CA2256701A1 - Detergent compositions - Google Patents

Abstract

There is provided a detergent composition suitable for use in laundry and dish washing methods comprising: (a) a cationic ester surfactant; and (b) a perfume composition, comprising a perfume component with a molecular weight from 150 to 350 or a precursor thereto, present at a level of from 0.5 % to 90 % by weight of said perfume composition.

Description

CA 022~6701 1998-11-26 Dete~ .t compositions Technical field The present invention relates to detergent compositions con~ining a cationic ester surfactant and perfume, which are suitable for use in laundry and dishwashing methods. The detergent compositions provide an improved perfume fabric substantivity.

Background 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 formulator of detergent compositions for use in laundry and dish washing methods. Surfactant components have traditionally been employed in detergent products to facilitate the removal of such greasy soils/stains. In particular, surfactant systems comprising cationic esters have been described for use in greasy soil/stain removal.

An aspect of successful formulation of commercial detergent products ismeasured by the resulting malodour of the cleaned surface and/or laundered fabric, especially after exposure to strong malodours (such as perspiration, smoke and/or kitchen odours, which are among the most persistent odours on dried cleaned fabrics and/or surfaces). Traditionally, perfumes are employed in detergents to mask these resulting malodour.

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

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CA 022~6701 1998-11-26 Wo 97/4~511 PCT/U$97/08234 US-A-4,228,042 discloses biodegradable cationic surfactants, includingcationic 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 removal is also described.

US-A-4,260,529 discloses laundry detergent compositions having a pH ofno greater than 11 cont~ining cationic ester surfactant and nonionic surfactant at defined weight ratios.

A problem can be that certain perfumes are not able to mask the malodours present in or on the fabric sufficiently during the cle~ning or washing process. This amounts to a resulting malodour after the cle~ning or washlng process.

It has been found that a partial solution to this problem can be achieved when perfumes with a high fabric substantivity are employed in the detergents. The fabric substantivity of perfumes is partly determined by their molecular weight and by their functionality/ polarity. It has been found that perfume with a molecular weight of from 150 to 350 have a high fabric substantivity. When these perfumes contain an oxygen comprising functional groups (such as ester, ketone, aldehyde, alcohol and ether groups) their fabric substantivity is further increased.

The Applicants have now found an improved solution to the problem described above. Fabric substantivity of the perfumes has been found to be increase when a perfume with a molecular weight of from 150 to 350 and a cationic ester surfactant are employed in a detergent composition.
Thus, it has been found that cationic ester surfactants enhance the fabric substantivity of the perfumes, especially when the perfumes contain an oxygen comprising functional groups. Hence, an improved m~kin~ of malodours and/or an improved resulting (perfume) odour of the fabric after the wash is provided.

The following mechanism is believed to be responsible for the improvedperfume substantivity. The perfumes, especially those comprising oxygen cont~ining func.ional groups, have a high affinity for cationically charged , .. . . .. . . . . . .

CA 022~6701 1998-11-26 WO 97t45511 PCT/US97108234 substances, such as positively charged fabric surfaces. Cationic ester surfactants are capable of interacting with a fabric surface to provide a positively charged fabric surface. The perfumes will have an improved fabric substantivity for the fabrics, positively charged by the cationic ester surfactant. It has been found that the use of an cationic ester surfactant thus can provide a surprisingly improved perfume substantivity on the ~ cleaned or washed fabric.

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

S~ m~ry of the Invention The detergent composition of the present invention comprises (a) a cationic ester surfactant; and (b) a perfume composition, comprising a perfume component with a molecular weight of from 150 to 350, or a precursor thereto present at a level of from 0.5% to 90% by weight of said perfume composition.

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

R5 +
(~(CH)nO b (X)U ( C H2 )m--~(Y)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, CA 022~6701 1998-ll-26 W O 97/45511 PCTrUS97/08234 OCOO, OCONH or N~ICOO group; R2, R3, R4, R6, R7, and R8 are independently selected from the group consisting of alkyl, alkenyl, hydroxyalkyl, hydroxy-alkenyl and alkaryl groups having from 1 to 4 carbon atoms; and 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 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.

In another preferred aspect said perfume component comprises an oxygen-cont~ining functional group.

Detailed description of the invention Cationic ester surfactant An essential element of the detergent compositions of the invention is a cationic ester surfactant. Preferably the cationic ester surfactant is present at a level from 0.1% to 20.0%, more preferably from 0.5% to 10%, most preferably from 1.0% to 5.0% by weight of the detergent composition.

The cationic ester surfactant of the present invention is a, preferablywater dispersible, compound having surfactant properties comprising at least one ester (i.e. -COO-) linkage and at least one cationically charged group.

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

In one preferred aspect the ester linkage and cationically charged group are separated from each other in the surfactant molecule by a spacer group consisting of a chain comprising at least three atoms (i.e. of three atoms chain length), preferably from three to eight atoms, more preferably from three to five atoms, most preferably three atoms. The atoms forming the spacer group chain are selected from the group consisting of carbon, nitrogen and oxygen atoms and any mixtures ., . ~

CA 022~6701 1998-11-26 wo 97/45511 PCT/US97/08234 thereof, with the proviso that any nitrogen or oxygen atom in said chain connects only with carbon atoms in the chain. Thus spacer groups having, for example, -O-O- (i.e. peroxide), -N-N-, and -N-O- linkages are excluded, whilst spacer groups having, for example -CH2-O- CH2-and -CH2-NH-CH2- linkages are included. In a preferred aspect the spacer group chain comprises only carbon atoms, most preferably the chain is a hydrocarbyl chain.

Preferred cationic ester surfactants are those having the formula:

R5 +
Rl-- (} (CH)nO b (X)U ( C H 2 )m--(Y)v--- (C H 2 )t--N - R3 M
- a wherein R1 is a Cs-C3 1 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, R3, ~, R6, R7, and R8 are independently selected from the group consisting of alkyl, alkenyl, hydroxyalkyl and hydroxy-alkenyl groups having from 1 to 4 carbon atoms and alkaryl groups; and Rs is independently 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 or v must be 1; and wherein M is a counter anion.

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

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

, . . .

R1 --- O--(CH)nO ~ (X)--- (CH2)m--N --R3 M-b a wherein R1 is a Cs-C31 linear or branched alkyl, alkenyl or alkaryl chain; X is selected from the group consisting of COO, OCO, OCOO, OCONH and NHCOO; R2, R3, and R4 are independently selected from the group consisting of alkyl and hydroxyalkyl groups having from 1 to 4 carbon atoms; and Rs is independently H or a C1-C3 alkyl group;
wherein the value of n lies in the range of from 0 to 8, the value of b lies in the range from 0 to 20, the value of a is either 0 or 1, and the value of m is from 3 to 8.

More preferably R2, R3 and R4 are independently selected from a Cl-C4 alkyl group and a C1-C4 hydroxyalkyl group. In one preferred aspect at least one, preferably only one, of R2, R3 and R4 is a hydroxyalkyl group.
The hydroxyalkyl preferably has from 1 to 4 carbon atoms, more preferably 2 or 3 carbon atoms, most preferably 2 carbon atoms. In another preferred aspect at least one of R2, R3 and R4 is a C2-C3 alkyl group, more preferably two C2-C3 alkyl groups are present.

In a preferred aspect two of R2, R3 and R4 and the nitrogen of the cationically charged group from part of a ring structure. Preferably, the ring structure contains another nitrogen atom or more preferably, an oxygen atom, or mixtures thereof. Preferably, the ring structure contains S to 8 atoms, most preferably 6 atoms.

In a highly preferred aspect two of R2, R3 and R4 and the nitrogen of the cationically charged group from part of a morpholino ring structure or a substituted morpholino ring structure. Highly preferred cationic ester surfactants of this type are the esters having the formula:

CA 02256701 1998-ll-26 W O97/45511 PCT~US97/08234 -R5 M /~\
R1---- ~ (CH)nO -- (X) (CH2)m 1~ ~~
-b - a Rg wherein Rl is a Cs-C31 linear or br~nehe~ allyl, alkenyl or alkaryl chain; X is selected from the group consisting of COO, OCO, OCOO, OCONH and NHCOO; Rg is selected from the group con~i~ting of allyl, alkenyl, hydroxyalkyl and hydroxy-alkenyl groups having from 1 to 4 carbon atoms and alkaryl groups; and Rs is independently H or a C1-C3 alkyl group; wherein the value of n lies in the range of from 0 to 8, the value of b lies in the range from 0 to 20, the value of a is either 0 or 1, and the value of m is from 3 to 8.

More ~refeldbly R2, R3 and R4 are independently selected from a Cl-C4 alkyl group and a C1-4 hydroxyalkyl group. In one preferred aspect at least one, preferably only one, of R2, R3 and R4 is a hydroxyalkyl group.
The hydroxyallyl preferably has from 1 to 4 carbon atoms, more preferably 2 or 3 carbon atoms, most preferably 2 carbon atoms. In another preferred aspect at least one of R2, R3 and R4 is a C2-C3 allyl group, more preferably two C2-C3 alkyl groups are present.

Highly prefelled water dispersible cationic ester surf~ct~nts are the esters having the formula:

R1--C--O--(CH2)m--N+--CH3 M-where m is from 1 to 4, preferably 2 or 3 and wherein Rl is a C 1 l-C1g linear or branched allyl chain.

CA 022~6701 1998-11-26 W O97/45511 PCTrUS97/08234 Particularly preferred choline esters of this type include the stearoylcholine ester quaternary methylammonium halides (Rl =C17 alkyl), palmitoyl choline ester quaternary methylammonium halides (R1=C1s alkyl), myristoyl choline ester quaternary methylammonium halides (R1=C13 alkyl), lauroyl choline ester methylammonium halides (R1 =C1 1 alkyl), cocoyl choline ester quaternary methylammonium halides (Rl=Cl1 C13 alkyl), tallowyl choline ester quaternary methylammonium halides (R1=C1s C17 alkyl), and any mixtures thereof.

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

Rl- O - C -(CH2)d C - O - CH2CH2- N - CH3 M

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

The particularly preferred choline esters, given above, may be preparedby the direct esterification of a fatty acid of the desired chain length with dimethylaminoethanol, in the presence of an acid catalyst. The reaction product is then quaternized with a methyl halide, preferably in the presence of a solvent such as ethanol, water, propylene glycol or preferably a fatty alcohol ethoxylate such as C1o-C1g fatty alcohol ethoxylate having a degree of ethoxylation of from 3 to 50 ethoxy groups per mole 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 trimethylamine, forming the desired cationic material.

Perfume composition CA 022~6701 1998-ll-26 W O 97/45511 PCTrUS97/08234-Another essential aspect of the present invention is a perfume composition, comprising at least one perfume component, with a molecular weight of from 150 to 350 and present at a level of from 0.5%
to 90%, preferably from 1.0% to 60%, more preferably from 2.0% to 20% by weight of the perfume composition. Preferably the perfume composition is present at a level of from 0.01 % to 10.0 %, more preferably from 0.1 % to 6%, most preferably from 0.4 % to 4.0% by weight of the detergent composition.

Preferably, the perfume component comprises an oxygen-cont~inin~
functional group. Preferred functional groups are aldehyde, ketone, alcohol or ether functional groups or mixtures thereof.

Examples of preferred functional groups of the perfume components and relevant molecular weights are:
-aliphatic ketones with a molecular weight of from 200 to 350;
-aromatic ketones with a molecular weight of from 150 to 300;
-aliphatic aldehydes with a molecular weight of from 160 to 350;
-aromatic aldehydes with a molecular weight of from 150 and 350;
-aromatic and aliphatic esters with a molecular weight from 160 to 350;
-aromatic and aliphatic esthers with a molecular weight of from 160 to 350;
-condensation products of aldehydes and amines with a molecular weight of from 190 to 350;
-macrocyclic lactone musks with a molecular weight of from 150 to 350.

Suitable aliphatic ketones are e.g.:

- 2,7,8, -trimethyl- 1 -acetyl-cyclododeca-2,5,7-triene - 7-acetyl-1,1,6,7,-tetramethyl-1,2,3,4,5,6,7,8,-octahydronaphthalene - isolongifolanone - ~mm~-irone - alpha-vetivone Suitable aromatic ketones are e.g.:
- 4-(p-hydroxyphenyl)-butan-2-one - 1,1,2,4,4,7-hexamethl-6-acetyl-tetralin , . . . .

CA 022~670l l998-ll-26 W O 97/45511 PCT~US97/08234-- benzophenone - methyl naphthyl ketone Suitable aliphatic aldehydes are e.g.:
- 2-methylhen.lçc~n~l - lln-lec~n~l - 4(4'-methyl-4'-hydroxypentyl)-cyclohex-3-ene carbaldehyde - 7-(formyl-5-isopropyl-2-methyl-bicyclo[2.2.2~oct-2-ene - 4-(tricyclo[5.2. 1 .0{2,6}]decylidene-8)-butanal - 4-(4'-metylpent-3-enyl)-cyclohex-3-ene carbaldehyde Suitable aromatic aldehydes are e.g.:
- alpha-hexylcinn~mic aldehyde - anisic aldehyde - helliotropin - 2-phenylpropanal - dihydrocinn~mic aldehyde - 3-(p-tert.butylphenyl)-2-methylpropanal Suitable condensaton products of aldehydes and amines are e.g.
- methyl N-(2,4-dimethyl-3-cyclohexenyl)methylidene-anthr~nil~te - methyl N-(3,7-dimethyl-7-hydroxy-octylidene)-anthranilate - methyl N-(4-(4'-methyl-4'-hydroxypentyl)cyclohex-3-enyl~methylidene~nthranilate Suitable macrocyclic lactone musks are e.g.:
- ethylene dodecanedioate - 11-oxahe~ lec~nolide - cyclopent~lec~nolide Additionally, the perfume component can also be a perfume precursor.
Perfume precursors are capable of forming a perfume component, with the characteristics described above, once exposed to wash conditions.
Preferably, the perfume precursor forms a perfume component by hydrolysis under a~ueous conditions.

CA 022~6701 1998-11-26 Preferred perfume precursors herein are nonionic or anionic esters of an allylic alcohol perfume having the formula:

R--[C--O--CR'2-CR'~CR 2]n wherein n is an integer of 1 or greater; and R is selected from the group consisting of C1 - C30, preferably Cl - C20, straight, branched or cyclic alkyl, alkenyl, alkynyl, alkylaryl, or aryl group, and represents the group attached to the carboxylate function of the carboxylic acid used to make the perfume ester. Each R', R", and each R"' selected from the group consisting of hydrogen, or a Cl - C20 straight, branched or cyclic alkyl, alkenyl, alkynyl, alkylaryl, or aryl group. R, R', R" and R"' are selected in such a manner that the molecular weight of the allylic alcohol is from l50to350.

In the most preferred embodiment, R' and R" are hydrogen, one R"' is hydrogen, methyl, or ethyl, and the other R"' is a straight, branched or cyclic C1 - C1o alkyl or alkenyl group. Also cis/trans (also referred to as Z/E) isomers at the double bond in the structure shown above and stereoisomers of the above structure are possible.

Preferred the perfume component is selected from the group comprising the esters of geraniol and/or nerol. Geraniol and nerol are trans/cis structural isomers (at the 2,3 position double bond) of the molecules having the formula HO-CH2-CH=C(CH3)-CH2-CH2-CH=C(CH3)2.

Additional detergent components The detergent compositions of the invention may also contain additionaldetergent components. The precise nature of these additional components, and levels of incorporation thereof will depend on the physical forrn of the composition, and the precise nature of the washing operation for which it is to be used.

, . ~ .. ... , . .. ~

W O 97/45511 PCTrUS97/08234 The compositions of the invention preferably contain one or more additional detergent components selected from additional surfactants, bleaches, builders, organic polymeric compounds, additional enzymes, suds suppressors, lime soap dispersants, soil suspension and anti-redeposition agents and corrosion inhibitors.

CA 022~6701 1998-ll-26 W O97/45511 PCT~US97/08234 -Additional surfactant The detergent compositions of the invention preferably contain an additional surfactant selected from anionic, nonionic, non-ester cationic, ampholytic, amphoteric and zwitterionic surfactants and mixtures thereof.

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 Laughlin 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 zwitteronic surfactants are generally used in combination with one or more anionic and/or nonionic surfactants.

Anionic surfactant The detergent compositions of the present invention preferably comprisean additional anionic surfactant. Essentially any anionic surfactants useful for detersive purposes can be comprised in the detergent composition.
These can include salts (including, for example, sodium, potassium, arnmonium, and substituted ammonium salts such as mono-, di- and triethanol~rnin~ salts) of the anionic sulfate, sulfonate, carboxylate and sarcosinate surfactants. Anionic sulfate surfactants are preferred.

Other anionic surfactants 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.c~lrated C12-Cl8 monoesters) diesters of sulfosuccinate (especially saturated and un~ lrated 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.

CA 022~670l l998-ll-26 W O 97/45511 PCT~US97/08234 -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-(Cl-C2 hydroxyalkyl) gll~c~mine 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 C1o-C1g 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-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.

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 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 olefln sulfonates, sulfonated polycarboxylic acids, alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfonates, and any mixtures thereof.

CA 022~6701 1998-11-26 W O 97/45511 PCT~US97/08234 Anionic carboxylate surfactant Suitable anionic carboxylate surfactants include the alkyl ethoxy carboxylates, the alkyl polyethoxy polycarboxylate surfactants and the soaps ('alkyl carboxyls'), especially certain secondary soaps as described herein.

Suitable alkyl ethoxy carboxylates include those with the formula RO(CH2CH20)X CH2COO-M+ wherein R is a C6 to Cl~. 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-(CHR1-CHR2-O)-R3 wherein R is a C6 to C1g alkyl group, x is from 1 to 25, R1 and R2 are selected from the group consisting of hydrogen, methyl acid radical, succinic acid radical, hydroxysuccinic acid radical, and mixtures thereof, and R3 is selected from the group consisting of hydrogen, substituted or unsubstituted hydrocarbon having between 1 and 8 carbon atoms, and mixtures thereof.

Suitable soap surfactants include the secondary soap surfactants which contain a carboxyl unit conn~cterl to a secondary carbon. Preferred secondary soap surfactants for use herein are water-soluble members selected from the group consisting of the water-soluble salts of 2-methyl-1-1m-lec~noic acid, 2-ethyl-1-decanoic acid, 2-propyl-1-nonanoic acid, 2-butyl-1-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 offormula R-CON (Rl) CH2 COOM, wherein R is a Cs-C17 linear or branched alkyl or alkenyl group, Rl is a C1-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.

CA 022~6701 1998-11-26 WO 97/45511 PCTtlJS97/08234 -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 of alkyl phenols, nonionic ethoxylated alcohols, nonionic ethoxylated/propoxylated fatty alcohols, nonionic ethoxylate/propoxylate condensates with propylene glycol, and the nonionic ethoxylate condensation products with propylene oxide/ethylene ~i~mine adducts.

Nonionic alkoxylated alcohol surfactant The condensation products of aliphatic alcohols with from 1 to 25 molesof 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 6 to 22 carbon atoms. Particularly preferred are the condensation products of alcohols having an alkyl group cont~ining 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 R2CONR1Z wherein: R1 is H, Cl-C4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl, ethoxy, propoxy, or a mixture thereof, preferable C1-C4 alkyl, more preferably C1 or C2 alkyl, most preferably C1 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 C11-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.

.... . .

CA 022~6701 1998-ll-26 W O 97/45511 PCTrUS97/08234 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~ining from 7 to 21, preferably from 9 to 17 carbon atoms and each R7 is selected from the 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~ining from 6 to 30 carbon atoms and a polysaccharide, e.g., a polyglycoside, hydrophilic group cont~ining from 1.3 to 10 saccharide units.

Preferred alkylpolyglycosides have the formula R20(CnH2nO)t(glycosyl)x wherein R2 is selected from the group consisting 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 surfactants for use herein include the amine oxide surfactants 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, acylamidopropoyl and alkyl phenyl group, or mixtures thereof, cont~ining 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, preferably from O to 3; and each R5 is an alkyl or hydroxyalkyl group .

CA 022~670l l998-ll-26 W O 97/45Sll PCTrUS97/08234 cont~inin~ from 1 to 3, or a polyethylene oxide group cont~inin~ from 1 to 3 ethylene oxide groups. Preferred are C1o-C1g alkyl dimethylamine oxide, and C10-l8 acylamido alkyl dimethylamine oxide.

A suitable example of an alkyl aphodicarboxylic acid is Miranol(TM) C2M Conc. m~mlf~ctured by Miranol, Inc., Dayton, NJ.

Zwitterionic surfactant Zwitterionic surfactants can also be incorporated into the detergent compositions hereof. These surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary 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 R1 is typically C1-C3 alkyl, and R2 is a C1-Cs hydrocarbyl group. Preferred 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 surfactants can also be used in the detergent compositions herein. Suitable cationic surfactants include the quaternary ammonium surfactants selected from mono C6-C16, preferably C6-C1o N-alkyl or alkenyl ammonium surfactants wherein the rem~inin~ N
positions are substituted by methyl, hydroxyethyl or hydroxypropyl groups.

.AIk~linity In the detergent compositions of the present invention preferably a ~lk~linity system is present to achieve optimal cationic ester surfactant performance. The ~lk~linity system comprises components capable of CA 022~6701 1998-11-26 providing ~ linity species in solution. By ~lk~linity species it is meant herein: carbonate, bicarbonate, hydroxide, the various silicate anions, percarbonate, perborates, perphosphates, persulfate and persilicate.
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.

Examples 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 Gerrnan Patent Application No. 2,321,001 published on November 15, 1973.

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.

Preferred crystalline layered silicates for use herein have the generalformula NaMSix02x+l 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 preferably 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.

Water-soluble builder compound The detergent compositions of the present invention preferably contain a water-soluble builder compound, typically present at a level of from 1 %

CA 022~6701 1998-11-26 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 forrns, 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 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 performance.

Suitable carboxylates cont~inin~ 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~ining 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 oxydisuccinates disclosedinBritishPatentNo. 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~ining Up to three carboxy groups per molecule, more particularly citrates.

CA 022~6701 1998-ll-26 W O 97/45511 PCTrUS97/08234 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 mixtures are also contemplated as useful builder components.

Borate builders, as well as builders cont~ining 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 arnmonium 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 detergent compositions of the present invention may contain a partially soluble or insoluble builder compound, typically present at a level of from 1 % to 80 % by weight, preferably from 10 % to 70 % by weight, most preferably from 20% to 60% weight of the composition.

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~ini~g 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 CA 022~670l l998-ll-26 W O 97/45511 PCT~US97/08234 B, Zeolite P, Zeolite X, Zeolite HS and mixtures thereof. Zeolite A hasthe 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.
Or~anic peroxyacid bleaching system A preferred feature of detergent compositions of the invention is an organic peroxyacid bleaching system. In one preferred 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. 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 con~ining 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 storage stability for the perhydrate salt in the granular product.

CA 0225670l l998-ll-26 W O 97/45511 PCTrUS97/08234 -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 the form of the monohydrate of nominal formula NaBO2H2O2 or the tetrahydrate NaB02H202-3H20 Alkali metal percarbonates, particularly sodium percalbGllate are preferred perhydrates herein. Sodium percarbonate is an addition compound having a formula co~les~onding to 2Na2CO3.3H2O2, and is available commercially as a cryshllin~ solid.

Potassium peroxymono~el~-l}fate is another inorganic perhydrate salt ofuse in the det~r~,enl 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 l!
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 105~ by weight of the detergent compositions.

CA 022~6701 1998-11-26 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 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.

Preferred L groups are selected from the group consisting of:

O~ O~Y , and --~~

1 3 L=l R3 Y
y -O--C H=C--C H=C H2--O--C H=C--C H=C H2 O O
Il Y~ 11 -O--C--R1 _N' 'NR4 --N ~NR4 Il 11 O O

CA 022~6701 1998-ll-26 W O 97/45511 PCTrUS97/08234 ---O--C=CHR4 , and N--c--CH--R4 R3 o and mixtures thereof, wherein Rl is an alkyl, aryl, or alkaryl group cont~ining 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 R1, 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 ammmonium groups The preferred solubilizing groups are -SO3-M +, -CO2-M +, -SO4-M +, -N (R )~X~ and O < --N(R )3 and most preferably -SO3-M+ and -CO2-M wherein ~ is an alkyl chain containing 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 percarboxylic precursor compounds of the imide type include the N-,N,N1N1 tetra acetylated alkylene diamines 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 preferred.

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

CA 02256701 1998-ll-26 W O 97/45511 PCTrUS97/08234-Amide substituted alkyl peroxyacid precursors Amide substituted alkyl peroxyacid precursor compounds are suitable herein, including those of the following general formulae:

O R5 O or R5 O O

wherein Rl is an alkyl group with from 1 to 14 carbon atoms, R2 is an alkylene group cont~inin~ from 1 to 14 carbon atoms, and R5 is H or an alkyl group cont~inin~ 1 to 10 carbon atoms and L can be essentially any leaving group. Amide substitl)te~ bleach activator compounds of this type are described in EP-A-0170386.

r~ll,el~oic acid precursor re~bel~oic acid precursor compounds provide perbenzoic acid on perhydrolysis. Suitable O-acylated pe.l,el~oic acid precursor compounds include the substi~lte~l and unsubstituted benzoyl oxybenzene sulfonates, and the benzoylation products of sorbitol, glucose, and all s~cch~rides with benzoylating agents, and those of the imide type including N-benzoyl succinimi~1e, tetrabenzoyl ethylene ~ min~ and the N-benzoyl s~bstinlte~
ureas. Suitable imi~l~7.ole type perbenzoic acid precursors include N-benzoyl imid~7.ole and N-benzoyl benzimidazole. Other useful N-acyl group-con~inin~ ~e~lJell~OiC acid precursors include N-benzoyl pyrrolidone, dibenzoyl taurine and benzoyl pyroglutamic acid.

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

Typically, cationic peroxyacid precursors are formed by substitl~tin~ the peroxyacid part of a suitable peroxyacid precursor compound with a positively charged functional group, such as an ammonium or alkyl CA 022F6701 1998-ll-26 ~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 substituted derivative thereof, precursor compound as described hereinbefore. Alternatively, the peroxyacid precursor compound may be an alkyl percarboxylic acid precursor compound or an amide substituted alkyl peroxyacid precursor as described hereinafter Cationic peroxyacid precursors are described in U.S. Patents 4,904,406;4,751,015; 4,988,4S1; 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 substituted alkyl or benzoyl oxybenzene sulfonates, N-acylated caprolactams, and monobenzoyltetraacetyl glucose benzoyl peroxides. Preferred cationic peroxyacid precursors of the N-acylated caprolactam class include the trialkyl ammonium methylene benzoyl caprolactams and the trialkyl ammonium methylene alkyl caprolactams.

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:

o [~"C--R1 wherein Rl is H, alkyl, alkaryl, aryl, or arylalkyl.

Preformed o~e~nic peroxyacid The organic peroxyacid bleaching system may contain, in addition to, oras an alternative to, an organic peroxyacid bleach precursor colllpound, a preformed organic peroxyacid, typically at a level of from 1 % to 15 % by weight, more ~lefelably from 1% to 10% by weight of the colllposilion.

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

O R5 O or R5 o o wherein Rl is an alkyl, aryl or alkaryl group with from 1 to 14 carbon atoms, R2 is an alkylene, arylene, and alkarylene group cont~inin~ from 1 to 14 carbon atoms, and RS is H or an alkyl, aryl, or alkaryl group co.~1;.i..;.~ 1 to 10 carbon atoms. Amide sulst;~ ç~ organic peroxyacid compounds of this type are described in EP-A-0170386.

Other organic peroxyacids include diacyl and tetraacylperoxides, especially diperoxydo~ec~n~ oc acid, diperoxytetr~ec~nedioc acid and diperoxyhex~lec~ne~ioc acid. Mono- and diperazelaic acid, mono- and dipe~ assylic acid and N-phthaloylaminoperoxicaproic acid are also suitable herein.

CA 022~6701 1998-ll-26 W O 97/45511 PCTrUS97/08234 -Bleach catalyst The compositions optionally contain a transition metal cont~ining 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~n~se cations, an auxiliary metal cation having little or no bleach catalytic activity, such as zinc or aluminl~m cations, and a sequestrant having de~med stability constants for the catalytic and auxiliary metal cations, particularly ethylene~i~minetetraacetic 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~ng~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-0)3(1,4,7-trimethyl-1,4,7-triazacyclononane)2-(PF6)2, MnIII2(u-O) 1 (u-OAc)2(1,4,7-trimethyl-1,4,7-triazacyclononane)2-(C104)2, MnIV4(u-0)6(1,4,7-triazacyclononane)4-(C104)2, MnIIIMnIV4(u-0)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.
549,272. Other li~n-ls 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~ng~nese (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~ng~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-O)2MnIVN4)+and [Bipy2MnIII(u-O)2MnIVbipy2] -(Cl04)3.

CA 022~6701 1998-11-26 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/multidentate ligand catalyst), U .S . 4,711,748 and European patent application, publication no. 224,952, (absorbed manganese on aluminosilicate catalyst), U.S.
4,601,845 (aluminosilicate support with m~n~;~nese and zinc or m~nesium salt), U.S. 4,626,373 (m~n~n~se/ligand catalyst), U.S.
4,119,557 (ferric complex catalyst), German Pat. specification 2,054,019 (cobalt chelant catalyst) C~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 (manganese gluconate catalysts).

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

Heavy metal ion sequestrants are generally present at a level of from 0.005% to 20%, preferably from 0.1% to 10%, more preferably from 0.25% to 7.5% and most preferably from 0.5% to 5% by weight of the compositlons.

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

Preferred among the above species are diethylene tri~min~ penta (methylene phosphonate), ethylene diamine tri (methylene phosphonate) hexamethylene ~ mine tetra (methylene phosphonate) and hydroxy-ethylene 1,1 diphosphonate.

CA 022~670l l998-ll-26 W O 97/45511 PCTrUS97108234 -Other suitable heavy metal ion sequestrant for use herein include nitrilotriacetic acid and polyaminocarboxylic acids such as ethylenediaminotetracetic acid, ethylenetriamine pentacetic acid, ethylenedi~mine disuccinic acid, ethylene~ mine diglutaric acid, 2-hydroxypropylen~ mine disuccinic acid or any salts thereof. Especially preferred is ethylene~liAmin~-N,N'-disuccinic acid (EDDS) or the alkali metal, ~lk~line earth metal, ammonium, 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 ~i~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 ~-~l~nin~-N,N'-tli~çetic 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-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), ethylene~ mine-N-N'-diglutaric acid (EDDG) and 2-hydroxypropylene~ mine-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, cellulases, endolases, esterases, pectinases, lactases and peroxidases conventionally incorporated into detergent compositions. Suitable enzymes are ~li.ccllssed in US Patents 3,519,570 and 3,533,139.

CA 022~6701 1998-11-26 WO 97/45511 PCT/US97tO8234 -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 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.

Preferred amylases include, for example, a-amylases obtained from a special strain of B licheniformis, described in more detail in GB-1,269,839 (Novo). Preferred commercially available amylases include for example, those sold under the tradename Rapidase by Gist-Brocades, and those sold under the tradename Termamyl and BAN by Novo In~ 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~inç~l, for example, from a lipase producing strain of Humicola sp., Thermomyces sp. or Pseudomonas sp. including Pseudomonas pseudoalcaligenes or Pseudomas fluorescens. Lipase from chemically or genetically modified mllt~ntS of these strains are also useful herein. A preferred lipase is derived from Pseudomonas pseudoalcaligenes, which is described in Granted European Patent, EP-B-0218272.

Another preferred lipase herein is obtained by cloning the gene from Humicola lanuginosa 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.

CA 022~6701 1998-ll-26 W O 97/45511 PCT~US97/08234 Organic polymeric compound Organic polymeric compounds are preferred additional components of the detergent 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 partic~ te component together. By organic 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 molecular weight organic polymeric compounds described as clay flocc~ ting agents herein.

Organic polymeric compound is typically incorporated in the detergent compositions of the invention at a level of from 0.1 % to 30%, prefelably from 0.5% to 15%, most preferably from 1 % to 10% by weight of the compositions.

Examples of organic polymeric compounds 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, acrylicacid, polyaspartic acid and vinyl alcohol, particularly those having an average molecular weight of from 5,000 to 10,000, are also suitable herein.

CA 022~6701 1998-11-26 Other organic polymeric compounds suitable for incorporation in the detergent 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 4000.

Suds suppressing system The detergent compositions of the invention, when formulated for use inmachine washing compositions, preferably comprise a suds suppressing system present at a level of from 0.01% to 15 %, preferably from 0.05 %
to 10%, 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 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 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~ stry, 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 022~6701 1998-11-26 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), fatty acid esters of monovalent alcohols, aliphatic C18-C40 ketones (e.g. stearone) N-alkylated amino triazines such as tri- to hexa-alkylmelamines or di- to tetra alkyl~ min~ 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 antifoam compound comprising in combination (i) polydimethyl siloxane, at a level of from 50% to 99%, preferably 75 % to 95 % by weight of the silicone 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 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 .. , , .. . .. ~ , .

CA 022~6701 1998-11-26 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 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.

Clay softening 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 flocculating agents.

Polymeric dye transfer inhibiting agents The detergent compositions herein may also comprise from 0.01 % to 10 %, preferably from 0.05 % to 0.5 % by weight of polymeric dye transfer inhibiting agents.

CA 02256701 1998-ll-26 W O 97/45511 PCTrUS97/08234 -The polymeric dye transfer inhibiting agents are preferably selected from polyarnine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinylpyrrolidonepolymers or combinations thereof.
a) Polyamine N-oxide polymers Polyarnine N-oxide polymers suitable for use herein contain units having the following structure formula:
p I

(I) Ax R

wherein P is a polymerisable unit, and 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 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:

(R1 ) X - IN (R2)Y

(R3)z or - N-(R1 )x wherein R1, R2, and R3 are aliphatic groups, aromatic, heterocyclic or alicyclic groups or combinations thereof, x or/and y or/and z is O or 1 and wherein the nitrogen of the N-O group can be ~ttac.he~l or wherein the CA 022~6701 1998-11-26 W O 97/45511 PCTrUS97/08234 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 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 attached 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.

CA 022~6701 1998-ll-26 W O 97/45511 PCT~US97/08234 -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, Canada 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 suitable polyvinylpyrrolidones which are commercially available from BASF Cooperation include Sokalan HP 165 and Sokalan HP 12.
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 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.
Optical bri~htener 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 formula:

CA 022~670l l998-ll-26 W O 97/45511 PCTrUS97/08234 N ~ C = C ~ I ~ N o~ R2 ~N
R2 SO3M SO3M R~

wherein R1 is selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl; R2 is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, morphilino, chloro and amino; and M is a salt-forming cation such as sodium or potassium.

When in the above formula, R1 is anilino, 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 Corporation. Tinopal-UNPA-GX is the preferred hydrophilic optical brightener useful in the detergent compositions herein.

When in the above formula, R1 is anilino, R2 is N-2-hydroxyethyl-N-2-methylamino and M is a cation such as sodium, the brightener is 4,4'-bis~(4-anilino-6-(N-2-hydroxyethyl-N-methylamino)-s-triazine-2-yl)amino]2,2'-stilbenedisulfonic acid disodium salt. This particular brightener species is commercially marketed under the tradename Tinopal SBM-GX by Ciba-Geigy Corporation.

When in the above formula, R1 is ~nilino, R2 is morphilino and M is a cation such as sodium, the brightener is 4,4'-bis[(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 agents Cationic fabric softening agents can also be incorporated into compositions in accordance with the present invention. Suitable cationic .. . ..

CA 022~6701 1998-11-26 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 15~ to 5~ by weight.

Other optional ingredients Other optional ingredients suitable for inclusion in the compositions of the invention include colours and filler salts, with sodium sulfate being a preferred filler salt.

pH of the compositions The present compositions preferably have a pH measured as a 1%
solution in distilled water of at least 8.5, preferably from 9.0 to 12.5, most preferably from 9.5 to 11Ø

Form of the compositions The compositions in accordance Wit}l the invention 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 washing machine by means of a dispensing device placed in the machine drum with the soiled fabric load.

In general, granular detergent compositions in accordance with the present invention can be made via a variety of methods including dry mixing, spray drying, agglomeration and granulation.

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 0.15mm 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 against the &~elluie 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 d~terge.l~ compositions in accordance withthe ~l~sellt 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 me~Al)red 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 eAL.e~ y to allow the COIllelltS of the funnel to be emptied into an aAially ~ligne-1 cylindrical cup disposed below the funnel. The funnel is 130 mm high and has internal ~ tefs of 130 mm and 40 mm at its respective upper and lower e~llell~ilies. It is mounted so that the lower eAlr~ y 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 rli~meter of 84 mm. Its nominal volume is 500 ml.

To carry out a mP~ 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 wêighed and the value obtained for the weight of powder doubled to provide a bulk dênsity in g/litre. Replicate mP~sl~rements are made as required.

Surfactant agglomerate particles The cationic êster surfactant herein, prêferably with additional surf~Gt~nts, is l,refelably present in granular compositions in the form of surfactant agglomerate particles, which may take thê form of flakes, prills, marumes, noodles, ribbons, but preferably take the form of granules. The most preferred way to process the particles is by agglomerating powders (e.g. aluminosilicate, carbonate) with high active surfactant pastes and to control the particle size of the resultant CA 022~6701 1998-11-26 agglomerates within speci~led 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 % byweight, 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.

T.~ln~ry washing method Machine laundry methods herein typically comprise treating soiled laundry with an aqueous 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 detergent composition it is meant from 40g to 300g of product dissolved or dispersed in a wash solution of volume from 5 to 65 litres, as are typical product dosages and wash solution volumes commonly employed in 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 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~ining the detergent product is placed inside the drum. At the commencement of the wash cycle of the washing machine water is CA 022~6701 1998-ll-26 W O 97/45511 pcTrus97lo8234 -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 detergent 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 permeable to liquid but impermeable to the solid product, which will allow release of dissolved product. Preferably, the detergent product will be rapidly released at the start of the wash cycle thereby providing transient localised high concentrations of product in the dmm of the washing machine at this stage of the wash cycle.

Preferred dispensing devices are reusable and are designed in such a way that container integrity is m~int~in~ll 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 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 w~shing medium. The support ring is provided with a masking arrangemnt to prevent egress of wetted, undissolved, product, this arrangement typically comprising radially CA 022~6701 1998-ll-26 W O 97t45511 PCTrUS97/08234 extending walls extending from a central boss in a spoked wheel configuration, or a similar 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.

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

CA 0225670l l998-ll-26 W O97/45511 PCTrUS97/08234 46 Example 1 Three per~ume compositions for incorporation into the detergent compositions of examples 2 to 10 were prepared according to the recipes A, B and C.

~erfume composition A
Parts by weight Benzyl salicylate 25 P-tert. butylcyclohexyl ~ret~te 15 Alpha-hexylcinn~mic aldehyde 15 Benzyl acetate 10 4-Acetoxy-3-pentyltetrahydropyran 8 Amyl salicylate 7 Citronellol 7 Tetrahydrolinalool S
Alpha-amylcinn~mic aldehyde S
7-Acetyl-1, 1 ,6,7-tetramethyl-1,2,3,4,5,6,7,8- 3 octahydronaphtalene CA 0225670l l998-ll-26 W O 97/45511 PCTrUS97/08234 Perfume composition B
Parts by weight Benzyl salicylate 20 Alpha-hexylcinn~mic aldehyde 20 P-tert. butylcyclohexyl ~cet~te 15 1,3,4,6,7,8-Hexahydro-4,6,6,7,8,8-hexamethyl- 10 cyclopenta(g)-2-benzopyran 1, 1,2,4,4,7-Hexamethyl-6-acetyle-tetralin 8 2-Phenylethanol 5 Benzyl ~cet~te 5 Coumarin 4 Geraniol 4 Tetrahydrolinalool 4 Methyl N-(2,4-dimethyl-3-cyclohexenyl)- 3 methylidene~nthranilate 4-(p-hydroxyphenyl)-butan-2-one 2 Perfume composition C
Parts by weight Benzyl salicylate 20 Alpha-hexylcinn~mic aldehyde 15 P-tert. butylcyclohexyl ~cet~te 15 1,1,2,4,4,7-Hexamethyl-6-acetyle-tetralin 12 1,3,4,6,7,8-Hexahydro~,6,6,7,8,8-hex~met~lyl- 8.5 cyclopenta(g)-2-benzopyran Benzyl ~cet~te 5 3-(p-tert.butylphenyl)-2-methylpopanal 4.S
Patchouli, acid washed 4.5 2,7,8-trimethyl-1-acetyl-cyclododeca-2,5,9-triene 44-(p-hydrozyphenyl)-butan-2-one 4 Methyl naphthyl ketone 2.5 Methyl N-(2,4-dimethyl-7-hydroxycyoctylidene)- 2 anthr~nil~tç
Oakrnoss synthetic 2 Karanal (trandename of Quest International) Abbreviations used in Examples In the d~ tergellL 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-C1s linear alkyl sulfate CxyEzS : Sodium Clx-Cly branched alkyl sulfate condensed with z moles of ethylene oxide C45E7 : A C 14 15 predomin~ntly linear primary alcohol condensed with an average of 7 moles of ethylene oxide PCT~US97/08234 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 I : R1COOCH2CH2.N+(CH3)3 with Rl = C11-cl3 CEQ II : RlCOOCH2CH2CH2N+(CH3)3 with R1 =
Cl l-C13 CEQ III : R1COO CH2 CH2 N+(CH3)2(cH2cH2OH) with R1=C11-C13 CEQ IV : R1 COOCH2CH2 N+ (CH3CH2)2(CH3) with Rl =Cl l-C13 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 gh)r~mi~e TPKFA : C12-C14 topped whole cut fatty acids STPP : Anhydrous sodium tripolyphosphate Zeolite A : Hydrated Sodium Aluminosilicate of forrnula Na12(A1~2Si~2)12. 27H20 having a primary particle size in the range from 0.1 to lO
micrometers NaSKS-6 : Crystalline layered silicate of forrnula ~ -Na2si2os Citric acid : Anhydrous citric acid Calbo,late : Anhydrous sodium carbonate with a particle size between 200~1m and 900~1m Bicarbonate : Anhydrous sodium bicarbonate with a particle size distribution between 400~1m and 1200~1m 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 ~lm CA 02256701 1998-ll-26 PCTrUS97/08234-MA/AA : Copolymer of 1:4 maleic/acrylic acid7 average molecular weight about 70,000.
CM(~ : 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 ~ndl~stries A/S
Cellulase : Cellulytic enzyme of activity 1000 CEVU/g sold by NOVO In~ ctries 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 1001cLU/g sold by NOVO Industries A/S under the tradename Lipolase Endolase : Endoglunase enzyme of activity 3000 CEVU/g sold by NOVO Industries A/S
PB4 : Sodium perborate tetrahydrate of nominal formula NaBo2.3H2o.H2o2 PB1 : Anhydrous sodium perborate bleach of nominal formula NaBo2.H2o2 Percarbonate : Sodium Percarbonate of nominal formula 2Na2C03 3H2~2 NOBS : Nonanoyloxybenzene sulfonate in the form of the sodium salt.
TAED : Tetraacetylethylene~ mine DTPMP : Diethylene triamine penta (methylene phosphonate), marketed by Monsanto under the Trade name Dequest 2060 Photoactivated: Sulfonated Zinc Phthlocyanine encapsulated in bleach dextrin soluble polymer Brightener 1 : Disodium4,4'-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.
Perfume A : Perfume composition A as described CA 0225670l l998-ll-26 PCT~US97/08234 in example 1 Perfume B : Perfume composition B as described in example 1 Perfume C : Perfume composition C as described in example 1.
HEDP ~ hydroxyethane diphosphonic acid PVNO : Polyvinylpyridine N-oxide PVPVI : Copolymerofpolyvinylpyrolidone and vinylimidazole SRP 1 : Sulfobenzoyl end capped esters with oxyethylene oxy and terephtaloyl backbone SRP 2 : Diethoxylated poly (1, 2 propylene terephtalate) 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.

CA 02256701 1998-ll-26 PCTrUS97/08234 In the following Examples all levels are quoted as % by weight of the composition:

Example 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 3.4 3.4 3.4 3.4 CEQ I - 0.8 4.5 2.0 - 0.7 CEQ II 6.0 0.5 - 0.7 2.0 0.8 QAS - - 0.8 - - 0.8 Zeolite A 18.1 18.1 18.1 18.1 18.1 18.1 Carbonate 13.0 13.0 13.0 27.0 27.0 27.0 Silicate 1.4 1.4 1.4 3.0 3.0 3.0 Sodiumsulfate 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 0.25 0.25 0.25 0.25 H E D P 0.3 0.3 0.3 0.3 0.3 0.3 CA 02256701 1998-ll-26 W O 97/45511 PCTrUS97/08234 - ' 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 MA/AA 0.3 0.3 0.3 0.3 0.3 0.3 CMC 0.2 0.2 0.2 0.2 0.2 0.2 Photoactivated 15 15 15 15 15 15 bleach (ppm) ppm ppm ppm ppm ppm ppm Brightener 1 0.09 0.09 0.09 0.09 0.09 0.09 Perfume A 0.1 0.2 0.3 0.1 0.1 0.1 Perfume B 0.2 0.1 0.1 0.3 0.1 0.1 Perfume C 0.1 0.1 0.1 0.1 0.3 0.1 Silicone antifoam 0.5 0.5 0.5 0.5 0.5 0.5 Misc/minors to 100~

Density in g/litre 850 850 850 850 850 850 CA 02256701 1998-ll-26 W O97/45511 PCTrUS97/08234 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 II 0.8 - 2.8 CEQ III 0.4 2.0 0.5 STPP 19.7 Zeolite A - 19.5 19.5 NaSKS-6/citric acid - 10.6 10.6 (79:21) Carbonate 6.1 21.4 21.4 Bicarbonate - 2.0 2.0 Silicate 6.8 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 (ppm) Brightener 1 0.08 0.19 0.19 Brightener 2 - 0.04 0.04 Perfume C 0.3 0.2 0.2 Silicone antifoam 0.5 2.4 2.4 Minors/misc to 100%

Example 4 The following detergent formulations, according to the present invention were prepared, where J is a phosphorus-cont~inin~ detergent composition, K is a zeolite-con~inin~ detergent composition and L is a compact detergent composition:

J K L

Blown Powder STPP 24.0 - 24.0 Zeolite A - 24.0 C45AS 9.0 6.0 13.0 M A/~ 2.0 4.0 2.0 L A S 6.0 8.0 11.0 T A S 2.0 CEQ I - 2.0 C E Q II - - 2.0 CEQ III 2.0 Silicate 7.0 3.0 3.0 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 B 0.3 0.3 0.4 Dry additives Carbonate 6.0 13.0 15.0 PB4 18.0 18.0 10.0 PB1 4.0 4.0 0 TAED 3.0 3.0 1.0 Photoactivated bleach 0.02 0.02 0.02 Protease 1.0 1.0 1.0 Lipase 0.4 0.4 0.4 Amylase 0.25 0.30 0.15 CA 02256701 1998-ll-26 Dry mixed sodium 3.0 3.0 5.0 sulfate B~l~nee (Moisture& 100.0 100.0 100.0 Miscellaneous) Density (g/litre) 630 670 670 PCTrUS97/08234 Example 5 The following nil bleach-cont~inin~ detergent formulations of par~icular use in the washing of colored clothing, according to the present invention were prepared:

M N O
Blown Powder Zeolite A 15 .0 15 .0 Sodium sulfate 0.0 5.0 LAS 3.0 3.0 CEQ I 0.5 0.5 0.5 CEQII 1.0 1.5 0.5 CEQIII 0.5 1.5 2.0 DTPMP 0.4 0.5 CMC 0.4 0.4 MA/AA 4.0 4 0 Agglomerates C45AS - - 11.0 LAS 6.0 5.0 TAS 3.0 2.0 Silicate 4.0 4.0 Zeolite A 10.0 15.0 13.0 CMC - - ~- 5 MA/AA - - 2.0 Carbonate 9.0 7.0 7.0 Spray On Perfume A 0.1 0.2 0.2 Perfume B 0.1 0.2 0.1 Perfilme C 0.2 0.1 0.1 C45E7 4.0 4.0 4.0 C25E3 2.0 2.0 2.0 Dry additives MA/AA - - 3.0 NaSKS-6 - - 12.0 Citrate 10.0 - 8.0 Bicarbonate 7.0 3.0 5.0 Carbonate 8.0 5.0 7.0 PVPVI/PVNO 0.5 0.5 0.5 Alcalase 0.5 0.3 0-9 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 PCTrUS97/08234 Example 6 The following detergent formula~ions, according to the present invention were prepared:

P Q R S

LAS 20.0 14.0 24.0 22.0 QAS 0.7 1.0 - 0.7 CEQ III 0.4 - 3.5 1.5 CEQ IV 1.5 2.4 - 1.5 TFAA - 1.0 C25~5/C45E7 - 2.0 - 0.5 C45E3S - 2.5 STPP 30.0 18.0 30.0 22.0 Silicate 9.0 5.0 10.0 8.0 Carbonate 13.0 7.5 - 5.0 Bicarbonate - 7.5 DTPMP 0.7 1.0 SRP 1 0.3 0.2 - 0.1 MA/~u~ 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 - lOppm bleach (ppm) Bri~htell~r 1 0.2 0.2 0.08 0.2 PBl 6.0 2.0 N O BS 2.0 1.0 Perfume B 0.1 0.2 0.3 0.5 R~l~nce 100 100 100 100 (Moisture and Miscellaneous) .

Example 7 The following detergent formulations, according to the present invention were prepared:

T U V

Blown Powder Zeolite A 30.0 22.0 6.0 Sodium sulfate 19.0 5.0 7.0 MA/AA 3.0 3.0 6.0 LAS 14.0 12.0 22.0 C45AS 8.0 7.0 7.0 CEQII - 0.7 2.5 CEQ IV 1.5 1.5 0.5 Silicate - 1.0 5.0 Soap - - 2.0 Brightener 1 0.2 0.2 0.2 Car~onate 8.0 16.0 20.0 DTPMP - 0.4 0.4 Spray On C45E7 1.0 1.0 1.0 Perfume C 0.6 - 0.5 0.2 Dry additives PVPVI/PVNO 0.5 0.5 0.S
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 e (Moisture 100 100 100 and Miscellaneous) CA 022~6701 1998-11-26 Example 8 The following high density and bleach-cont~inin~ detergent formulations, according to the present invention were prepared:

W X Y

Blown Powder Zeolite A 15.0 15.0 15.0 Sodim sulfate 0.0 5.0 0.0 LAS 3.0 3.0 3.0 CEQ II 0.5 0.5 CEQ III 0.9 1.2 2.5 QAS - 1.5 1.5 DTPMP 0.4 0.4 0.4 CMC 0.4 0.4 0.4 MA/AA 4.0 2.0 2.0 Agglomerates LAS 5.0 5.0 5.0 TAS 2.0 2.0 1.0 Silicate 3.0 3.0 4.0 Zeolite A 8.0 8.0 8.0 Carbonate 8.0 8.0 4.0 Spray On Perfume B 0.8 0.1 0.3 C45E7 2.0 2.0 2.0 C25E3 2.0 - -Dry additives -Citrate 5.0 - 2.0 Bicarbonate - 3.0 Carbonate 8.0 15.0 10.0 TAED 6.0 2.0 5.0 PB1 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 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~nce (Moisture and 100.0 100.0 100.0 Miscellaneous) Density (g/litre) 850 850 850 CA 02256701 1998-ll-26 Example 9 The following high density detergent formulations, according to the present invention were prepared:

Z AA

Agglomerate C45AS 11.0 14.0 CEQ IV 0.8 2.2 Zeolite A 15.0 6.0 Carbonate 4.0 8.0 MA/AA 4.0 2.0 CMC 0.5 0.5 DTPMP 0.4 0.4 Spray On C25E5 5.0 5.0 Perfume C 0.5 0.3 Dry Adds HEDP 0.5 0.3 SKS 6 13.0 10.0 Citrate 3.0 1.0 TAED 5.0 7.0 Percarbonate 20.0 20.0 SRP 1 0.3 0.3 Protease 1.4 1.4 Lipase 0.4 0.4 Cellulase 0.6 0.6 Amylase 0.6 0.6 Silicone antifoam 5.0 5.0 Brightener 1 0.2 0.2 Brightener 2 0.2 R~l~nce (Moisture and 100 100 Miscellaneous) Density (g/litre) 850 850 CA 022~6701 1998-ll-26 W O 97/45511 PCT~US97/08234 Example 10 The following liquid detergent formulations, according to the present invention were prepared:

AB AC AD AE AF AG AH AI

CEQI 0.4 1.0 0.8 0.4 2.0 1.5 1.5 2.5CEQII 0.6 1.2 0.7 0.4 1.2 0.5 2.5 1.5 LAS 10. 13.0 9.0 - 25.0 - - -o C25AS 4.0 1.0 2.0 10. - 13.0 18.0 15.0 o C25E3S 1.0 - - 3.0 - 2.0 2.0 4.0C25E7 6.0 8.0 13. 2.5 - - 4.0 4.0 o TPAA - - - 4.5 - 6.0 8.0 8.0 QAS - - - - 3.0 1.0 TP KF A 2.0 - 13. 2.0 - 15.0 7.0 7.0 o Rapeseed fatty acids - - - 5.0 - - 4.0 4.0 Citric acid 2.0 3.0 1.0 1.5 1.0 1.0 1.0 1.0 Dodecenyl/tetradecenyl 12. 10.0 - - 15.0 succinic acid 0 Oleic acid 4.0 2.0 1.0 - 1.0 F.th~nol 4.0 4.0 7.0 2.0 7.0 2.0 3.0 2.0 1,2Propanediol 4.0 4.0 2.0 7.0 6.0 8.0 10.0 13.-Mono F.th~nol Amine - - - 5.0 - - 9.0 9.0 Tri F.th~nQl Amine - - 8 NaOH up to pH 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 pe-~t~ ine D TP M P 1.0 1.0 0.5 1.0 2.0 1.2 1.0 S R P 2 0.3 - 0.3 0.1 - - 0.2 0.1 P V N O - - - - - - - 0.10 Protease 0.5 0.5 0.4 0.2 - 0.5 0.3 0.6 s , .

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 ~-rull-e A 0.1 0.2 0.3 0.5 0.6 0.6 0.5 0.4 Bentonite clay - - - - 4.0 4.0 Suspending clay SD3 - - - - 0.6 0.3 - -R~l~n~e (Moisture and lO0 100 100 100 100 100 100 100 Miscellaneous)

Claims (10)

WHAT IS CLAIMED IS:

1. A detergent composition comprising (a) a cationic ester surfactant; and (b) a perfume composition, comprising a perfume component with a molecular weight from 150 to 350 or a precursor thereto, present at a level of from 0.5% to 90% by weight of said perfume composition.

2. A detergent composition according to Claim 1 wherein said cationic ester surfactant is present at a level from 0.5% to 10.0% by weight of the detergent composition.

3. A detergent composition according to Claims 1 or 2 wherein the cationic ester surfactant is selected from those having the formula:
wherein R1 is a C5-C31 linear or branched alkyl, alkenyl or alkaryl chain or M-, N+(R6R7R8)(CH2)S; X and Y, independently, are selected from the group consisting of COO, OCO, O, CO, OCOO, CONH, NHCO, OCONH and NHCOO wherein at least one of X
or Y is a COO, OCO, OCOO, OCONH or NHCOO group; R2, R3, R4, R6, R7, and R8 are independently selected from the group consisting of alkyl, alkenyl, hydroxyalkyl, hydroxy-alkenyl and alkaryl groups having from 1 to 4 carbon atoms; and R5 is independently H or a C1-C3 alkyl group; wherein the values of m, n, s and t independently lie in the range of from 0 to 8, the value of b lies in the range from 0 to 20, and the values of a, u and v independently are either 0 or 1 with the proviso that at least one of u or v must be 1; and wherein M is a counter anion.

4. A detergent composition according to Claim 3 wherein R2,R3 and R4 are independently selected from the group consisting of -CH3 and -CH2CH2OH.

5. A detergent composition according to Claim 3 wherein both R2 and 3 are C2-C3 alkyl groups.

6. A detergent composition according to Claim 3 wherein the cationic ester is selected from the choline esters having the formula:
wherein m is from 1 to 4 and R1 is a C11-C19 linear or branched alkyl chain.

7. A detergent composition according to any of Claims 1 to 6 wherein said perfume component comprises an oxygen-containing functional group.

8. A detergent composition according to any of Claims 1 to 7 wherein the perfume component is an ester of an allylic alcohol perfume.

9. A detergent composition according to any of Claims 1 to 8 wherein the perfume component is present at a level from 0.1 % to 4.0 %
by weight of the detergent composition.

10. A method of washing laundry in a domestic washing machine in which a dispensing device containing an effective amount of a solid detergent composition according to any of Claims 1 to 11 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.