CA2261349C - A detergent composition - Google Patents

Abstract

The invention relates to a detergent composition comprising at least 13 % of a perborate bleach, a tri-protonic or multi-protonic acid source and an alkali ne source capable of reacting together to produce a gas.

Description

A Detereent Composition Technical Field The present invention relates to a detergent composition comprising high levels of perborate bleach and a tri- or mufti protonic acid and alkali source. The detergent compositions are useful for laundry and dish washing methods.
Backr~round to the Invention There is a trend amongst commercially available granular detergents towards higher bulk densities and towards granular detergent compositions which have a higher content of detergent active ingredients, such as bleach. Such detergents offer greater convenience to the consumer. The desire for such concentrated products ensures that the amount of filler materials are reduced and packaging materials will, ultimately, be disposed of.
Amongst consumers there is also a need for detergents which provide improved bleachable stain removal. Therefore, in the recent past detergents have been developed which contain various types of bleaches, which can be incorporated at high levels.
Detergents, comprising high levels of bleach can lead to poor solubility properties, arising from low rate of dissolution or the formation of gels, and thus to poor dispensing of the product, either from the dispensing drawer of a washing machine, or from a dosing device placed with the laundry inside the machine. This poor dispensing is often caused by gelling of particles, which have high levels of surfactant and especially perborate bleach, upon contact with water. The gel prevents a proportion of the detergent powder from being solubilized in the wash water which reduces the effectiveness of the powder. This is a particular problem at low water pressures and/or at lower washing temperature.
EP-A-0 639 637 discloses the replacement of perborate bleach with an alkali metal percarbonate to improve the dispensing profile and dissolution rate of a detergent.
Citrate or mixtures of citrate with sulphate or carbonate can be used to coat the percarbonate bleach. EP-A-0 639 639 contains a similar disclosure in this respect.

WO 98/04668 PCT/US97/129b3 The use of effervescence to improve the dispensability of granular materials has been used extensively in pharmaceutical preparations. The most widely used effervescent system in this respect is citric acid in combination with bicarbonate.This effervescent system has also been described for improving the dispersibility of pesticidal compositions for controlling water-borne pests, e.g. GB-A-2,184,946.
EP-A-0 534 525 discloses the use of particulate citric acid with a specified particle size range of 350 to 1500 microns.
US -A-5, 114,647 discloses a sanitising composition comprising granules of alkali metal carbonate and aliphatic carboxylic acid of a particle size of 150 to 2,000 microns.
EP-A-0 333 223 discloses a bathing preparation comprising fumaric acid having an average particle size of 50-500 microns.
The Applicants have found that a problem of the poor dispensing of perborate bleach and particularly perborate monohydrate bleach, is the formation of a localized high concentratation of bleach, which will contact the fabric. This can lead to fabric damage. This problem can especially be encountered with detergent compositions comprising high levels of perborate (monohydrate) bleach. However, these high concentrations are often required for an optimum bleachable stain removal.
The problem of poor dispensing may be exacerbated when high levels of surfactants are present. High levels of surfactants can lead to problems of solid detergent particles remaining in the washing machine and on washed clothes.
The Applicants now have found that this particular problem can be solved or reduced when there is provided a tri- or mufti protonic acid, such as a citric acid and an alkali source, capable of producing a gas when reaction together. We have found that the addition of such an acid and an alkali source to a detergent composition, containing perborate bleach, improves the solubility and/or dispersion of the detergent and the perborate bleach therein, in the wash water and eliminates or reduces the problems of fabric damage by high concentrate bleach remaining in the washing machine and on washed clothes.

The improved dispensing of the perborate bleach amounts to an overall improved and more efficient performance and particularly improved bleachable stain removal.
Furthermore, it has been found that if the detergent compositions also comprise high levels of surfactants, such as anionic, cationic and nonionic surfactants, dispensing of surfactants can also be improved by the inclusion of these acid and an alkali sources (capable of producing a gas when reaction together), whilst the performance of the surfactants is maintained. This eliminates or reduces the problems of solid surfactant particles remaining in the washing machine and on washed clothes and it helps to minimise the formation of high concentrations of insoluble clumps.
Furthermore, since the surfactants are more efficiently dispensed into the wash water, the overall performance of the surfactants is more efficient and an overall improved cleaning, stain removal a.nd soil suspending can be achieved.
Summary of the Invention According to the present invention there is provided a detergent composition comprising an anionic surfactant, perborate bleach at a level of at least 13% of a perborate component, by weight of the composition, citric acid and an alkali source wherein said citric acid and alkali source are capable of reacting together in the presence of water to produce a gas and a cationic C6-C~g N-alkyl or alkenyl mono- or bis-alkoxylated amine surfactant wherein the weight ratio of anionic surfactant to cationic surfactant is from 15:1 to 1:1.
Detailed Description of the Invention Alkali Source In accordance with the present invention, an alkali source is present in the detergent composition such that it has the capacity to react with the acid to produce a gas.
Preferably this gas is carbon dioxide, and therefore the alkali is a carbonate, or a suitable derivative thereof.

The detergent composition of the present invention preferably contains from about 2%
to about 75%, preferably from about 5% to about 60%, most preferably from about 10% to about 30% by weight of the alkali source. When the alkali source is present in an agglomerated detergent particle, the agglomerate preferably contains from about 10% to about 60% of the alkali source.
In a preferred embodiment, the alkali source is a carbonate. Examples of preferred carbonates are the alkaline earth and alkali metal carbonates, including sodium carbonate, bicarbonate and sesqui-carbonate and any mixtures thereof with ultra-fine calcium carbonate such as are disclosed in German Patent Application No.
2,321,001 published on November 15, 1973. Alkali metal percarbonate salts may also be included in the detergent compositions and are also suitable sources of carbonate species and are described below in more detail.
The alkali source may also comprise other components, such as a silicate.
Suitable silicates include the water soluble sodium silicates with an Si02: Na20 ratio of from 1.0 to 2.8, with ratios of from l .b 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 Si02: Na20 ratio of 2.0 is the most preferred silicate.
Alkali metal persilicates are also suitable sources of alkali herein.
Other suitable sources will be known to those skilled in the art.
Tri-or multi protonic acid In accordance with the present invention, a tri- or multi protonic acid is present in the detergent composition such that the it is capable of reacting with the source of alkali in the presence of water to produce a gas.
The source of acidity may be any suitable tri-protonic or multi-protonic acid or mixtures thereof. Preferably, the acid source is a tri-protonic acid, most preferably this is a citric acid.
Derivatives include a salt or ester of the acid. The source of acidity is preferably non-hygroscopic, which can improve storage stability. However, a hydrated and especially monohydrate acidic source can be useful herein. The acid is preferably water-soluble.

The acid is preferably present at a level of from 0.1 % to 50%, more preferably from 0.5% to 25%, even more preferably from 1% to 12%, most preferably from 1% to 7%
by weight of the composition. The present invention allows the use of levels as low as 5 about 0.25% to about 5%.
Preferably, 80% or more of the acid has a particle size in the range of from about 1 SO
microns to about 710 microns, with preferably at least about 37% by weight of the acid source having a particle size of about 350 microns or less. Preferably, 100% of the acid has a particle size of about 710 microns or less. Alternatively, greater than about 38%, more preferably 38.7%, of the particulate acid source has a particle size of about 350 microns or less.
The particle size of the acid is calculated by sieving a sample of the source of acidity on a series of Tyler sieves. For example, a Tyler seive mesh 100 corresponds to an aperature size of 150 microns. The weight fractions thereby obtained are plotted against the aperture size of the sieves.
Perborate component Another essential ingredient of the detergent compositions of the present invention is a perborate component, present at a level of at least 13% by weight of the composition.
More preferably, the perborate is present at a level of from 13% to 40% by weight, even more preferably from 15% to 30% by weight and most preferably from 17% to 25% by weight of the compositions.
The perborate is preferably in the form of a salt, normally in the form of the alkali metal, preferably sodium salt.
The perborate bleach is most preferably a sodium perborate in the form of the monohydrate, of nominal formula NaB02H202. Another highly preferred perborate bleach is the tetrahydrate, of nominal formula NaB02H202.3H20.

The perborate bleach may be included as the crystalline solid without additional protection. However, preferred executions of certain granular compositions utilize a coated form of the perborate bleach which provides better storage stability for the perhydrate salt in the granular product. Suitable coatings comprise inorganic salts such as alkali metal silicate, carbonate or borate salts or mixtures thereof, or organic materials such as waxes, oils, or fatty soaps.
Preferably, the detergent composition comprises a bleach activator, such as TAED or a hydrophobic bleach activator, as described below. Preferably the activator is present at a level of from 0.5% to 15%, more preferably from 1.0% to 10%, most preferably from 2.0% to 6% by weight of the detergent composition.
Optionally, a bleach catalyst can be present, as described below.
Surfactants In a highly preferred embodiment of the invention the detergent compositions comprise one or more surfactants, selected from the group consisting of anionic, cationic and nonionic surfactants.
The surfactant or surfactants are preferably present at a level of from 1 % to 60%, more preferably from 3% to 45%, most preferably from 7% to 35% by weight of the detergent composition.
Anionic surfactant The detergent composition of the present invention preferably comprises one or more anionic surfactants. Any anionic surfactant useful for detersive purposes is suitable.
Examples include salts (including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine 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 unsaturated C 12-C 18 monoesters) diesters of sulfosuccinate (especially saturated and unsaturated diesters), N-acyi 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.
The anionic surfactant can be present at a level of 0.5% to 60%, preferably at a level of from 3% to 50%, more preferably of from 5% to 35%, most preferably from 6%
to 20% by weight of the composition.
The ratio of the anionic surfactant to the cationic surfactant is preferably from 25:1 to 1:3, more preferably from 15:1 to 1:1. most preferably from 10:1 to 1:1.
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-C 1 ~ acyl-N-(C 1-C4 alkyl) and -N-(C1-C2 hydroxyalkyl) glucamine sulfates, and sulfates of alkylpolysaccharides such as the sulfates of alkylpolyglucoside (the nonionic nonsulfated compounds being described herein).
Alkyl sulfate surfactants are preferably selected from the linear and branched primary Cg-C22 alkyl sulfates, more preferably the C 11-C 15 branched chain alkyl sulfates and the C 12-C 14 linear chain alkyl sulfates.
Alkyl ethoxysulfate surfactants are preferably selected from the group consisting of the C 10-C 1 g 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 C 11-C 1 g, most preferably C 11-C 15 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-linear alkylbenzene sulfonates, alkyl ester sulfonates, C6-C22 primary or secondary alkane sulfonates, C6-C24 olefin sulfonates, sulfonated polycarboxylic acids, alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfonates, and any mixtures thereof.
Anionic carboxylate surfactant Suitable anionic carboxylate surfactants include the alkyl ethoxy carboxylates, the alkyl polyethoxy polycarboxylate 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 CH2C00-M+ wherein R is a C6 to C 1 g 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)X-R3 wherein R is a C6 to C 1 g 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 connected 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-undecanoic 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 of formula R-CON
(R1) CH2 COOM, wherein R is a CS-Cl~ linear or branched alkyl or alkenyl group, R 1 is a C 1-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.
Cationic surfactant Another preferred component of the detergent composition of the invention is a cationic surfactant, which can be present at a level of from 0.1 % to 30% by weight of the detergent composition.
Preferably the cationic surfactant is selected from the group consisting of cationic ester surfactants, cationic mono-alkoxylated amine surfactants, cationic bis alkoxylated amine surfactants and mixtures thereof.
The cationic surfactant is preferably present at a level of from 0.1 % to 20%, more 1 S preferably from 0.4% to 12%, most preferably from 0.5% to 5% by weight of the detergent composition.
The ratio of the anionic surfactant to the cationic surfactant is preferably from 25:1 to 1:3, more preferably from 15:1 to 1:1. most preferably from 10:1 to 1:1.
The ratio of cationic surfactant to nonionic surfactant is preferably from 1:30 to 10:1, more preferably from 1:20 to 1:1, most preferably from 1:12 to 1:2.
Cationic ester surfactant The cationic surfactant may comprise a cationic ester surfactant.
If present in the detergent composition of the invention, the cationic ester surfactant is preferably present at a level from 0.1 % to 20.0%, more preferably from 0.4%
to 12%, most preferably from 0.5% to 5.0% by weight of the detergent composition.
The cationic ester surfactant is preferably a water 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 5 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 thereof, with the 10 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 1 S hydrocarbyl chain.
Preferred cationic ester surfactants are those having the formula:
RZ
RS
R1O _ (CH)n0 (X)u - ( C H 2 )m (y)v (C H 2 )t _ N ~ R3 M_ b a wherein Rl is a CS-C31 linear or branched alkyl, alkenyl or alkaryl chain or M-.
N+(R.6R~Rg)(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 fir' is a COO, OCO, OCOO, OCONH or NHCOO group; R2, R3, R4, R6, R~, and Rg 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 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, a and v independently are either 0 or 1 with the proviso that at least one of a or v must be l; and wherein M is a counter anion.

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

Rq O (CH)n0 (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 Cl-C3 alkyl group; wherein the value of n lies in the range of from 0 to 8, the value of b lies in the range from 0 to 20, the value of a is either 0 or l, and the value of m is from3to8.
More preferably R2, R3 and R4 are independently selected from a C 1-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 5 to 8 atoms, most preferably 6 atoms.

1n 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:

R O I M_ (CH)~O (X) (CHZ)m--N p b a R9 wherein R1 is a CS-C31 linear or branched alkyl, alkenyl or alkaryi chain; X
is selected from the group consisting of COO, OCO, OCOO, OC~ONH and NHCOO; Rg is 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 C 1-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 C1-C4 alkyl group and a C 1-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.1n another preferred aspect at least one of R2, R3 and R~ is a C2-C3 alkyl group, more preferably two C2-C3 alkyl groups are present.
Highly preferred water dispersible cationic ester surfactants are the esters having the formula:

R~ -C-O-(CH2)rn-N+-CH3 M' where m is from 1 to 4, preferably 2 or 3 and wherein R I is a C I I -C 19 linear or branched alkyl chain.
Particularly preferred choline esters of this type include the stearoyl choline ester quaternary methylammonium halides (RI=CIA alkyl), palmitoyl choline ester quaternary methylammonium halides (Rl=CI5 alkyl), myristoyl choline ester quaternary methylammonium halides (R I=C 13 alkyl), lauroyl choline ester methylammonium halides (RI=CI I alkyl), cocoyl choline ester quaternary methylammonium halides (R 1=C I I _C 13 alkyl), tallowyl choline ester quaternary methylammonium halides (RI=C15_CI~ alkyl), and any mixtures thereof.
Other suitable cationic ester surfactants have the structural formulas below, wherein d may be from 0 to 20.
IS

R -O-~-( CH )-C-O-CH CH -N~ CH M
1 2 d 2 2 ' 3 M CH3-N ~ CH2-CH2-O-C-( CHz ) a 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 prepared by 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 C I 0-C 1 g 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.

Cationic mono-alkoxylated amine surfactants The cationic surfactant of the present invention can contain a cationic mono-alkoxylated amine surfactant, which has the general formula:
Rl /ApR4 ~N+ X_ R2~ ~R3 wherein R1 is an alkyl or alkenyl moiety containing from about 6 to about 18 carbon atoms, preferably 6 to about 16 carbon atoms, most preferably from about 6 to about 11 carbon atoms; R2 and R3 are each independently alkyl groups containing from one to about three carbon atoms, preferably methyl; R4 is selected from hydrogen (preferred), methyl and ethyl, X- is an anion such as chloride, bromide, methylsulfate, sulfate, or the like, to provide electrical neutrality; A is selected from C1-C4 alkoxy, especially ethoxy (i.e., -CH2CH20-), propoxy, butoxy and mixtures thereof; and p is from 1 to about 30, preferably 1 to about 15, most preferably 1 to about 8.
Highly preferred cationic mono-alkoxylated amine surfactants for use herein are of the formula R1\ /(CH2CH20)i-S H
\N+ XO
CH3/ \CH3 wherein R 1 is C6-C 1 g hydrocarbyl and mixtures thereof, preferably C6-C 14, especially C6-C 11 alkyl, preferably Cg and C 10 alkyl, and X is any convenient anion to provide charge balance, preferably chloride or bromide.
As noted, compounds of the foregoing type include those wherein the ethoxy (CH2CH20) units (E0) are replaced by butoxy, isopropoxy [CH(CH3)CH20] and [CH2CH(CH30] units (i-Pr) or n-propoxy units (Pr), or mixtures of EO and/or Pr and/or i-Pr units.
_____T _~-...._ ____._ ___...,..__._...~._ WO 98/04668 PCT/US97/129b3 When used in granular detergent compositions cationic mono-alkoxylated amine surfactants wherein the hydrocarbyl substituent R1 is C6-C11, especially C10, are preferred, because they enhance the rate of dissolution of laundry granules, especially under cold water conditions, as compared with the higher chain length materials.
S
The levels of the cationic mono-alkoxylated amine surfactants used in detergent compositions of the invention can range from 0.1% to 20%, more preferably from 0.4% to 12%, most preferably from 0.5% to 5.0% by weight of the composition.
10 Cationic bis-alkoxylated amine surfactant The cationic surfactant of the invention can be a cationic bis-alkoxylated amine surfactant, which has the general formula:
R\ /ApR3 \N+ X
R2~ ~A,qRa wherein R 1 is an alkyl or alkenyi moiety containing from about 6 to about 18 carbon atoms, preferably 6 to about i6 carbon atoms, more preferably 6 to about 1 l, most preferably from about 8 to about 10 carbon atoms; R2 is an alkyl group containing from one to three carbon atoms, preferably methyl; R3 and R4 can vary independently and are selected from hydrogen (preferred), methyl and ethyl, X- is an anion such as chloride, bromide, methylsulfate, sulfate, or the like, sufficient to provide electrical neutrality. A and A' can vary independently and are each selected from C1-C4 alkoxy, especially ethoxy, (i.e., -CH2CH20-), propoxy, butoxy and mixtures thereof; p is from 1 to about 30, preferably 1 to about 4 and q is from 1 to about 30, preferably 1 to about 4, and most preferably both p and q are 1.
Highly preferred cationic bis-alkoxylated amine surfactants for use herein are of the formula R\ +/CH2CHZOH
N X
CH3/ 'CHZCH20H

WO 98/04668 PCT/~TS97/12963 wherein R1 is C6-C I g hydrocarbyl and mixtures thereof, preferably Cg, Cg, C
10, C 12~ C 14 alkyl and mixtures thereof. X is any convenient anion to provide charge balance, preferably chloride. With reference to the general cationic bis-alkoxylated amine structure noted above, since in a preferred compound R1 is derived from (coconut) C 12-C 14 alkyl fraction fatty acids, R2 is methyl and ApR3 and A'qR4 are each monoethoxy.
Other cationic bis-alkoxylated amine surfactants useful herein include compounds of the formula:
R~ /(CH2CH~0)pH
N+ X-RZ'~ ~(CH2CH20)qH
wherein R I is C6-C I g hydrocarbyl, preferably C6-C I4 alkyl, independently p is 1 to about 3 and q is 1 to about 3, R2 is CI-C3 alkyl, preferably methyl, and X is an anion, especially chloride or bromide.
Other compounds of the foregoing type include those wherein the ethoxy (CH2CH20) units (E0) are replaced by butoxy (Bu) isopropoxy [CH(CH3)CH20]
and [CH2CH(CH30] units (i-Pr) or n-propoxy units (Pr), or mixtures of EO
and/or Pr and/or i-Pr units.
When used in granular detergent compositions in accord with the invention, cationic bis alkoxylated amine surfactants wherein the hydrocarbyl substituent RI is C6-CI I, especially Cg or CIO, are preferred cationic surfactants, because they enhance the rate of dissolution of laundry granules, especially under cold water conditions, as compared with the higher chain length materials.
The levels of the cationic bis-alkoxylated amine surfactants used in detergent compositions of the invention can range from 0.1 % to 20%, preferably from 0.4% to I2%, most preferably from 0.5% to about 5.0%, by weight of the detergent composition.
Alkoxylated nonionic surfactant _ ._ .._. _..... ____.___.. _. ..____._._ Another preferred surfactant in accord with the detergent composition of the invention is a nonionic surfactant present at a level of from 0.1 % to 40%, more preferably from 0.2% to 20% by weight, most preferably from 0.5% to 5% by weight of the detergent composition.
S
The ratio of cationic surfactant to nonionic surfactant is preferably from 1:30 to 10:1, more preferably from 1:20 to 1:1, most preferably from 1:12 to 1:2.
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 diamine adducts.
Nonionic alkoxylated alcohol surfactant The condensation products of aliphatic alcohols with from 1 to 25 moles of alkylene oxide, particularly ethylene oxide and/or propylene oxide, are suitable for use herein.
The alkyl chain of the aliphatic alcohol can either be straight or branched, primary or secondary, and generally contains from 6 to 22 carbon atoms. Particularly preferred are the condensation products of alcohols having an alkyl group containing 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, C1-C4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl, ethoxy, propoxy, or a mixture thereof, preferable C1-C4 alkyl, more preferably C 1 or C2 alkyl, most preferably C 1 alkyl (i.e., methyl); and R2 is a CS-C31 hydrocarbyl, preferably straight-chain CS-C 1 g alkyl or alkenyi, more preferably straight-chain Cg-C 17 alkyl or alkenyl, most preferably straight-chain C 11-C
17 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 WO 98/04668 PC'T/US97/1Z963 alkoxylated derivative (preferably ethoxylated or propoxylated) thereof. Z
preferably will be derived from a reducing sugar in a reductive amination reaction; more preferably Z is a glycityl.
A preferred nonionic polyhydroxy fatty acid amide surfactant for use herein is a C 15-C 17 alkyl N-methyl glucamide. The ratio of polyhydroxy fatty acid amide to cationic ester surfactant is preferably between 1:1 to 1:8, more preferably 1:2.5. It has been found that such surfactant systems are able to reduce 'lime soap' formation and deposition of encrustation on the fabric.
Nonionic fatty acid amide surfactant Suitable fatty acid amide surfactants include those having the formula:
R6CON(R7)2 wherein R6 is an alkyl group containing from 7 to 21, preferably from 9 to 17 carbon atoms and each R7 is selected from the group consisting of hydrogen, C 1-C4 alkyl, C 1-C4 hydroxyalkyl, and -(C2H40)xH, where x is in the range of from 1 to 3.
Nonionic alk~polvsaccharide surfactant Suitable alkylpolysaccharides for use herein are disclosed in U.S. Patent 4,565,647, Llenado, issued January 21, 1986, having a hydrophobic group containing from 6 to carbon atoms and a polysaccharide, e.g., a polyglycoside, hydrophilic group containing from 1.3 to 10 saccharide units.
25 Preferred alkylpolyglycosides have the fonmula R20(CnH2n0)t(glycosyl)x wherein R2 is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, 30 hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups contain from 10 to 18 carbon atoms; n is 2 or 3; t is from 0 to 10, and x is from 1.3 to 8.
The glycosyl is preferably derived from glucose.
Additional detergent components The detergent compositions of the invention may also contain additional detergent components. The precise nature of these additional components, and levels of incorporation thereof will depend on the physical form of the composition, and the precise nature of the washing operation for which it is to be used.
The compositions of the invention preferably contain one or more additional detergent components selected from surfactants, additional bleaches, builders, organic polymeric compounds, enzymes, suds suppressors, lime soap dispersants, soil suspension and anti-redeposition agents and corrosion inhibitors.
Additional surfactant The detergent compositions of the invention cancontainsone or more surfactants selected from ampholytic, amphoteric and zwitterionic surfactants and mixtures thereof.
A typical listing of ampholytic, and zwitterionic classes, and species of these surfactants, is given in U.S.P. 3,929,678 issued to Laughlin and Hearing 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.
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(OR4)xN0(RS)2 wherein R3 is selected from an alkyl, hydroxyalkyl, acylamidopropoyl and alkyl phenyl group, or mixtures thereof, containing from 8 to 26 carbon atoms; R4 is an alkylene or hydroxyalkylene group containing from 2 to 3 carbon atoms, or mixtures thereof; x is from 0 to 5, preferably from 0 to 3;
and each RS is an alkyl or hydroxyalkyl group containing from 1 to 3, or a polyethylene oxide group containing from 1 to 3 ethylene oxide groups. Preferred are C 10-C 1 g alkyl dimethylamine oxide, and C10-18 acylamido alkyl dimethylamine oxide.

A suitable example of an alkyl aphodicarboxylic acid is Miranol(TM) C2M Conc.
manufactured by Miranol, Inc., Dayton, NJ.
Zwitterionic surfactant Zwitterionic surfactants can also be incorporated into the detergent compositions or components thereof in accord with the invention. 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 I O 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+R2C00-wherein R is a C6-C 1 g hydrocarbyl group, each R 1 is typically C 1-C3 alkyl, and R2 is a C 1-15 CS hydrocarbyl group. Preferred betaines are C12_18 dimethyl-ammonio hexanoate and the C10-I8 acylamidopropane (or ethane) dimethyl (or diethyl) betaines.
Complex betaine surfactants are also suitable for use herein.
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 % to 80% by weight, preferably from 10% to 70% by weight, most preferably from 20% to 60% by weight of the composition.
Suitable water-soluble builder compounds include the water soluble monomeric polycarboxylates, or their acid forms, homo or copolymeric polycarboxylic acids or their salts in which the polycarboxylic acid comprises at least two carboxylic radicals 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 monomeric or oligomeric in type although monomeric polycarboxylates are generally preferred for reasons of cost and performance.

Suitable carboxylates containing one carboxy group include the water soluble salts of lactic acid, glycolic acid and ether derivatives thereof. Polycarboxylates containing two carboxy groups include the water-soluble salts of succinic acid, malonic acid, (ethylenedioxy) diacetic acid, malefic acid, diglycolic acid, tartaric acid, tartronic acid and fiunaric acid, as well as the ether carboxylates and the sulfinyl carboxylates.
Polycarboxylates containing 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 CA 973,771, and the oxypolycarboxylate materials such as 2-oxa-1,1,3-propane tricarboxylates described in British Patent No.
1,387,447.
Polycarboxylates containing four carboxy groups include oxydisuccinates disclosed in British Patent No. 1,261,829, 1,1,2,2-ethane tetracarboxylates, 1,1,3,3-propane tetracarboxylates and 1,1,2,3-propane tetracarboxylates. Polycarboxylates containing 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 containing up to three carboxy groups per molecule, more particularly citrates.
Borate builders, as well as builders containing borate-forming materials that can produce borate under detergent storage or wash conditions are useful water-soluble builders herein.
Suitable examples of water-soluble phosphate builders are the alkali metal tripolyphosphates, sodium, potassium and ammonium pyrophosphate, sodium and potassium and ammonium pyrophosphate, sodium and potassium orthophosphate, sodium polymetalphosphate in which the degree of polymerization ranges from about 6 to 21, and salts of phytic acid.
Parllal1u 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[(A102)z(Si02)y].
xH20 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, containing from 10% to 28%, more preferably from 18% to 22% water in bound form.
The aluminosilicate zeolites can be naturally occurring materials, but are preferably synthetically derived. Synthetic crystalline aluminosilicate ion exchange materials are available under the designations Zeolite A, Zeolite B, Zeolite P, Zeolite X, Zeolite HS
and mixtures thereof. Zeolite A has the formula Na 12 [A102) 12 (Si02)12]~ X20 wherein x is from 20 to 30, especially 27. Zeoiite X has the formula Nag6 [(A102)g6(Si02)106]~ 276 H20.
Preferred crystalline layered silicates for use herein have the general formula NaMSix02x+1.yH20 wherein M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20. Crystalline layered sodium silicates of this type are disclosed in EP-A-0164514 and methods for their preparation are disclosed in DE-A-3417649 and DE-A-3742043. Herein, x in the general formula above preferably has a value of 2, 3 or 4 and is preferably 2. The most preferred material is 8-Na2Si205, available from Hoechst AG as NaSKS-6.
Additional perhvdrate bleaches Additional to the perborate bleach, a metal percarbonates, particularly sodium percarbonate can be an optinal perhydrates herein. Sodium percarbonate is an addition compound having a formula corresponding to 2Na2C03.3H202, and is available commercially as a crystalline solid.
Potassium peroxymonopersulfate, sodium per is another optinal inorganic perhydrate salt of use in the detergent compositions herein.
Organic_peroxvacid bleaching s s 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, such as the perborate bleach of the claimed invention. In an alternative preferred execution a preformed organic peroxyacid is incorporated directly into the composition. Compositions containing mixtures of a hydrogen peroxide source and organic peroxyacid precursor in combination with a preformed organic peroxyacid are also envisaged.
Peroxyacid bleach precursor Peroxyacid bleach precursors are compounds which react with hydrogen peroxide in a perhydrolysis reaction to produce a peroxyacid. Generally peroxyacid bleach precursors may be represented as O
X-C-L
where L is a leaving group and X is essentially any functionality, such that on perhydroloysis the structure of the peroxyacid produced is O
E) X-C-OOH

WO 98!04668 PCT/US97/12963 Peroxyacid bleach precursor compounds are preferably incorporated at a level of from 0.5% to 20% by weight, more preferably from 1 % to 15% by weight, most preferably from 1.5% to 10% by weight of the detergent compositions.
Suitable peroxyacid bleach precursor compounds typically contain one or more 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 rg ouDs 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:
Y R3 RsY
-O ~ , -O ~ Y , and -O
O O
-N-C-R~ II
-N N -N-C-CH-R
' ~ ~ R3 Y , Y

-O-C H=C-C H=C H2 -O-C H=C-C H=C H2 _,_.__ _~.___ O C H -O Y C
~NR
_O-C-R~ -NwC/NRa _NwC/ a II II
O O

R O Y
-O-C=CHRa , and -N-S-CH-Ra and mixtures thereof, wherein Rl is an alkyl, aryl, or alkaryl group containing from 1 5 to 14 carbon atoms, R3 is an alkyl chain containing from 1 to 8 carbon atoms, R4 is H
or R3, and Y is H or a solubilizing group. Any of Rl, R3 and R4 may be substituted by essentially any functional group including, for example alkyl, hydroxy, alkoxy, halogen, amine, nitrosyl, amide and ammonium or alkyl ammmonium groups.
10 The preferre 3solubilizing groups are -S03-M+, -C02-M+, -S04-M+, -N3 (R3)4X-and O<--N(R )3 and most preferably -S03-M and -C02-M wherein R 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 15 cation, with sodium and potassium being most preferred, and X is a halide, hydroxide, methylsulfate or acetate anion.
Alkyl nercarboxvlic acid bleach precursors 20 AIkyl percarboxylic acid bleach precursors form percarboxylic acids on perhydrolysis.
Preferred precursors of this type provide peracetic acid on perhydrolysis.
Preferred alkyl percarboxyIic precursor compounds of the imide type include the N-,N,N 1 N I tetra acetylated alkylene diamines wherein the alkylene group contains from 25 1 to 6 carbon atoms, particularly those compounds in which the alkylene group contains 1, 2 and 6 carbon atoms. Tetraacetyl ethylene diamine (TAED) is particularly preferred.

Other preferred alkyl percarboxylic acid precursors include sodium 3,5,5-tri-methyl hexanoyloxybenzene sulfonate (iso-NOBS), sodium nonanoyloxybenzene sulfonate (HOBS), sodium acetoxybenzene sulfonate (ABS) and pentaacetyl glucose.
Amide substituted alkyl neroxyacid~precursors Amide substituted alkyl peroxyacid precursor compounds are suitable herein, including those of the following general formulae:
R1 ~__ C-N__R2~C_-L R1 _~N-C-R2-.C-L
O~ R b or R O O
wherein R1 is an alkyl group with from 1 to 14 carbon atoms, R2 is an alkylene group containing from 1 to 14 carbon atoms, and RS is H or an alkyl group containing 1 to 10 carbon atoms and L can be essentially any leaving group. Amide substituted bleach activator compounds of this type are described in EP-A-017038b.
Perbenzoic acid precursor Perbenzoic acid precwsor compounds provide perbenzoic acid on perhydrolysis.
Suitable O-acylated perbenzoic acid precursor compounds include the substituted and unsubstituted benzoyl oxybenzene sulfonates, and the benzoylation products of sorbitol, glucose, and all saccharides with benzoylating agents, and those of the imide type including N-benzoyl succinimide, tetrabenzoyl ethylene diamine and the N-benzoyl substituted areas. Suitable imidazole type perbenzoic acid precursors include N-benzoyl imidazole and N-benzoyl benzimidazoie. Other useful N-acyl group-containing perbenzoic acid precursors include N-benzoyl pyrrolidone, dibenzoyl taurine and benzoyl pyroglutamic acid.
Cationic oeroxvacid~recursors Cationic peroxyacid precursor compounds produce cationic peroxyacids on perhydrolysis.

Typically, cationic peroxyacid precwsors are formed by substituting the peroxyacid part of a suitable peroxyacid precursor compound with a positively charged functional group, such as an ammonium or alkyl ammmonium 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 precwsor compound to be so cationically substituted may be a perbenzoic acid, or substituted derivative thereof, precwsor compound as described hereinbefore. Alternatively, the peroxyacid precwsor compound may be an alkyl percarboxylic acid precwsor compound or an amide substituted alkyl peroxyacid precwsor as described hereinafter.
Cationic peroxyacid precwsors are described in U.S. Patents 4,904,406;

4,751,015;
4,988,451; 4,397,757; 5,269,962; 5,127,852; 5,093,022; 5,106,528; U.K.
1,382,594;
EP 475,512, 458,396 and 284,292; and in JP 87-318,332.
Examples of preferred cationic peroxyacid precwsors are described in WO

and U.S. Patent Nos. 5.686,015; 5,460,747; 5,578,136 and 5,584,888.
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 precwsors of the N-acylated caprolactam class include the trialkyl ammonium methylene benzoyl caprolactams and the trialkyl ammonium methylene alkyl caprolactams.
Benzoxazin organic peroxyacid precwsors Also suitable are precwsor 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
l l C\O
of N C'_'R~
wherein R 1 is H, alkyl, alkaryl, aryl, or arylalkyl.
Preformed organic peroxyacid The organic peroxyacid bleaching system may contain, in addition to, or as an alternative to, an organic peroxyacid bleach precursor compound, a preformed organic peroxyacid , typically at a level of from 1 % to 15% by weight, more preferably from 1 % to 10% by weight of the composition.
A preferred class of organic peroxyacid compounds are the amide substituted compounds of the following general formulae:
R~- l -N R2 C -OOH R~ -N---C-R2- C-OOH
O R5 Ipl ~ 5 ~~
or R O p wherein R 1 is an alkyl, aryl or alkaryl group with from 1 to 14 carbon atoms, R2 is an alkylene, arylene, and alkarylene group containing from 1 to 14 carbon atoms, and RS
is H or an alkyl, aryl, or alkaryl group containing 1 to 10 carbon atoms.
Amide substituted organic peroxyacid compounds of this type are described in EP-A-O 170386.
Other organic peroxyacids include diacyl and tetraacylperoxides, especially diperoxydodecanedioc acid, diperoxytetradecanedioc acid and diperoxyhexadecanedioc acid. Mono- and diperazelaic acid, mono- and diperbrassylic acid and N-phthaloylaminoperoxicaproic acid are also suitable herein.
Bleach catalyst The compositions optionally contain a transition metal containing bleach catalyst. One suitable type of bleach catalyst is a catalyst system comprising a heavy metal canon of defined bleach catalytic activity, such as copper, iron or manganese canons, an auxiliary metal cation having little or no bleach catalytic activity, such as Zinc or aluminum cations, and a sequestrant having defined stability constants for the catalytic and auxiliary metal cations, particularly ethylenediaminetetraacetic acid, ethylenediaminetetra(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 manganese-based complexes disclosed in U.S. Pat. 5,246,621 and U.S. Pat. 5,244,594. Preferred examples of these catalysts include MnIV2(u-O)3(1,4,7-trimethyl-1,4,7-triazacyclononane)2~(PF6)2, MnIII2(u-O)1(u-OAc)2(1,4,7-trimethyl-1,4,7-triazacyclononane)2-(C104)2, MnIV4(u-O)6(1,4,7-triazacyclononane)4-(C104)2, MnIIIMnIV4(u-O)1(u-OAc)2-(1,4,7-trimethyl-1,4,7-triazacyclononane)2-(C104)3, and mixtures thereof. Others are described in European patent application publication no. 549,272. Other ligands 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 manganese (IV) complexes such as Mn(1,4,7-trimethyl-1,4,7-triazacyclononane)(OCH3)3-(PF6).
Still another type of bleach catalyst, as disclosed in U.S. Pat. 5,114,606, is a water-soluble complex of manganese (III), and/or (IV) with a Iigand 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]-(C104)3.
Further suitable bleach catalysts are described, for example, in European patent application No. 408,131 (cobalt complex catalysts), European patent applications, publication nos. 384,503, and 306,089 (metallo-porphyrin catalysts), U.S.
4,728,455 (manganese/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 manganese and zinc or magnesium salt), U.S. 4,626,373 (manganese/ligand catalyst), U.S. 4,119,557 (fernc complex catalyst), German Pat. specification 2,054,019 (cobalt chelant catalyst) Canadian 866,191 (transition metal-containing salts), U.S. 4,430,243 (chelants with manganese cations and non-catalytic metal cations), and U.S. 4,728,455 (manganese gluconate catalysts).
5 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 10 components may also have calcium and magnesium chelation capacity, but preferentially they show selectivity to binding heavy metal ions such as iron, manganese and copper.
Heavy metal ion sequestrants are generally present at a level of from 0.005%
to 20%, 1 S 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 compositions.
Suitable heavy metal ion sequestrants for use herein include organic phosphonates, such as the amino alkylene poly (alkylene phosphonates), alkali metal ethane 1-20 hydroxy disphosphonates and nitrilo trimethylene phosphonates.
Preferred among the above species are diethylene triamine penta (methylene phosphonate), ethylene diamine tri (methylene phosphonate) hexamethylene diamine tetra (methylene phosphonate) and hydroxy-ethylene 1,1 diphosphonate.
Other suitable heavy metal ion sequestrant for use herein include nitrilotriacetic acid and polyaminocarboxylic acids such as ethylenediaminotetracetic acid, ethylenetriamine pentacetic acid, ethylenediamine disuccinic acid, ethylenediamine diglutaric acid, 2-hydroxypropylenediamine disuccinic acid or any salts thereof.
Especially preferred is ethylenediamine-N,N'-disuccinic acid (EDDS) or the alkali metal, alkaline 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 diacetic 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 (3 -alanine-N,N'-diacetic acid, aspartic acid-N,N'-diacetic acid, aspariic acid-N-monoacetic acid and irninodisuccinic 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), ethylenediamine-N-N'-diglutaric acid (EDDG) and 2-hydroxypropylenediamine-N-N'-disuccinic acid (HPDDS) are also suitable.
En~me 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 alkaline proteases, esterases, cellulases, pectinases, lactases and peroxidases conventionally incorporated imo detergent compositions.
Suitable enzymes are discussed in US Patents 3,519,570 and 3,533,139.
Preferred commercially available protease enzymes include those sold under the trademarks Alcalase, Savinase, Primase, Dwazym, and Esperase by Novo Industries A/S (Denmark), those sold under the trademarks Maxatase, Maxacal and Maxapem by Gist-Brocades, those sold by Genencor International, and those sold under the trademarks 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 trademark Rapidase by Gist-Brocades, and those sold under thetrademarksTermamyl and HAN
by Novo Industries A/S. Amylase enzyme may be incorporated into the composition 3z 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 of from 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 obtained, for example, from a lipase producing strain of Humicola sp., Thermomyce~ sp. or Pseudomonas sp.
including Pseudomonas pseudoalcali enes or Pseudomas fluorescens. Lipase from chemically or genetically modified mutants of these strains are also useful herein. A
preferred lipase is derived from Pseudomonas pseudoalcaliRenes, which is described in Granted European Patent, EP-B-0218272.
Another preferred lipase herein is obtained by cloning the gene from Humicola lanueinosa and expressing the gene in Asner ~g'llus 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 mark Lipolase. This lipase is also described in U.S. Patent 4,810,414, Huge-Jensen et al, issued March 7, 1989.
Organic polymeric compound Organic polymeric compounds are preferred 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 particulate 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 flocculating agents herein.
Organic polymeric compound is typically incorporated in the detergent compositions of the invention at a leve) of from 0.1 % to 30%, preferably 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 malefic 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.
Terpoiymers containing monomer units selected from malefic acid, acrylic acid, polyaspartic acid and vinyl alcohol, particularly those having an average molecular weight of from 5,000 to 10,000, are also suitable herein.
Other organic polymeric compounds suitable for incorporation in the 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.
Another organic compound, which is a preferred clay dispersant/ anti-redeposition agent, for use herein, can be the ethoxylated cationic monoamines and diamines of the formula:
~ H3 ~ H3 X-f-OCH2CH2)n- i +-CH2-CH2-~CH2)a b ~ + CH2CH20 )n X
(CH2CH20 -j~ X (CH2CH20 ~ X
wherein X is a nonionic group selected from the group consisting of H, C 1-C4 alkyl or hydroxyalkyl ester or ether groups, and mixtures thereof, a is from 0 to 20, preferably from 0 to 4 (e.g. ethylene, propylene, hexamethylene) b is 1 or 0;
for cationic monoamines (b=0), n is at least 16, with a typical range of from 20 to 35; for cationic diamines (b=1), n is at least about 12 with a typical range of from about 12 to about 42.
Other dispersants/ anti-redeposition agents for use herein are described in EP-B-011965 and US 4,659,802 and US 4,664,848.
Suds suppressing system The detergent compositions of the invention, when formulated for use in machine 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 industry, encompasses a variety of relatively high molecular weight polymers containing siloxane units and hydrocarbyl group of various types. Preferred silicone antifoam compounds are the siloxanes, particularly the polydimethylsiloxanes having trimethylsilyl end blocking units.
Other suitable antifoam compounds include the monocarboxylic fatty acids and soluble salts thereof. These materials are described in US Patent 2,954,347, issued September 27, 1960 to Wayne St. John. The monocarboxylic fatty acids, and salts thereof, for use as suds suppressor typically have hydrocarbyl chains of 10 to 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 5 esters (e.g. fatty acid triglycerides), fatty acid esters of monovalent alcohols, aliphatic C 1 g-C40 ketones (e.g. stearone) N-alkylated amino triazines such as tri- to hexa-alkylmelamines or di- to tetra alkyldiamine chlortriazines formed as products of cyanuric chloride with two or three moles of a primary or secondary amine containing 1 to 24 carbon atoms, propylene oxide, bis stearic acid amide and monostearyl di-10 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 15 a silicone antifoam compound comprising in combination (i) polydimethyl silvxane, at a level of from 50% to 99%, preferably 75%
to 95% by weight of the silicone antifoam compound; and 20 (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 weight; a particularly preferred silicone glycol rake TM
copolymer of this type is DC0544, commercially available from DOW
Corning under the trademark DC0544;
(c) an inert carrier fluid compound, most preferably comprising a C 16-C 18 ethoxylated alcohol with a degree of ethoxylation of from 5 to 50, preferably 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-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 containing 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 containing from 12 to 20 carbon atoms, or a mixture thereof, with a melting point of from 45°C to 80°C.
Cla~softenine system The detergent compositions may contain a clay softening system comprising a clay mineral compound and optionally a clay flocculating 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.
The polymeric dye transfer inhibiting agents are preferably selected from polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinylpyrrolidonepolymers or combinations thereof.
al Polyamine N-oxide polymers Polyamine N-oxide polymers suitable for use herein contain units having the following structure formula T .._.. ... _. w _ (~) Ax R
wherein P is a polymerisable unit, and O O O
A is NC, CO, C, -O-, -S-, -N-; x is O or 1;
R are aliphatic, ethoxylated aliphatics, aromatic, heterocyciic 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:
O

(R1) x _ ~ -(R2)Y
(Rg)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 0 or 1 and wherein the nitrogen of the N-O group can be attached or wherein the nitrogen of the N-O group forms part of these groups. The N-O group can be part of the polymerisable unit (P) or can be attached to the polymeric backbone or a combination of both.
Suitable polyamine N-oxides wherein the N-O group forms part of the polymerisable unit comprise polyamine N-oxides wherein R is selected from aliphatic, aromatic, alicyclic or heterocyclic groups. One class of said polyamine N-oxides comprises the group of polyamine N-oxides wherein the nitrogen of the N-O group forms part of the 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 pyridine, 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~ Cot~olvmers of N-vinvlpyrrolidone 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.
Polyvinylpyrrolidone The detergent compositions herein may also utilize polyvinylpyrroiidone ("PVP") having an average molecular weight of from 2,500 to 400,000. Suitable polyvinylpyrrolidones are commercially available 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 polyvinylpyrroMidones 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) Polvvinxlimidazole 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:
Ri R2 N H H N
N 0>--N O C_C O Ij -~O N
~N H H N
R2 S03M S03M 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 canon such as sodium or potassium.
When in the above formula, R1 is anilino, R2 is N-2-bis-hydroxyethyl and M is a canon 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 trademark Tinopal-UNPA-GX
by Ciba-Geigy Corporation. Tinopal-CTNPA-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-hydroxyethyl-N-methylamino)-s-triazine-2-yl)aminoJ2,2'-stilbenedisulfonic acid disodium salt. This particular brightener species is commercially marketed under the S trademark Tinopal SBM-GX by Ciba-Geigy Corporation.
When in the above formula, R1 is anilino, R2 is morphilino and M is a canon 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 10 commercially marketed under the trademark Tinopal AMS-GX by Ciba Geigy Corporation.
Cationic fabric softening agents 15 Cationic fabric softening agents can also be incorporated into compositions in accordance with the present invention. Suitable cationic fabric softening agents include the water insoluble tertiary amines or dilong chain amide materials as disclosed in GB-A-1 514 276 and EP-B-0 011 340.
20 Cationic fabric softening agents are typically incorporated at total levels of from 0.5%
to 15% by weight, normally from 1 % to 5% by weight.
Other optional ingredients 25 Other optional ingredients suitable for inclusion in the compositions of the invention include perfumes, colours and filler salts, wish 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 10.0, preferably from 10.0 to 12.5, most preferably from 10.5 to 12Ø
Form of the compositions The detergent composition of the invention can be made via a variety of methods, including dry-mixing and agglomerating of the various compounds comprised in the detergent composition. The acidic source of the invention is preferably dry-added.
S The compositions in accordance with 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.
The mean particle size of the base composition of granular compositions in accordance with the invention can be from 0.1 mm to S.0 mm, but it should preferably be such that no more that 5% of particles are greater than 1.7mm in diameter and not more than S% of particles are less than 0.1 Smm in diameter.

The term mean particle size as defined herein is calculated by sieving a sample of the-composition into a number of fractions (typically 5 fractions) on a series of Tyler sieves. The weight fractions thereby obtained are plotted against the aperture size of the sieves. The mean particle size is taken to be the aperture size through which SO%
by weight of the sample would pass.
The bulk density of granular detergent compositions in accordance with the present invention typically have a bulk density of at least S00 g/litre, more preferably from 6S0 g/litre to 1200, more preferably to 8S0 g/litre. Bulk density is measured by means 2S 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 extremity to allow the contents of the funnel to be emptied into an axially aligned cylindrical cup disposed below the funnel.
The funnel is 130 mm high and has internal diameters of 130 mm and 40 mm at its respective upper and lower extremities. It is mounted so that the lower extremity is 140 mm above the upper surface of the base. The cup has an overall height of mm, an internal height of 87 mm and an internal diameter of 84 mm. Its nominal volume is S00 ml.
To carry out a measurement, the funnel is filled with powder by hand pouring, the flap 3S valve is opened and powder allowed to overfill the cup. The filled cup is removed from the frame and excess powder removed from the cup by passing a straight edged implement eg; a knife, across its upper edge. The filled cup is then weighed and the value obtained for the weight of powder doubled to provide a bulk density in g/litre.
Replicate measurements are made as required.
The composition is preferably soluble in cold or cool water, i.e. the composition readily dissolves/disperses in water at a temperature between about 0°C
and 32.2°C, preferably between about 1.6°C and 10°C.
Surfactant aeQlomerate pa,ticles The surfactant system herein is preferably present in granular compositions in the form of surfactant agglomerate particles, which may take the form of flakes, prills, marumes, noodles, 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 site of the resultant agglomerates within specified limits. Such a process involves mixing an effective amount of powder with a high active surfactant paste in one or more agglomerators such as a pan agglomerator, a Z-blade mixer or more preferably an in-line mixer such as those manufactured by Schugi (Holland) BV, 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 Mark).
A high active surfactant paste comprising from 50% by weight to 95% by weight, preferably 70% by weight to 85% by weight of surfactant is typically used. The paste may be pumped into the agglomerator at a temperature high enough to maintain 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.
In an especially preferred embodiment of the present invention, the detergent composition is in the form of powder or a granulate containing more than about 5%
by weight of of the alkali, preferably (bi-)carbonate or percarbonate. The carbonate material is either dry-added or delivered via agglomerates. The addition of the acid, preferably citric acid, (up to 10%) may be introduced into the product as a dry-add, or via a separate particle.

Laundry 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 containing the detergent product is placed inside the drum. At the commencement of the wash cycle of the washing machine water is introduced into the drum and the drum periodically rotates. The design of the dispensing device should be such that it permits containment 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 drum 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 maintained 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 4l -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.
W094/11562.
Especially preferred dispensing devices are disclosed in European Patent Application Publication Nos. 0343069 & 0343070. The latter Application discloses a device comprising a flexible sheath in the form of a bag extending from a support ring defining an orifice, the orifice being adapted to admit to the bag sufficient product for one washing cycle in a washing process. A portion of the washing medium flows through the orifice into the bag, dissolves the product, and the solution then passes outwardly through the orifice into the washing medium. The support ring is provided with a masking arrangemnt to prevent egress of wetted, undissolved, product, this arrangement typically comprising radially extending walls extending from a central boss in a spoked wheel configuration, or a similar structure in which the walls have a helical 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.
Packaeine 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 laminates.

Abbreviations used in following Examples 5 In the detergent compositions, the abbreviated component identifications have the following meanings:
LAS : Sodium linear C 12 alkyl benzene sulfonate TAS . Sodium tallow alkyl sulfate 10 C45AS : Sodium C 14-C 15 linear alkyl sulfate CxyEzS . Sodium C 1 x-C 1 y branched alkyl sulfate condensed with z moles of ethylene oxide C45E7 : A C 14_ 15 Predominantly linear primary alcohol condensed with an average of 7 moles of ethylene oxide 15 C25E3 . A C 12-I S branched primary alcohol ondensed 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 : R 1 COOCH2CH2.N+(CH3 )3 with R 1 = C

20 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 : C 16-C 18 alkyl N-methyl glucamide TPKFA : C 12-C 14 topped whole cut fatty acids 25 STPP . Anhydrous sodium tripolyphosphate Zeolite A : Hydrated Sodium Aiuminosilicate of formula Nal2(A102Si02)12~ 2~H20 having a primary particle size in the range from 0.1 to 10 micrometers NaSKS-6 : Crystalline layered silicate of formula 30 8 -Na2Si205 Citric acid : Anhydrous citric acid Carbonate : Anhydrous sodium carbonate with a particle size between 200 p,m and 900pm Bicarbonate : Anhydrous sodium bicarbonate with a particle size 35 distribution between 400p,m and 1200pm Silicate : Amorphous Sodium Silicate (Si02:Na20;
2.0 ratio) ' 46 Sodium sulfate : Anhydrous sodium sulfate Citrate : Tri-sodium citrate dihydrate of activity 86.4%
with a particle size distribution between 425pm and 850pm MAIAA . Copolymer of 1:4 maleic/acrylic acid, average molecular weight about 70,000.

CMC : Sodium carboxymethyl ceilulose ' Protease : Proteolytic enzyme of activity 4KNPU/g sold by NOVO

Industries A/S under the trademark Savinase Alcalase . Proteolytic enzyme of activity 3AU/g sold by NOVO

Industries A/S

Cellulase . Cellulytic enzyme of activity 1000 CEVU/g sold by NOVO Industries A/S under the trademarkCarezyme ~Yl~e : Amylolytic enzyme of activity 60KNU/g sold by NOVO

Industries A/S under the trademark Termamyl 60T

Lipase : Lipolytic enzyme of activity 1 OOkLU/g sold by NOVO Industries A/S under the trademark Lipolase Endolase : Endoglunase enzyme of activity 3000 CEVU/g sold by NOVO Industries A/S

PB4 : Sodium perborate tetrahydsate of nominal formula NaB02.3H20.H202 PB 1 : Anhydrous sodium perborate monohydrate bleach of nominal formula NaB02.H202 Percarbonate . Sodium Percarbonate of nominal formula 2Na2C03.3H202 NOBS : Nonanoyloxybenzene sulfonate in the form of the sodium salt.

TAED . Tetraacetylethylenediamine DTPMP : Diethylene triamine penta (methylene phosphonate), marketed by Monsanto under the Trade mark bequest 2060 Photoactivated : Sulfonated Zinc Phthlocyanine encapsulated in bleach dextrin soluble polymer Hrightener 1 : Disodium 4,4'-bis(2-sulphostyryl)biphenyl Brightener 2 : Disodium 4,4'-bis(4-anilino-6-morpholino-1.3.5-triazin-2-yl)amino) stilbene-2:2'-disulfonate.

HEDP : l , l -hydroxyethane diphosphonic acid PVNO : Polyvinylpyridine N-oxide PVPVI : Copolymer of polyvinylpyrolidone and vinylimidazole SRP 1 : Sulfobenzoyl end capped esters with oxyethylene oxy and terephtaloyl backbone SRP 2 : Diethoxylated poly (1, 2 propylene terephthalate) 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.

Alkalinity : % weight equivalent of NaOI-I, as obtained using the alkalinity release test method described herein.

In the following Examples all levels are quoted as % by weight of the composition:

Example 1 The following granular laundry detergent compositions A , B, C and D of bulk density 650 g/litre were prepared in accord with the invention:
A B C D

LAS 5.61 4.76 7.5 8.5 TAS 1.86 1.57 3.5 1.4 C45AS 2.24 3.89 2.2 3.5 C25AE3S 0.76 1.18 1.1 1.1 C45E7 - 5.0 4.0 -C25E3 5.5 - - 3.0 CEQ 2.0 2.0 - -QAS - _ - 1.0 STPP - _ _ _ Zeolite A 19.5 19.5 19.5 16.5 NaSKS-6/citric acid 10.6 10.6 10.6 I 0.6 (79:21 ) Carbonate 21.4 21.4 16.4 18.2 Bicarbonate 2.0 2.0 2.0 -Silicate - - - 3.0 Sodium sulfate - 14.3 - -PBI 13.7 15.0 14.0 17.5 TAED 3.1 - 4.2 -DETPMP 0.2 0.2 0.2 0.2 HEDP 0.3 0.3 0.3 0.3 Protease 0.85 0.85 0.85 0.85 Lipase 0.15 0.15 0.15 0.15 Cellulase 0.28 0.28 0.28 0.28 Amylase 0.1 0.1 0.1 -.1 MA/AA I .6 1.6 I .6 I .6 CMC 0.4 0.4 0.4 0.4 Photoactivated bleach 27 ppm 27 ppm 27 ppm 27 pp (ppm) Brightener 1 0.19 0.19 0.19 0.19 Brightener 2 0.04 0.04 0.04 0.04 Perfume 0.3 0.3 0.3 0.3 Silicone antifoam 2.4 2.4 2.4 2.4 Citric acid 1.5 3.5 4.0 4.5 Minors/misc to 100%

Example 2 The following detergent formulations, according to the present invention were prepared.
E F G

Blown Powder STPP 14.0 - 14.0 Zeolite A - 20.0 -C45AS 9.0 6.0 8.0 MA/AA 2.0 4.0 2.0 LAS 6.0 8.0 9.0 TAS 2.0 1.0 1.0 CEQ 1.5 3.0 -Silicate 7.0 8.0 8.0 CMC 1.0 1.0 0.5 Brightener 2 0.2 0.2 0.2 Soap 1.0 1.0 1.0 DTPMP 0.4 0.4 0.2 Spray On C45E7 2.5 2.5 2.0 C25E3 2.5 2.5 2.0 Silicone antifoam 0.3 0.3 0.3 Perfume 0.3 0.3 0.3 Dry additives Carbonate 26.0 23.0 25.0 PB 1 18.0 I 8.0 13.5 PB4 - 4.0 -TAED 3.0 3.0 1.0 Photoactivated bleach 0.02 0.02 0.02 Protease 1.0 1.0 1.0 Lipase 0.4 0.4 0.4 Amylase 0.25 0.30 0.15 Dry mixed sodium sulfate3.0 3.0 5.0 Citric acid 2.5 7.0 5.0 Balance (Moisture & 100.0 100.0 100.0 Miscellaneous) Density (g/litre) 630 670 670 Example 3 The following detergent formulations according to the present invention were 5 prepared:
H I

Blown Powder Zeolite A 15.0 -Sodium sulfate 5.0 -LAS 3.0 -QAS 0.5 1.0 DTPMP 0.4 CMC 0.4 -MA/AA 4.0 -Agglomerates C45AS - 11.0 LAS 6.0 -_.__ _ _ __._,~ ___. __ ___ r $1 TAS 3.0 -Silicate 4.0 Zeolite A 10.0 13.0 CMC - 0.5 M~~ - 2.0 Carbonate 9.0 7.0 PB 1 18.5 -PB4 - 20.0 TAED 4.5 5.5 Spray On Perfume 0.3 0.5 C45E7 4.0 4.0 C25E3 2.0 2.0 Dry additives MA/AA - 3.0 NaSKS-6 - 12.0 Citric acid 5.0 3.0 Citrate 10.0 8.0 Bicarbonate 7.0 5.0 Carbonate 8.0 7.0 PVPVI/PVNO 0.5 0.5 Alcalase 0.5 0.9 Lipase 0.4 0.4 Amylase 0.6 0.6 Cellulase 0.6 0.6 Silicone antifoam 5.0 5.0 Dry additives Sodium sulfate 0.0 0.0 Balance (Moisture and Miscellaneous)100.0 100.0 Density (g/litre) 700 700 Example 4 The following detergent formulations, according to the present invention were prepared:

J K L M

LAS 12.0 12.0 12.0 10.0 QAS 0.7 1.0 - 0.7 TFAA - 1.0 - -C25E5/C45E7 - 2.0 - 0.5 C45E3S - 2.5 - -CEQ - - 1.0 1.0 STPP 30.0 18.0 15.0 -Silicate 9.0 7.0 10.0 -Carbonate 15.0 10.5 15.0 25.0 Bicarbonate - 10.5 DTPMP 0.7 1.0 - -SRP 1 0.3 0.2 - 0.1 MA/AA 2.0 1.5 2.0 1.0 CMC 0.8 0.4 0.4 0.2 Protease 0.8 1.0 0.5 0.5 Amylase 0.8 0.4 - 0.25 Lipase 0.2 0.1 0.2 0.1 Cellulase 0.15 0.05 - -Photoactivated 70ppm 45ppm - lOppm bleach (ppm) Brightener 1 0.2 0.2 0.08 0.2 PB 1 8.0 17.0 - -NOBS 2.0 1.0 - -TAED - - 4.0 5.2 PB4 10.0 - 15.5 7.5 Citric acid 3.5 5.0 3.0 7.0 Balance (Moisture100 100 100 100 and Miscellaneous) Example 5 The following high density and bleach-containing detergent formulations, according to the present invention were prepared:
T..__..__.____ . . __..._. _.~ _.. ...._.~..._ _...._.._... ___..~~~.. _...

N O P

Blown Powder Zeolite A 10.0 15.0 6.0 Sodium sulfate 19.0 5.0 7.0 MA/AA 3.0 3.0 6.0 LAS 10.0 8.0 10.0 C45AS 4.0 5.0 7.0 QAS 0.5 1.0 -Silicate - 1.0 7.0 Soap - - 2.0 Brightener 1 0.2 0.2 0.2 Carbonate 28.0 26.0 20.0 DTPMP - 0.4 0.4 Spray On C45E7 1.0 1.0 1.0 Dry additives PVPVI/PVNO 0.5 0.5 0.5 Protease 1.0 1.0 1.0 Lipase 0.4 0.4 0.4 Amylase 0.1 0.1 0.1 Cellulase 0.1 0.1 0.1 NOBS - 6.1 4.5 PB l 17.0 15.0 16.0 Sodium sulfate - 6.0 -Citric acid 2.5 3.5 4.5 Balance (Moisture 100 100 100 and Miscellaneous) Example 6 The following detergent formulations, according to the present invention were prepared:

Q R

Blown Powder Zeolite A 15.0 15.0 Sodim sulfate 0.0 0.0 LAS 3.0 3.0 QAS - 1.5 QAS 0.5 -DTPMP 0.4 0.4 CMC 0.4 0.4 MA/AA 4.0 2.0 Agglomerates LAS 4.0 4.0 TAS 2.0 1.0 Silicate 3.0 4.0 Zeolite A 8.0 8.0 Carbonate 8.0 6.0 Spray On Perfume 0.3 0.3 C45E7 2.0 2.0 C25E3 2.0 -Dry additives Citric acid 2.0 5.5 Citrate 5.0 2.0 Bicarbonate - -Carbonate 8.0 10.0 TAED 6.0 5.0 PB4 - 9.0 PB 1 15.5 10.0 Polyethylene oxide of MW - 0.2 5,000,000 Bentonite clay - 10.0 Protease 1.0 1.0 Lipase 0.4 0.4 Amylase 0.6 0.6 Cellulase 0.6 0.6 _ _ .___ _____ Silicone antifoam 5.0 5.0 Dry additives Sodium sulfate 10.0 0,0 Balance (Moisture and 100.0 100.0 Miscellaneous) Example 7 The following detergent formulations, according to the present invention were 5 prepared:
S T

Agglomerate C45AS 11.0 14.0 ZeoIite A 15.0 6.0 Carbonate 4.0 8.0 MA/AA 4.0 2.0 CMC 0.5 0.5 DTPMP 0.4 0.4 Spray On C25E5 5.0 5.0 Perfume 0.5 0.5 Dry Adds Citric acid 4.5 3.0 HEDP 0.5 0.3 Carbonate i 0.0 -SKS 6 10.0 13.0 Citrate 3.0 1.0 TAED 5.0 7.0 PB 1 20.0 20.0 SRP I 0.3 0.3 Protease 1.4 1.4 Lipase 0.4 0.4 WO 98!04668 PCT/US97/12963 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 -Balance (Moisture and 100 100 Miscellaneous)

Claims (14)

Claims:

1. A detergent composition comprising an anionic surfactant, perborate bleach at a level of at least 13% of a perborate component, by weight of the composition, citric acid and an alkali source wherein said citric acid and alkali source are capable of reacting together in the presence of water to produce a gas and a cationic C6-C18 N-alkyl or alkenyl mono- or bis-alkoxylated amine surfactant wherein the weight-ratio of anionic surfactant to cationic surfactant is from 15:1 to 1:1.

2. A detergent composition according to claim 1 where the cationic surfactant is present at a level of from 0.4% to 12% by weight of the composition.

3. A detergent composition according to claim 1 wherein the acid has a particle size of about 710 microns or less.

4. A detergent composition according to claim 1 wherein said perborate component is in the form of a monohydrate.

5. A detergent composition according to claim 1 wherein said perborate component is in the form of a tetrahydrate.

6. A detergent composition according to claim 1 where said anionic surfactant is a linear or branched C10-C18 alkyl sulfate surfactant.

7. A detergent composition according to claim 1 further comprising a nonionic alkoxylated surfactant.

8. A detergent composition according to claim 1 where the anionic surfactant is present at a level of 5% to 35% by weight of the composition.

9. A detergent composition according to claim 1 wherein the alkali source comprises an alkaline salt selected from an alkali metal or alkaline earth metal carbonate, bicarbonate or sesqui-carbonate.

10. A detergent composition according to claim 1 wherein the alkali source is present in an amount of from about 2% to about 75% by weight of the composition.

11. A detergent composition according to any one of claims 1 to 10 wherein the alkali source is present in an amount of from about 10% to about 30% by weight of the composition.

12. A detergent composition according to claim 1 wherein one or more bleach activators are present.

13. A detergent composition according to claim 12 wherein said bleach activator is tetraacetylethylenediamine (TAED).

14. A detergent composition according to claim 12 wherein said bleach activator is a hydrophobic bleach activator.