casein.
EP-A-528,859 describes a suitable alkyl iminodiacetic acid sequestrant.
Dipicolinic acid and 2-phosphonobutane 1,2,4-tricarboxylic acid are alos suitable. Glycinamide-N,N'-disuccinic acid (GADS), ethylen~ mine-N-N'-diglutaric acid (EDDG) and 2-hydroxypropylene~ min~-N-N'-disuccinic acid (E~PDDS) are also suitable.

Enzyme Another preferred ingredient useful in the de~e~,en~ compositions is one or more additional enzymes.

Preferred additional enzymatic materials include the commercially available lipases, cll~in~e~ amylases, neutral and ~lk~line proteases, esterases, cellulases, pectinases, lactases and peroxidases conventionally incorporated into deter~,enl compositions. Suitable enzymes are discussed in US Patents 3,519,570 and 3,533,139.

Preferred commercially available protease enzymes include those sold under the tradenames Alcalase, Savinase, Primase, Durazym, and Esperase by Novo Industries A/S (Denmark), those sold under ~e tradename ~x~t~e, 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.

Preferred amylases include, for example, oc-amylases obtained from a special strain of B licheniformis, described in more detail in GB-1,269,839 (Novo). Preferred commercially available amylases include ~or example, those sold under the tradename Rapidase by Gist-Brocades, and those sold under the tradename Termamyl and BAN by Novo Tn~ stries A/S.
Amylase enzyme may be incorporated into the composition in accordance with the invention at a level of from 0.0001% to 2% active enzyme by weight of the composition.

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

The lipase may be fungal or bacterial in origin being obt~in~l, for 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 ~rom Pseudomonas pseudoalcaligenes, which is described in Granted European Patent, EP-B-0218272.

Another preferred lipase herein is obtained by clonin~ the gene from Humicola l~ml~inosa and expressing the gene in Asper~illus 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.

Organic polymeric compound CA 02247829 l998-08-3l W O 97/329~5 PCTAUS97/03111 Organic polymeric compounds are preferred additional components of the detergent compositions herein, and are preferably present as components of ~ any particulate components where they may act such as to bind the particulate component together. By orga~ic polymeric compound it is meant herein essentially any polymeric organic compound commonly used as dispersants, and anti-redeposition and soil suspension agents in detergent compositions, including any of the high nnolecular weight organic polymeric compounds described as clay flocc~ t;ng agents herein.

Organic polymeric compound is typically incorporated in the detergent compositions of the invention at a level o~ from 0.1 % to 30 ~, preferably from 0.5 % to lS %, most preferably from 1 % to 10~ by weight of the compositions.

Examples of organic polymeric compoun~s include the water soluble organic 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 S,000 to 10,000, are also suitable herein.

Other organic polymeric compounds suitable for incorporation in the detelgellL 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 preferably about 400~).

Suds suppressing system The detergent compositions herein, when forrnulated ~or use in machine washing compositions, preferably comprise a suds suppressing system present at a level of from 0.0~ % to 15%, preferably from 0.05% to 105~, most preferably from 0. ~ % 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 fo~min~ or sudsing produced by a solution of a detergent composition, particularly in the presence of agitation of that solution.

Particularly preferred antifoam compounds for use herein are silicone antifoarn 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 ~e industry, encompasses a variety of relatively high molecular weight polymers cont~inin~ siloxane units and hydrocarbyl group of various types. Preferred silicone antifoam compounds are the siloxanes, particularly the 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 CA 02247829 l998-08-3l W O 97/32955 PCT~US97/03111 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 lithium salts, and ammonium and alkanolammonium salts.

Other suitable antifoam compounds include, for example, high molecular weight fatty esters (e.g. fatty acid triglycerides), i~atty acid esters of monovalent alcohols, aliphatic C~g-C40 ketones (e.g. stearone) N-alkylated amino triazines such as tri- to hexa-alkylmel~mines or di- to tetra alkyl~ mine chlortriazines formed as products of cyanuric chloride with two or three moles of a primary or secondary amine cont~inin~ 1 to 24 carbon atoms, propylene oxide, bis stearic acid amide and monostearyl di-alkali metal (e.g. sodium, potassium, lithium) phosphates and phosphate esters.

A preferred suds suppressing system comprises (a) antifoam compound, preferably silicone antifoam compound, most preferably a silicone antifoarn compound comprising in combination (i) polydimethyl siloxane, at a level of from 50% to 99%, preferably 75 % to 95 % by weight of the silicone antifoam compound; and (ii) silica, at a level of from 1% to 50%, preferably 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 W O 97/32955 PCT~US97/03111 ethylene oxide to propylene oxide ratio of from 1:0.9 to 1:1.1, at a level of from 0.55~ to 10%, preferably 1 % to 10% by weight; a particularly preferred silicone glycol rake copolymer of this type is DCO544, commercially available from DOW Corning under the tradename DCO544;

(c) an inert carrier fluid compound, most preferably comprising a C16-C1g ethoxylated alcohol with a degree of ethoxylation of from 5 to 50, preferably 8 to 15, at a level of from 5~ to 80%, preferably 10 % to 70%, by weight;

A highly preferred particulate suds suppressing system is described in EP-A-0210731 and comprises a silicone antifoam compound and an organic carrier material having a melting point in the range 50~C to 85~C, wherein the organic carrier material comprises a monoester of glycerol and a fatty acîd having a carbon chain cont~inin~ 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.

Clay softenin~ system The detergent compositions may contain a clay softening system comprising a clay mineral compound and optionally a clay flocc~ ting 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~ ting agents.

Polymeric dye transfer inhibitin~ a~ents CA 02247829 l998-08-3l W O g7/32955 PCT~US97/03111 The detergent compositions herein may also comprise from 0.01% to 10 ~, preferably from O.OS ~ to 0.5 % by weight of polymeric dye transfer inhibiting agents.

The polymeric dye transfer inhibiting agents are preferably selected from polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinylpyrrolidonepolymers or combinations thereof.

a) Polyamine N-oxide polymers Polyamine N-oxide polymers suitable for use herein contain units havingthe following structure formula:
p (I) Ax R

wherein P is a polymerisable unit, and A is NC, Co, C, -O-, -S-, -N-; x is O or 1;

R are aliphatic, ethoxylated aliphatics, aromatic, heterocyclic or alicyclic groups or any combination thereof where~o the nitrogen of the N-O group can be attached 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:

CA 02247829 l998-08-3l W O 97/32955 PCT~US97/03111 R1) X-N-(R2)Y

(R3)zor N-(R1 ~x wherein Rl, R2, and ~3 are al;phatic 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. Qne 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 R-group. Preferred polyamine N-oxides are those wherein R is a heterocyclic group such as pyrridine, pyrrole, imidazole, pyrrolidine, piperidine, quinoline, acridine and derivatives thereof.

Other suitable polyamine N-oxides are the polyamine oxides whereto the N-O group is ~ hed to the polymerisable unit. A preferred 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.
Examples of these classes are polyamine oxides wherein R is a heterocyclic compound such as pyrridine, pyrrole, imidazole 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-vinylimidazole and N-vinylpyrrolidone having an average molecular weight range of from 5,000 to 50,000. The preferred copolymers have a molar ratio of N-vinylimidazole 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, ~'~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 CoIporation. Other suitable polyvinylpyrrolidones which are commercially available from BASF
~ Cooperation include Sokalan HP 165 andl Sokalan HP 12.
d) Polyvinyloxazolidone The delelgellt 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) Polyvinylimi(1~7.ole The detergent compositions herein may also utilize polyvinylimidazole as polymeric dye transfer inhibiting agent. Said polyvinylimidazoles preferably have an average molecular weight of from 2,500 to 400,000.

W O 97132955 PCT~US97/03111 Optical brightener The detergent compositions herein also optionally contain from about 0.005 ~ to 5 % by weight of certain types of hydrophilic optical brighteners.

Hydrophilic optical brighteners useful herein include those having the structural formuIa:

R~ R2 N~O~ I ~C=C~ 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~min~, morphilino, chloro and amino; and M is a salt-forming cation such as sodium or potassium.

~ When in the above formula, Rl is ~nilin~, 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 marketed under the tradename Tinopal-UNPA-GX by Ciba-Geigy Corpora~ion.
Tinopal-UNPA-GX is the preferred hydrophilic optical briglltellef useful in the delelgellt compositions herein.

When in the above formula, Rl is ~nilino, 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-6-(N-2-hydroxyethyl-N-methyl~min~ )-s-triazine-2-yl)aminol2,2'-stilbenedisulfonic acid disodium salt. This particular brightener species is commercially marketed under the tradename Tinopal 5BM-GX by Ciba-Geigy Corporation.

W O 97/32955 PCT~US97/03111 When in the above formula, Rl is anilino, R2 is morphilino and M is a - cation such as sodium, the brightener is 4,4'-bisr(4-anilino-6-morphilino-s-triazine-2-yl)amino]2,2'-stilbenedisulfonic acid, sodium salt. This particular brightener species is commercially marketed under the tradename Tinopal AMS-GX by Ciba Geigy Corporation.

Cationic fabric softening a~ents Cationic fabric softening agents can also be incorporated into the detergent compositions herein. Suitable cationic fabric softening agents include the water insoluble tertiary amines or dilong chain amide materials as disclosed in GB-A-l 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 l ~o to 5 % by weight.

Other optional ingredients Other optional ingredients suitable for inclusion in the detergell~
compositions herein include perfumes, colours and filler salts, with sodium sulfate being a preferred filler salt.

pH of the compositions The present deter~ellt compositions preferably have a pH measured as a 1% solution in distilled water of at least 10.0, ~leferably from 10.0 to 12.5, most preferably from 10.5 to 12Ø

Form of the compositions The deteLgellL compositions herein can take a variety of physical forms including granular, tablet, bar and liquid forms. The compositions are particularly the so-called concentrated granular detergent compositions adapted to be added to a w~hin~ machine by means of a dispensing device placed in the machine drum with the soiled fabric load.

CA 02247829 l998-08-3l W 097/32955 PCT~US97/03111 38 The mean particle size of the components of granular compositions in accordance with the invention should preferably 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. lSmm 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 against 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 herein 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 consisting of a conical funnel moulded rigidly on a base and provided with a flap valve at its lower e~ elllily to allow the contents of the funnel to be emptied into an axially aligned 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 e~l~elllily 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.

To carry out a measurement, 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 passing a straight edged implement eg; a knife, across its upper edge. The filled cup is then weighed and the value obtained for ~e weight of powder doubled to provide a bulk density in g/litre. Replicate measurements are made as required.

Surfactant agglomerate particles W O 97/32955 PCT~US97/03111 . 39 The surfactant system herein is preferably present in granular compositions in the form of surfactant agglomerate particles, which may take the form of flakes, prills, marumes, noodles, ri~bons, but preferably take the form of granules. The most preferred way to process the particles is by agglomerating powders (e.g. aluminosilicate, carbonate) with high active surfactant 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 agglomerators such as a pan agglomerator, a Z-blade mixer or more preferably an in-line mixer such as those manufactured by Schugi (Holland) BV, 29 Chroomstraat 8211 AS, Lelystad, Netherlands, and Gebruder Lodige Maschinenbau GmbH, D-4790 Paderborn 1, Elsenerstrasse 7-9, Postfach 2050, Germany. Most preferably a high shear mixer is used, such as a Lodige CB (Trade Name).

A high active surfactant paste comprising from 50% by weight to 95 ~ by weight, preferably 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.

n~lry washing method Machine laundry methods herein typically comprise treating soiled laundry with an a~ueous wash solution in a washing machine having dissolved or dispensed therein an effective amount of a machine laundry detergent composition in accord with the invention. By an effective amount of the de~ genl composition it is meant from 40g to 300g of product dissolved or dispersed in a wash solution of volume from S to 65 litres, as are typical product dosages and wash solution volumes commonly employed in conventional machine laundry methods.

In a preferred use aspect a dispensing device is employed in the washing method. The dispensing device is charged with the deter~,el~ product, and CA 02247829 l998-08-3l W O 97132955 PCT~US97/03111 is used to introduce the product directly into the d~m of the washing machine before the commencement of the wash cycle. Its volume capacity should be such as to be able to contain sufflcient detergent product as would normally be used in the w~hing method.

Once the washing machine has been loaded w;th laundry the dispensing device cont~in~ the detergent 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 detergent 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 detelgenl product during the wash the device may possess a number of openings through which the product may pass.
Alternatively, the device may be made of a material which is permea~e to liquid but impermeable to the solid product, which will allow release ~ r dissolved product. Preferably, the detergent product will be rapidly released at the start of the wash cycle thereby providing transient localised high concentrations o~ product in the drum of the w~hin~ machine at this stage of the wash cycle.

Preferred dispensing devices are reusable and are designed ;n such a way that container integrity is m~int~inlo-l in both the dry state and during the wash cycle. Especially preferred dispensing 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 and EP-A-0288346. An article by J.Bland published in Manufacturing Chemist, November 1989, pages 41-46 also describes especially preferred 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 detergent compositions herein is disclosed in PCT
Patent Application No. WO94/11562.

W O 97/32955 PCT~US97/03111 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 nnedium flows through the orifice into ~he bag, dissolves the product, and the solution then passes outwardly through the ori~lce into the washing medium. The support ring is provided with a m~kin~ arrangemnt to prevent egress of wetted, undissolved, product, this arrangement typically comprising radially extending walls extending from a central boss in a spoked wheel configuration, or a similar structure in which the walls have a helical ~orm.

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 colltellls" such as is disclosed in European published Patent ~pplication No. 0018678.
Alternatively it may be forrned 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 00119~8. 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.

Pack~ for the coml)osilions Commercially marketed executions of the bleaching compositions can be packaged in any suitable container includling those constructed from paper, cardboard, plastic materials and any suitable l~min~tes. A preferred pack~in~ execution is described in European Application No.
94921505.7.

Abbreviations used in Examples W O 97/32955 PCTrUS97/03111 . 42 In the detergent compositions, the abbreviated component identifications have the following me~nin~:

LAS : Sodium linear C12 alkyl benzene sulfonate TAS : Sodium tallow alkyl sulfate C45AS : Sodium C14-C 15 linear alkyl sulfate CxyEzS : Sodium C lx~C ly 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 C25E3 : A C12 15 branched primary alcohol condensed with an average of 3 moles of ethylene oxide C25E5 : A C12 15 branched primary alcohol condensed with an average of 5 moles of ethylene oxide CEQ : RlcoocH2cH2.N~(cH2cH3oH)(c~3)2 with R1 = C1 1- C 13 QAS : R2 ~ N + (cH3~2(c2H4oH) with R2 = C 12 - C 14 Soap : Sodium linear alkyl carboxylate derived from an 80/20 mixture of tallow and coconut oils.
TFAA : C16-C1g alkyl N-methyl glucamide TPKFA : C12-C14 topped whole cut fatty acids STPP : Anhydrous sodium tripolyphosphate Zeolite A : Hydrated Sodium Aluminosilicate offormula Na12(A1~2Si~2)12. 27H20 having a primary particle size in the range from 0.1 to 10 micrometers NaSKS-6 : Cryst~llin~ layered si~icate of formula ~ -Na2Si20s Citric acid : Anhydrous citric acid Carbonate : Anhydrous sodium carbonate wi~ a particle size between 200,um and 900~Lm Bicarbonate : Anhydrous sodium bicarbonate with a particle size distribution between 400,um and 1200,um CA 02247829 l998-08-3l W O 97/32955 PCTrUS97/03111 Silicate : Amorphous Sodium Silicate (SiO2:Na20; 2.0 ratio) Sodium sulfate: Anhydrous sodium sulfate Citrate : Tri-sodium citrate dihydrate of activity 86.4%
with a particle size dListribution between 425,um and 850 ,um 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 NOVO Industries A/S under the tradename Savinase Alcalase : Proteolytic enzyme of activity 3AU/g sold by NOVO Tn-lll.ctries A/S
Cellulase : Cellulytic enzyme of activity 1000 CEVU/g sold by NOVO Tn-lllstries A/S under the tradename Carezyme Amylase : Amylolytic enzyme of activity 60KNU/g sold by NOVO Industries A/S under the tradename Termamyl 60T
Lipase : Lipolytic enzyme of activity 100kLU/g sold by NOVO Industries A/S under the tradename Lipolase Endolase : Endoglunase enzyme of activity 3000 CEVU/g sold by NOVO Tn~ stries A/S
PB4 : Sodium perborate tetrahydrate of nominal formula NaB02.3H20-H202 PBl : Anhydrous sodium perborate monohydrate bleach of nominal formula NaBo2.H2o2 Percarbonate : Sodium Percarbonate of nominal formula - 2Na2C03-3H202 NOBS : Nonanoyloxybenzene sulfonate in the form of the sodium salt.
TAED : Tetraacetylethylen~ min~

CA 02247829 l998-08-3l W O 97132955 PCT~US97/03111 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-~nilin~-6-morpholino-1.3.5-triazin-2-yl)amino) stilbene-2:2'-disulfonate.
HEDP : 1,1-hydroxyethane diphosphonic acid PVNO : Polyvinylpyridine N-oxide PVPVI : Copolymer of polyvinylpyrolidone and vinylimidazole SRP 1 : Sulfobenzoyl end capped esters with oxyethylene oxy and terephtaloyl backbone SRP 2 : Die~oxylated 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.
~lk~linity : % weight equivalent of NaOH, as obtained using the ~lk~linity release test method described herein.

In the following Fx~mrles all levels are quoted as % by weight of the composition:

W O 97/32955 PCT~US97/03111 l~xample 1 Into a 500 ml round-bottom flask fitted with a short Vigreux column attached to a condenser fitted with a measuring cylinder was added methyl dodecanoate (36.0g, 0.168 mol), N-methyldiethanolamine (120.0g, 1.00 mol) and sodium methoxide (O.Sg, 0.015 mol). The reaction was heated to reflux for 2.5 days, collecting the methanol in the measuring cylinder.

The reaction mixture was dissolved in chloroform (350 ml), washed with saturated sodium chloride solution ~2xlO0 ml), and dried over magnesium sulfate. The chloroform was removed by rotary evaporation to give the ester amine as a brown liquid. dissolved in acetone (300 ml).

Into a 500 ml round-bottomed flask fitted with dry-ice condenser / drying tube and magnetic stirrer and cooled with a dry-ice acetone bath was added the acetone solution of the ester amine obtained as above. The reaction mixture was cooled to -10 ~C and methylbromide (30 ml, 99g, 1.04 mol) was added via gr~ te~l cylinder to the reaction. The reaction was kept between -10 ~C and 0 ~C ~or 4 hours and then allowed to warm to room temperature. After st~n~lin~ overnight, a quantity of solid product formed.
The product was collected by filtration, washed with acetone, placed in an evaporating dish and dried overnight in a vacuum dessicator over phosphorus pentoxide to give the desired cationic ester (16g, 24% yield based on methyl do~ec~noate).

W O 97/3295S PCT~US97/03111 E~ample 2 The following laundry detergent compositions A to F were prepared in accord with the invention:

A B C D E F
LAS 8.0 8.0 8.0 8.0 8.0 8.0 C25E3 3.4 3.4 5.4 3.4 2.4 3.4 CEQ 2.0 0.8 1.0 1.5 0.8 0.8 QAS - - 0. 8 - - 0.4 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 D ET P M P 0.25 0.25 0.25 0.25 0.25 0.25 H E D P 0.3 0.3 0.3 0.3 0.3 0.3 Protease 0.26 0.26 0.26 0.26 0.26 0.26 Amylase 0.1 0.1 0.1 0.1 0.1 0.1 W O 9713295~ PCT~US97/03111 MA/AA 0.3 0 3 0.3 0 3 0 3 0 3 CMC 0.2 0.2 0.2 0.2 0.2 0.2 Photoactivated 15 15 15 15 15 15bleach (ppm) ppm ppm ppm ppm ppm ppm 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 97132955 PCTrUS97/03111 Example 3 The following granular laundry detergent compositions G to I of bulk density 750 g/litre were prepared in accord with the invention:

G H
LAS 5.25 5.61 4.76 TAS 1.25 1.86 1.57 C45AS - 2.24 3.89 C25AE3S - 0.76 1.18 C45E7 3.25 - 5.0 C25E3 - 5.5 CEQ 0.8 2.0 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 W O 97/32955 PCT~US97/03111 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 (ppm) Brightener 1 0.08 0.19 0.19 Brightener 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 97/32955 PCTrUS97/03111 Example 4 The following detergent formu}ations, in accord with the present invention were prepared, where J is a phosphorus-cont~inin~ detergent composition, K is a zeolite-cont~inin~ detergent composition and L is a compact detergent composition:

J K L
Blown Powder STPP 14.0 - 14.0 Zeolite A - 20.0 C45AS 9.0 6.0 8.0 MA/AA 2.0 4.0 2.0 LAS 6.0 8.0 9.0 TAS 2.0 CEQ 1.5 3.0 3.5 Silicate 7.0 8.0 8.0 CMC 1.0 1.0 0.5 Brightener 2 0.2 0.2 0.2 Soap 1.0 1.0 1.0 DTPMP 0.4 0.4 0.2 Spray On C45E7 2.5 2.5 2.0 C25E3 2.5 2.5 2.0 Silicone antifoam 0.3 0.3 0.3 Perfume 0.3 0.3 0.3 Dry additives Carbonate 26.0 23.0 25.0 PB4 18.0 18.0 10 PB1 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 W O 97132955 PCTrUS97103111 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 W O 97132955 PCTrUS97/03111 Example 5 The following nil bleach-cont~inin~ detergent formulations of particular use in the washing of colored clothing, in accord with the present invention were prepared:

M N O
Blown Powder Zeolite A 15.0 15.0 Sodium sulfate 0.0 5.0 LAS 3.0 3.0 CEQ 2.0 1.5 1.3 DTPMP 0.4 0.5 CMC 0.4 0.4 MA/AA 4.0 4.0 Agglomerates C45AS - - 11.0 LAS 6.0 5.0 TAS 3.0 2.0 Silicate 4.0 4.0 Zeolite A 10.0 15.0 13.0 CMC - - 0.5 MA/AA - - 2.0 Carbonate 9.0 7.0 7.0 Spray On Perfilme 0.3 0.3 0.5 C45E7 4.0 4.0 4.0 C25E3 2.0 2.0 2.0 Dry additives MA/AA - - 3.0 NaSKS-6 - - 12.0 Citrate 10.0 - 8.0 Bicarbonate 7.0 3.0 5.0 Carbonate 8.0 5.0 7.0 PVPVIIPVNO 0.5 0.5 0.5 Alcalase 0.5 0.3 0.9 CA 02247829 l998-08-3l W O 97/32955 ' PCT~US97/03111 Lipase 0.4 0.4 0.4 Amylase 0.6 0.6 0.6 Cellulase 0.6 0.6 0.6 Silicone antifoam 5.0 5.0 5.0 Dry additives Sodium sulfate 0.0 9.0 0.0 Balance (Moisture and 100.0 100.0 100.0 Miscellaneous) Density ~g/litre) 700 700 700 W O 97/32955 PCTrUS97/03111 ~xample 6 The following detergent formulations, in accord with the present invention were prepared:
P Q R S

LAS 12.0 12.0 12.0 10.0 Q~S 0.7 1.0 - 0.7 TFAA - 1.0 C25E5/C45E7 - 2.0 - 0.5 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 Lipase 0.2 0.1 0.2 0.1 Cellulase 0.15 0.05 Photoactivated 70ppm 45ppm - 10ppm bleach (ppm) Bri~,htellel 1 0.2 0.2 0.08 0.2 PBl 6.0 ~.0 - -NOBS 2.0 1.0 R~l~nce 100 100 100 100 (Moisture and Miscellaneous) W O 97/32955 PCT~USg7/03111 Example 7 The following detergent formulations, in accord with the present invention were prepared:

T U V

Blown Powder Zeolite A 10.0 15.0 6.0 Sodium sulfate 19.0 5.0 7.0 MA/AA 3.0 3.0 6.0 LAS 10.0 8.0 10.0 C45AS 4.0 5.0 7.0 CEQ 2.0 2.0 2.Q
Silicate - 1.0 7.0 Soap - - 2.0 Brightener 1 0.2 0.2 0.2 Carbonate 28.0 26.0 20.0 DTPMP - 0.4 0.4 Spray On C45E7 1.0 1.0 1.0 Dry additives PVPVI/PVNO 0.5 0.5 0.5 Protease 1.0 1.0 1.0 Lipase 0.4 0.4 0.4 Amylase 0.1 0.1 0.1 Cellulase 0.1 0.1 0.1 NOBS - 6.1 4.5 PB1 1.0 5.0 6.0 Sodium sulfate - 6.0 Balance (Moisture 100 100 100 and Miscellaneous) W O 97/32955 PCTrUS97/03111 :l~xample 8 The following high density and bleach-cont~inin~ detergent formulations, in accord with the present invention were prepared:

W X Y

Blown Powder Zeolite A 15.0 15.0 15.0 Sodim sulfate 0.0 5.0 0.0 LAS 3.0 2.0 3.0 QAS - 1.5 1.5 CEQ 2.0 1.5 2.0 DTPMP 0.4 0.4 0.4 C M C 0.4 0.4 0.4 MA/AA 4.0 2.0 2.0 Agglomerates LAS 4.0 4.0 4.0 T AS 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 2.0 2.0 2.0 C25E3 2.0 - -Dry additives Citrate 5.0 - 2.0 Bicarbonate - 3.0 CarboIlate 8.0 15.0 10.0 TAED 6.0 2.0 5.0 PBl 14.0 7.0 10.0 Polyethylene oxide of MW - - 0.2 5,000,000 Bentonite clay - - 10.0 Protease 1.0 1.0 1.0 W O 97/329S5 PCTrUS97/03111 Lipase 0.4 0.4 0.4 Amylase 0.6 0.6 0.6 Cellulase 0.6 0.6 0.6 Silicone antifoam 5.0 5.0 5.0 Dry additives Sodium sulfate 0.0 3.0 0.0 B~l~n~e (Moisture and 100.0 100.0 100.0 Miscellaneous~
Density (g/litre) 850 850 850 W O 97/3295~ PCTrUS97/03111 Example 9 The following high density detergent formulations, in accord with the present invention were prepared:

Z AA

Agglomerate C45AS 11.0 14.0 CEQ 3.0 3.5 Zeolite A 15.0 6.0 Carbonate 4.0 8.0 MA/AA 4.0 2.0 CMC 0.5 0.5 DTPMP 0.4 0.4 Spray On C25E5 5.0 5.0 Perfume 0.5 0.5 Dry Adds HEDP 0.5 0.3 SKS 6 13.0 10.0 Citrate 3.0 1.0 TAED 5.0 7.0 Percarbonate 20.0 20.0 SRP 1 0.3 0.3 Protease 1.4 1.4 Lipase 0.4 0.4 Cellulase 0.6 0.6 Arnylase 0.6 0.6 Silicone antifoam 5.0 5.0 Brightener 1 0.2 0.2 Brightener 2 0.2 Balance (Moisture and 100 100 Miscellaneous) Density (g/litre) 850 850

Claims (15)

WHAT IS CLAIMED IS:

1. A cationic ester surfactant comprising at least one ester linkage and at least one cationically charged group characterized in that said cationically charged group is an ammonium group substituted by at least one hydroxyalkyl group.

2. A cationic ester surfactant according to either of Claims 1 or 2 wherein said hydroxyalkyl group contains from 1 to 4 carbon atoms.

3. A cationic ester surfactant according to either of Claims 1 or 2 having the formula:

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

4. A cationic ester surfactant according to any of Claims 1 to 3 wherein said ammonium group is substituted by one hydroxyalkyl group.

5. A cationic ester surfactant according to either of Claims 3 or 4 wherein R2 is a CH2CH2OH group and both R3 and R4 are CH3 groups.

6. A cationic ester surfactant according to Claim 5 having the formula:

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

7. A process for making a cationic ester surfactant according to Claim 6 comprising the steps of:

(i) amidation of a fatty acid (R1COOH), fatty acid ester (R1COOR n) or fatty acid halide (R1COOHal) by reaction with diethanolamine;

(ii) heating the amidation product to force its rearrangement to an ester amine; and (iii) quaternization of the resulting ester amine with a quaternizing agent selected from the group consisiting of methyl halide, methyltosylate, dimethylsulfate and any mixtures thereof.

8. A process according to Claim 7 wherein said quaternization step is conducted in the presence of a solvent selected from the group consisting of ethanol, propylene glycol and C10-C18 fatty alcohol ethoxylate having a degree of ethoxylation of from 3 to 50 ethoxy groups per mole.

9. A surfactant system comprising in combination a cationic ester surfactant according to any of Claims 1 to 6 and an anionic and/or nonionic surfactant.

10. A surfactant system according to Claim 9 comprising both anionic and nonionic surfactant wherein the weight ratio of anionic surfactant to cationic ester surfactant in the surfactant system is from 3:1 to 50:1, and the weight ratio of nonionic surfactant to cationic ester surfactant in the surfactant system is from 3:1 to 50:1.

11. A surfactant system according to either of Claims 9 or 10 wherein said anionic surfactant is an anionic sulfate surfactant.

12. A detergent composition containing a surfactant system according to any of Claims 9 to 11 and one or more additional detergent components selected from the group consisting of an alkalinity system, bleaches, builders, organic polymeric compounds, enzymes, suds suppressors, lime soap dispersants, soil suspension and anti-redeposition agents, corrosion inhibitors and any mixtures thereof.

13. A detergent composition according to Claim 12 comprising (a) from 1 % to 90 % by weight of the composition of a surfactant system comprising an anionic surfactant and a cationic ester surfactant according to any of Claims 1 to 5 present at a weight ratio of anionic to cationic ester surfactant of from 3:1 to 15:1; and (b) from 1.5 % to 95 % by weight of the composition of an alkalinity system comprising alkaline salts selected from the group consisting of alkali metal or alkaline earth carbonate, bicarbonate, hydroxide or silicate, including crystalline layered silicate, salts and any mixtures thereof.

14. A detergent composition according to either Claims 12 or 13 additionally containing perfume.

15. A method of washing laundry in a domestic washing machine in which a dispensing device containing an effective amount of a solid detergent composition according to any of Claims 12 to 14 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.