Detergent particle

Technical Field

The present invention relates to a particle containing cationic compounds with particulate/ clay-soil removal/anti-redeposition properties and a carrier material, for use in detergent compositions or components thereof and a process for making the particle.

Background to the Invention

A particularly important property of a detergent composition is its ability to remove particulate type soils from a variety of fabrics during laundering. Perhaps the most important particulate soils are the clay-type soils. Clay soil particles generally comprise negatively charged layers of aluminosilicates and positively charged cations (e.g. calcium) which are positioned between and hold together the negatively charged layers.

in addition to clay soil removal, there is a need to keep the removed soil in suspension during the laundering (or dish washing) cycle. Soil which is removed from the fabric and suspended in the wash water can redeposit on the surface of the fabric. This redeposited soil causes a dulling or "greying" effect which is especially noticeable on white fabrics. To minimise this problem, anti-redeposition agents can be included in the detergent composition.

For example EP-B-1 1 1 965 discloses the use in detergents of cationic compounds, which have both clay-soil removal and anti-redeposition properties.

US 4.659,802 and US 4,664,848 describe quaternized amines which have clay-soil removal and anti-redeposition properties and which can be used in combination with anionic surfactants.

The prior art teaches that these cationic compounds can be introduced into a detergent composition via an aqueous slurry, whereafter the product is atomised and spray dried.

However, it has been found that the incorporation of the above described cationic compound in granular detergent compositions or components thereof as described in the prior art may result in problems such as malodour to the final detergent and discolouration of the (white) final detergent.

The Applicants have now found that these problems can be ameliorated by the use of a carefully chosen ratio of cationic compound to carrier material, or when a specific carrier material absorbs or encapsulates the cationic. (partially) quaternized ethoxylated (poly) amines (which have clay-soil removal/anti-redeposition properties). The present invention therefor provides a particle in which the cationic compound is absorbed or bound or encapsulated in such a way that the particle formed is water-soluble, flowable and (temperature-) stable, and has an acceptable odour and colour in the final detergent.

Another advantage of the carrier materials used herein is that they also have detergent properties, such as builder capacities.

Particles produced according to the preferred process for making the particle are found to be very effective, having particularly good flowability, stability and solubility, whilst overcoming malodour and discolouration problems.

Detergent compositions or components thereof, containing this particle, are also envisaged herein.

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

Summary of the Invention

The present invention relates to a particle comprising one or more cationic compounds, which are cationic, (partially) quaternized ethoxylated (poly) amine compounds with particulate/ clay-soil removal / anti-redeposition properties, and a carrier material and optionally other material. Furthermore the present invention relates to a process for making this particle and the use thereof in detergent compositions or components thereof.

In more detail, the present invention relates to a particle comprising

(a) a water-soluble cationic compound having clay soil removal/anti- redeposition properties, which is selected from the group consisting of:

1 ) ethoxylated cationic monoamines having the formula:

R ²

R ² — N ⁺ — L — X

R ²

2) ethoxylated cationic diamines having the formula:

wherein M* is an N+ or N group; each M2 is an N+ or N group, and at least one M is an N+ group;

3) ethoxylated cationic polyamines having the formula:

(R ³ ) _d

4) mixtures thereof;

O O 0 O O wherein A ¹ is— C — , — CO— , — NCN — , — CN — , — OCN— , R R R R R R

O O O O O CO— , — OCX)— , — OC— , CNC — or O— ,

R

R is H or C1 -C4 alkyl or hydroxyalkyl, R is C2-C12 alkylene, hydroxyalkylene, alkenylene, arylene or alkarylene, or a C2- 3 oxyalkylene moiety having from 2 to about 20 oxyalkylene units provided that no O-N bonds are formed; each R^ is C\ - CΔ alkyl or hydroxyalkyl, the moiety -L-X, or two R^ together form the moiety - (CH2) _r -A2-(CH2).y-, wherein A^ is -O- or -CH2-, r is 1 or 2, s is 1 or 2 and r + s is 3 or 4; each R^ is Cj-Cg alkyl or hydroxyalkyl, benzyl, the moiety L-X, or two R- or one R2 and one R^ together form the moiety -(CH2) _r -A2-(CH2),s-; R^ is a substituted C3-C12 alkyl, hydroxyalkyl, alkenyl, aryl or alkaryl group having p substitution sites; R^ is C1-C12 alkenyl, hydroxyalkylene, alkenylene, arylene or alkarylene, or a C2-C3 oxyalkylene moiety having from 2 to about 20 oxyalkylene units provided that no O-O or O-N bonds are formed; X is a nonionic group selected from the group consisting of H, C1-C4 alkyl or hydroxyalkyl ester or ether groups, and mixtures thereof; L is a hydrophilic chain which contains the polyoxyalkylene moiety

-[(R ⁶ O) (CH2CH2O)„> wherein R ⁶ is C3-C4 alkylene or hydroxyalkylene and m and n are numbers such that the moiety -(CH2CH2θ) _rt - comprises at least about 50% by weight of said polyoxyalkylene moiety; d is 1 when M^ is N+ and is 0 when M^ is N; n is at least about 16 for said cationic monoamines, is at least about 6 for said cationic diamines and is at least about 3 for said cationic polyamines; p is from 3 to 8; q is 1 or 0; t is 1 or 0, provided that t is 1 when q is l;and

(b) a powdered carrier material, wherein the ratio of (a) to (b) is from 1 : 15 to 4:1 by weight.

The invention also relates to a particle comprising:

(a) a water-soluble cationic compound having clay soil removal/anti- redeposition properties, selected from the compounds mentioned in (a) above; and

(b) an aluminosilicate carrier material.

Detailed description of the invention

The particle

In a first aspect of the present invention, the particle of the present invention comprises a water-soluble cationic compound and one or more powdered carrier materials, present in a ratio from 1 : 15 to 4: 1 by weight, more preferably from 1 :7 to 1 :1, most preferably from 1 :4 to 1 : 1.5 by weight. In a second aspect, the present invention provides a particle comprising a water-soluble cationic compound and one or more aluminosilicate carrier materials.

Optionally other detergent ingredients can be present in the particle, preferably anionic surfactants and/ or polyethylene glycols (as described herein).

The particle size of the particles in accord with the present invention should preferably be such that no more of than 15% of the particles are greater than 1.8mm in diameter and no more than 15% of the particles are smaller than 0.25mm in diameter. Preferably the mean particle size is such that 10% to 50% of the particles has a particle size of from 0.2mm to 0.7mm 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 sieves, preferably Tyler sieves. The weight fractions thereby obtained are plotted against the

aperture size of the sieves. The mean particle size is taken to be the aperture size through which 50% by weight of the sample would pass.

Cationic compound

An essential feature of the present invention is a water-soluble cationic compound which has particulate/ clay-soil removal/anti-redeposition properties and which is selected from the group consisting of cationic mono- di- and polyamines.

In the particle in accord with the present invention the ratio of cationic compound to the powdered carrier material and preferably to the aluminosilicate carrier material is from 1 :15 to 4: 1 by weight, more preferably from 1 :7 to 1 :1, most preferably from 1 :4 to 1 : 1.5 by weight.

If the particle in accord with the invention is present in a detergent composition, the water-soluble cationic compound is preferably present in the detergent composition at a level of from 0.01% to 30%, more preferably from 0.1% to 15% , most preferably from 0.2% to 3.0% by weight of the detergent composition.

If the cationic compound does not have a desirable colour, particularly when the compound is not white, the cationic compound can be discoloured before incorporation in the particle of the invention by any standard method.

Cationic amines

The water-soluble cationic compounds of the present invention, which are useful in granular detergent compositions or components thereof, include ethoxylated cationic monoamines, ethoxylated cationic diamines and ethoxylated cationic polyamines as previously defined.

In the preceding formulae for the cationic amines, R^ can be branched

(e-g-

CH,

cyclic (e.g.

or most preferably linear

(e.g. — CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ — )

alkylene, hydroxyalkylene, alkenylene, alkarylene or oxyalkylene. Rl is preferably C2-C( _j alkylene for the ethoxylated cationic diamines. Each R^ is preferably methyl or the moiety -L-X; each R^ is preferably C \ -C4 alkyl or hydroxyalkyl, and most preferably methyl.

The positive charge of the N+ groups is offset by the appropriate number of counter anions. Suitable counter anions include C1-, Br-, SO3-2, PO4-2, MeOSO3- and the like. Particularly preferred counter anions are Cl- and Br-.

X can be a non-ionic group selected from hydrogen (H), C1-C4 alkyl or hydroxyalkyl ester or ether groups, or mixtures thereof. Preferred esters or ethers are the acetate ester and methyl ether, respectively. The particularly preferred nonionic groups are H and the methyl ether.

In the preceding formulae, hydrophilic chain L usually consists entirely of the polyoxyalkylene moiety -[(R ⁶ O) (CH2CH2.O„ ]. The moieties -(R ⁶ O)m- and - (CH2CH2θ)n- of the polyoxyalkylene moiety can be mixed together or preferably form blocks of -(R θ) _m - and -(CH2CH2θ) _n - moieties. R*> is preferably C3H6 (propylene); m

is preferably from 0 to about 5 and is most preferably 0, i.e. the polyoxyalkylene moiety consists entirely of the moiety -(CH2CH2O) _n -. The moiety -(CH2CH2θ) _π - preferably comprises at least about 85% by weight of the polyoxyalkylene moiety and most preferably 100% by weight (m is O).

In the preceding formulas, M 1 and each M^ are preferably an N+ group for the cationic diamines and polyamines.

Preferred ethoxylated cationic monoamines and diamines have the formula:

wherein X and n are defined as before, a is from 0 to 20, preferably from 0 to 4 (e.g. ethylene, propylene, hexamethylene) b is 1 or 0. For preferred cationic monoamines (b=0), n is preferably at least about 16, with a typical range of from about 20 to about 35. For preferred cationic diamines (b=l), n is at least about 12 with a typical range of from about 12 to about 42.

In the preceding formula for the ethoxylated cationic polyamines, R4 (linear, branched, or cyclic) is preferably a substituted C3-C6 alkyl, hydroxyalkyl or aryl group; Al is preferably

O

CN — ;

H

n is preferably at least about 12, with a typical range of from about 12 to about 42; p is preferably from 3 to 6. When R^ is a substituted aryl or alkaryl group, q is preferably 1 and R^ is preferably C2-C alkylene. When R^ is a substituted alkyl,

hydroxyalkyl, or alkenyl group, and when q is 0, R^ is preferably a C2-C3 oxyalkylene moiety; when q is 1 , R^ is preferably C2-C3 alkylene.

These ethoxylated cationic polyamines can be derived from polyamino amides such as:

These ethoxylated cationic polyamines can also be derived from polyaminopropyleneoxide derivatives such as:

CH ₃ - (OC ₃ H ₆ ) _c — NH ₂

wherein each c is a number from 2 to about 20.

Carrier material

Another essential component of the particle of the present invention is one or more powdered carrier materials.

In the particle in accord with the first aspect of the present invention the ratio of cationic compound to the powdered carrier material and preferably to the aluminosilicate carrier material is from 1 :15 to 2:1 by weight, more preferably from 1 :7 to 1 : 1 , most preferably from 1 :4 to 1 : 1.5 by weight.

The carrier material will preferably be a white, free-flowing material with a low water content, preferably less than 25%. more preferably less than 15%, most preferably less than 10% by weight of the carrier material.

The carrier material preferably has a porous or crystalline structure, providing thus a carrier material with a high surface area for a better interaction with the water-soluble cationic compound (and optionally other detergent ingredients).

Preferred carrier materials are certain inorganic and organic powders or salts, more preferably certain water-soluble and partially or largely water insoluble builder materials.

Suitable organic powders include alkyl or alkylene sulphates, borates or phosphates, preferably alkyl sulphates.

Preferred inorganic powdered carrier materials include carbonates, bicarbonates. silicates, sulphates and phosphates.

Suitable water-soluble builder materials include the water soluble monomeric polycarboxylates, or their acid forms.

A highly preferred carrier material is citrate or citric acid.

Other highly preferred examples of carrier materials which are largely water insoluble builder materials and which are essential in the second aspect of the invention, include the aluminosilicates, preferably sodium aluminosilicates. Zeolites are highly preferred.

Suitable aluminosilicate zeolites have the unit cell formula Na _z [(AlO2) _z (SiO2)y]- xH _? O 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 such that no more than 25%, more preferably no more than 10%. most preferably no more than 5% structure bound water is present, by weight of the aluminosilicate zeolite.

The aluminosilicate zeolites can be naturally occurring materials, but are preferably synthetically derived. Synthetic crystalline aluminosilicate ion exchange materials for use herein are available under the designations Zeolite A, Zeolite B, Zeolite P, Zeolite X, Zeolite HS and mixtures thereof.

Another preferred aluminosilicate zeolite carrier material is zeolite MAP builder.

Zeolite MAP is described in EP 384070A (Unilever). It is defined as an alkali metal alumino-silicate of the zeolite P type having a silicon to aluminium ratio not greater than 1.33, preferably within the range from 0.9 to 1.33 and more preferably within the range of from 0.9 to 1.2.

Of particular interest is zeolite MAP having a silicon to aluminium ratio not greater than 1.15 and, more particularly, not greater than 1.07.

In a preferred aspect the alumino silicates, especially zeolite MAP, have a particle size, expressed as a d5Q value of from 1.0 to 10.0 micrometres, more preferably from 2.0 to 7.0 micrometres, most preferably from 2.5 to 5.0 micrometres.

The d5o value indicates that 50% by weight of the particles have a diameter smaller than that figure. The particle size may, in particular be determined by conventional analytical techniques such as microscopic determination using a scanning electron microscope or by means of a laser granulometer. Other methods of establishing d50 values are disclosed in EP 384070A.

The carrier material comprised in the particle of the present invention can comprise a single carrier material. Preferred carrier materials are mentioned above. Alumino

silicate materials are particularly preferred. Preferably one of the preferred carrier materials forms at least 50%, more preferably more than 70%, most preferably more than 80% by weight of the carrier material in the particle.

Process for making of a particle

The particle can be made by mixing or spray drying of the carrier material and cationic compound, and optionally other ingredients.

In a preferred aspect, the cationic compound is purified before formation of the particle. A particularly preferred purification step can be the removal from the cationic compound of volatile compounds which can cause a malodour. by use of a steam stripping process, whereafter the cationic compound can be incorporated in a particle in accord with the present invention. An example is disclosed in EP 1 1 1 965A.

Preferably, the particle of the present invention is made via an agglomeration process.

This preferred agglomeration process comprises the following steps:

(a) heating of the water-soluble cationic compound to obtain a melted compound;

(b) agglomerating the melted compound of (a) with the carrier material to a agglomerate particle;

(c) cooling the agglomerate particle of (b).

Suitable agglomeration techniques used for step (B) are described in more detail in the Applicants co-pending European Application EP-A-643130. In a highly preferred agglomeration process the melted compound of the present invention is intimately mixed with the powdered carrier material in a high shear mixer, such as a Loedige® CB unit. The agglomerate particles may be finished in further mixing units, such as a Loedige® KM, or a fluidised bed.

In step (c) the agglomerate particles are preferably cooled in a fluidised bed cooler by passing cool air.

Additionally, more than one carrier materials can be added in step (b).

Optional detergent ingredients can also be added in step (b). However, preferably optional detergent ingredients are added to the melted compound before step (b).

Optionally, in step (c) the agglomerate particle is dried before cooled, preferably by use of a fluid bed dryer by passing hot air.

Another technique for obtaining the particle of the present invention is by use of spray drying techniques. Suitable techniques for spraying the melted compound onto powdered carrier material(s) are described in the Applicants co-pending Patent Application WO9405761, published on 17th March 1994.

Optional ingredients in the particle

Optional ingredients can be comprised in the particle of the present invention, which can be selected from the additional detergent components described hereinafter. When comprised in the particle they are preferably present at a level of :rom 0.05% to 30%, more preferably from 0.5% to 20%, most preferably from 1.0% to 15% by weight of the particle.

Preferred optional detergent ingredients present in the particle of the present invention are anionic surfactants, preferably alkyl sulphates, alkyl benzene sulphonates or alkyl sulphates condensed with ethylene oxide and polyethylene glycols, preferably with a molecular weight of from 5000 to 10000.

Another preferred ingredient in the particles of the present invention is a cationic polymers, which has clay-soil removal/ anti-redeposition properties, as described in the next paragraph.

Detergent compositions or components thereof

The particle of the present invention can be incorporated in detergent compositions (or be combined with components thereof).

If the particle in accord with the invention is present in a detergent composition thereof, this will be done in such a manner that the water-soluble cationic compound is preferably present in the detergent composition at a level of from 0.01% to 30%, more preferably from 0.1% to 15% , most preferably from 0.2% to 3.0% by weight of the detergent composition.

The precise nature of the additional detergent ingredients (some of which can also be comprised in the particle of the present invention as optional ingredient) of these detergent compositions or components thereof, and levels of incorporation thereof will depend on the physical form of the composition or component thereof, and the precise nature of the washing operation for which it is to be used.

The detergent compositions or components thereof preferably contain one or more additional detergent components selected from (additional) surfactants, (additional) builders, sequestrants, bleach, bleach precursors, bleach catalysts, organic polymeric compounds, additional enzymes, suds suppressors, lime soap dispersants, additional soil suspension and anti-redeposition agents soil releasing agents, perfumes and corrosion inhibitors.

(Additional) Surfactant

The detergent compositions or components thereof preferably contain an (additional) surfactant selected from anionic, nonionic. cationic. ampholytic, amphoteric and zwitterionic surfactants and mixtures thereof.

A typical listing of anionic, nonionic, ampholytic, and zwitterionic classes, and species of these surfactants, is given in U.S. P. 3,929,678 issued to Laughlin and Heuring on December 30, 1975. Further examples are given in "Surface Active Agents and Detergents" (Vol. I and II by Schwartz, Perry and Berch). A list of

suitable cationic surfactants is given in U.S. P. 4,259,217 issued to Murphy on March 31, 1981.

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

Anionic surfactant

The detergent compositions or components thereof preferably comprise an additional anionic surfactant. Essentially any anionic surfactants useful for detersive purposes can be comprised in the detergent composition. These can include salts (including, for example, sodium, potassium, 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 Cp-C, „ monoesters) diesters of sulfosuccinate (especially saturated and unsaturated C^-C , . diesters), N-acyl sarcosinates. Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tallow oil.

Anionic 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 C5-C]7 acyl-N-(Cι -C4 alkyl) and -N-(Cj-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 C i o- 18 alkyl sulfates, more preferably the C i \ -C \ 5 branched chain alkyl sulfates and the C \ 2-C ] 4 linear chain alkyl sulfates.

Alkyl ethoxysulfate surfactants are preferably selected from the group consisting of the Cio-C _j 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 _{j }} -C i g, most preferably C \ \ -C \ 5 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 C5-C20 linear alkylbenzene sulfonates, alkyl ester suifonates, C5-C22 primary or secondary alkane sulfonates, Cg-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(CH2CH2θ) _x CFbCOO'M ^" wherein R is a Cg to Cjg 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-(CHRj-CHR2-O)-R3 wherein R is a Cg to C jg alkyl group, x is from 1 to 25, K\ 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-l-octanoic acid and 2-pentyl-l-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 (Ri) CH2 COOM, wherein R is a C5-CJ 7 linear or branched alkyl or alkenyl group, Ri is a C1-C4 alkyl group and M is an alkali metal ion. Preferred examples are the myristyl and oleoyl methyl sarcosinates in the form of their sodium salts.

Alkoxylated nonionic surfactant

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

Preferred alkoxylated surfactants can be selected from the classes of the nonionic condensates of alkyl phenols, nonionic ethoxylated alcohols, nonionic ethoxylated/propoxylated fatty alcohols, nonionic ethoxy late/propoxy late 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 polyhvdroxy fatty acid amide surfactant

Polyhydroxy fatty acid amides suitable for use herein are those having the structural formula R ² CONR ¹ Z wherein : RI is H, C1-C4 hydrocarbyl. 2-hydroxy ethyl, 2- hydroxy propyl, ethoxy, propoxy, or a mixture thereof, preferable C1-C4 alkyl, more preferably C\ or C2 alkyl, most preferably Ci alkyl (i.e., methyl); and R2 is a C5- C31 hydrocarbyl, preferably straight-chain C5-C 19 alkyl or alkenyl, more preferably straight-chain C9-C \η alkyl or alkenyl, most preferably straight-chain C\ j-C 57 alkyl or alkenyl, or mixture thereof; and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof. Z preferably will be derived from a reducing sugar in a reductive amination reaction: more preferably Z is a glycityl.

Nonionic fattv acid amide surfactant

Suitable fatty acid amide surfactants include those having the formula: R^CON(R^)2 wherein R^ is an alkyl group containing from 7 to 21, preferably from 9 to 17 carbon atoms and each R^ is selected from the group consisting of hydrogen, C]-C4 alkyl, C1-C4 hydroxyalkyl, and -(C2H4θ) _x H, where x is in the range of from 1 to 3.

Nonionic alkylpolysaccharide surfactant

Suitable alkylpolysaccharides for use herein are disclosed in U.S. Patent 4,565.647, Llenado, issued January 21, 1986, having a hydrophobic group containing from 6 to 30 carbon atoms and a polysaccharide, e.g., a polyglycoside, hydrophilic group containing from 1.3 to 10 saccharide units.

Preferred alkylpolyglycosides have the formula

R2θ(C _n H _2n O)t(glycosyl) _x

wherein R ² is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups contain from 10

to 18 carbon atoms; n is 2 or 3; t is from 0 to 10, and x is from 1.3 to 8. The glycosyl is preferably derived from glucose.

Amphoteric surfactant

Suitable amphoteric surfactants for use herein include the amine oxide surfactants and the alkyl amphocarboxylic acids.

Suitable amine oxides include those compounds having the formula R3(OR ) _x Nθ(R5)2 wherein R- is selected from an alkyl, hydroxyalkyl, acylamidopropoyl and alkyl phenyl group, or mixtures thereof, containing from 8 to 26 carbon atoms; R^ 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 R5 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 Cio-Cj g alkyl dimethylamine oxide, and CjQ-lg acylamido alkyl dimethylamine oxide.

A suitable example of an alkyl aphodicarboxylic acid is Miranol(TM) C2M Cone, manufactured by Miranol, Inc., Dayton, NJ.

Zwitterionic surfactant

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

Suitable betaines are those compounds having the formula R(R')2N ⁺ R2COO" wherein R is a Cg-Cjg hydrocarbyl group, each R is typically C1-C3 alkyl, and R ² is a C1-C5 hydrocarbyl group. Preferred betaines are C 12- 18 dimethyl-ammonio hexanoate and the C \ Q. \ g acylamidopropane (or ethane) dimethyl (or diethyl) betaines. Complex betaine surfactants are also suitable for use herein.

Cationic surfactants

Suitable cationic surfactants to be used in the detergent compositions or components thereof, herein include the quaternary ammonium surfactants selected from mono Cg-C j 6, preferably Cβ-C ] Q N-alkyl or alkenyl ammonium surfactants wherein the remaining N positions are substituted by methyl, hydroxyethyl or hydroxypropyl groups.

Another suitable group of cationic surfactants which can be used in the detergent compositions or components thereof, for use herein are cationic ester surfactants.

The cationic ester surfactant is a, preferably 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 Nos. 4228042, 4239660 and 4260529.

In one preferred aspect the ester linkage and cationically charged group are separated from each other in the surfactant molecule by a spacer group consisting of a chain comprising at least three atoms (i.e. of three atoms chain length), preferably from three to eight atoms, more preferably from three to five atoms, most preferably three atoms. The atoms forming the spacer group chain are selected from the group consisting of carbon, nitrogen and oxygen atoms and any mixtures thereof, with the proviso that any nitrogen or oxygen atom in said chain connects only with carbon atoms in the chain. Thus spacer groups having, for example, -O-O- (i.e. peroxide), - N-N-. and -N-O- linkages are excluded, whilst spacer groups having, for example - CFb-O- CH2- and -CH2-NH-CH2- linkages are included. In a preferred aspect the spacer group chain comprises only carbon atoms, most preferably the chain is a hydrocarbyl chain.

Cationic polymers

The detergent composition or components thereof can comprise additional polymeric cationic ethoxylated amine compounds with particulate/ clay-soil removal/ anti- redeposition, selected from the group consisting of water-soluble cationic polymers. These polymers comprise a polymer backbone, at least 2M groups and at least on L- X group, wherein M is a cationic group attached to or integral with the backbone; X is a nonionic group selected from the group consisting of H, C\ -CA alkyl or hydroxyalkyl ester or ether groups, and mixtures thereof; and L is a hydrophilic chain connecting groups M and X or connecting X to the polymer backbone.

The polymeric cationic ethoxylated amine compounds can be present in detergent compositions at a level of from 0.01% to 30%, more preferably from 0.1% to 15%, most preferably from 0.2% to 3% by weight of the detergent composition.

As used herein, the term "polymer backbone" refers to the polymeric moiety to which groups M and L-X are attached to or integral with. Included within this term are oligomer backbones (2 to 4 units), and true polymer backbones (5 or more units).

As used herein, the term "attached to " means that the group is pendent from the polymer backbone, examples of which are represented by the following general structures A and B:

L X

I X

B

As used herein, the term "integral with" means that the group forms part of the polymer backbone, examples of which are represented by the following general structures C and D:

M- M

L L

X X

D

Any polymer backbone can be used as long as the cationic polymer formed is water- soluble and has clay soil removal/anti-redeposition properties. Suitable polymer backbones can be derived from the polyurethanes, the polyesters, the polyethers, the polyamides, the polyimides and the like, the polyacrylates, the polyacrylamides, the polyvinylethers, the polyethylenes, the polypropylenes and like polyalkylenes, the polystyrenes and like polyalkarylenes, the polyalkyleneamines, the polyalkyleneimines, the polyvinylamines, the polyalylamines, the polydiallylamines, the polyvinylpyridines, the polyaminotriazoles, polyvinyl alcohol, the aminopolyureylenes, and mixtures thereof.

M can be any compatible cationic group which comprises an N ⁺ (quartemary), positively charged center. The quartemary positively charged center can be represented by the following general structures E and F:

E

Particularly preferred M groups are those containing a quartemary center represented by general structure E. The cationic group is preferably positioned close to or integral with the polymer backbone.

The positive charge of the N ⁺ centres is offset by the appropriate number of counter anions. Suitable counter anions include Cl", Br", SO32-, SO4-", PO42-, MeOSO3" and the like. Particularly preferred counter anions are Cl" and Br.

X can be a nonionic group selected from hydrogen (H), C ] -C4 alkyl or hydroxyalkyl ester or ether groups, and mixtures thereof. The preferred ester or ether groups are the acetate ester and methyl ether, respectively; The particularly preferred nonionic groups are H and the methyl ether.

The cationic polymers suitable for use in granular detergent compositions in accord with the present inventions normally have a ratio of cationic groups M to nonionic groups X of from about 1 : 1 to about 1 :2. However, for example, by appropriate copolymerization of cationic, nonionic (i.e. containing the group L-X), and mixed cationic/nonionic monomers, the ratio of cationic groups M to nonionic groups X can be varied. The ratio of groups M to groups X can usually range from about 2:1 to about 1 :10. In preferred cationic polymers, the ratio is from about 1 : 1 to about 1 :5. The polymers formed from such copolymerization are typically random, i.e. the cationic, nonionic and mixed cationic/nonionic monomers copolymerize in a nonrepeating sequence.

The units which contain groups M and groups L-X can comprise 100% of the cationic polymers of the present invention. However, inclusion of other units (preferably nonionic) in the polymers is also permissible. Examples of other units include acrylamides, vinyl ethers and those containing unquaternized tertiary amine groups (M * ) containing an N centre. These other units can comprise from 0% to about 90% of the polymer (from about 10% to 100% of the polymer being units containing M and L-X groups, including M^-L-X groups). Normally, these other units comprise from 0% to about 50% of the polymer (from about 50% to 100% of the polymer being units containing M and L-X groups).

The number of groups M and L-X each usually ranges from about 2 to about 200. Typically the number of groups M and L-X are each from about 3 to about 100. Preferably, the number of groups M and L-X are each from about 3 to about 40.

Other than moieties for connecting groups M and X, or for attachment to the polymer backbone, hydrophilic chain L usually consists entirely of the polyoxyalkylene moiety -[(RO) _m (CH2 ^c ^2°)n The moieties -(R'O) _TO - and - (CH2CH2θ) _w - of the polyoxyalkylene moiety can be mixed together, or preferably form blocks of -(R'O) - and -(CH2CH2θ) _π - moieties. R' is preferably C3H6 (propylene); m is preferably from 0 to about 5, and most preferably 0; i.e. the polyoxyalkylene moiety consists entirely of the moiety -(CH2CH2O),,-. The moiety -(CH2CH2θ) _n - preferably comprises at least about 85% by weight of the polyoxyalkylene moiety, and most preferably 100% by weight (m is 0). For the moiety -(CH2CH2O)„-, n is usually from about 3 to about 100. Preferably n, is from about 12 to about 42.

A plurality (2 or more) of moieties -L-X can also be hooked together and attached to group M or to the polymer backbone, examples of which are represented by the following general structures G and H:

G H

Structures such as G and H can be formed, for example, by reacting glycidol with group M or with the polymer backbone, and ethoxylating the subsequently formed hydroxy groups.

Representative classes of cationic polymers of the present invention are as follows:

A. Polyurethane, Polyester, Polyether, Polyamide or like Polymers.

One class of suitable cationic polymers are derived from polyurethanes, polyesters, polyethers, polyamides and the like. These polymers comprise units selected from those having formulas I, II and III:

wherein A is

o o o o o

NC — , — CN — , — CO — , — OC — - or — C — ;

R R

X is 0 or 1 ; R is H or C1-C4 alkyl or hydroxyalkyl; Rl is C2-C12 alkylene, hydroxyalkylene, alkenylene, cycloalkylene, arylene or alkarylene, or a C2-C3 oxyalkylene moiety having from 2 to abut 20 oxyalkylene units provided that no O-O or O-N bonds are formed with A^; when x is 1, R ² is -R ⁵ - except when A* is

o

or is -(O 8) _y - or -OR ⁵ - provided that no O-O or N-O bonds are formed with A^ , and R3 is -R ⁵ - except when A^ is

O

— c— ,

or is -(R8θ)-.y or -R ⁵ O- provided that no O-O or O-N bonds are formed with A^ ; when x is 0, R ² is

(OR ⁸ ) _y — , — OR ⁵ — , — COR ⁵ — ,— OCR ⁵ — ,— OCR ⁵

O O O

— NCR ⁵ — ,— NCOR ⁵ — , — CNR ⁵ — , or — OCNR ⁵ — , RO RO OR OR

and R3 is -R ⁵ -; R ^A is C1-C4 alkyl or hydroxyalkyl, or the moiety -(R )fc- [(C3H6θ) _m (CH2CH2θ)„]-X; R ⁵ is C1-C12 alkylene, hydroxyalkylene, alkenylene, arylene, or alkarylene; each R° is C 1 4 alkyl or hydroxyalkyl, or the moiety - (CH ₂ ) _r -A -(CH2)s-, wherein A ² is -O- or -CH2-; R ⁷ is H or R ⁴ ; R» is C ₂ -C ₃ alkylene or hydroxyalkylene; X is H,

o

— CR ⁹ ,

-R or a mixture thereof, wherein R^ is C [ -C alkyl or hydoxyalkyl; k is 0 or 1 ; m and n are numbers such that the moiety -(CH2CH2θ) _Λ - comprises at least about 85% by weight of the moiety -[(C3HgO) (CH2CH2θ) _π ]-; m is from 0 to about 5; n is at least about 3; r is 1 or 2, s is 1 or 2, and r + s is 3 or 4; y is from 2 to about 20; the number of u, v and w are such that there are at least 2 N ⁺ centers and at least 2 X groups.

In the above formulas, A* is preferably

o o

II Ij NC - — or CN — ; i I

R R

A ² is preferably -O-; x is preferably 1 ; and R is preferably H. Rl can be linear (e.g. -CH ₂ -CH2-CH ₂ -,

CB,

1 ^J

CH2 ) or branched (e.g. - H2 - CH — ,— CH )

alkylene, hydroxyalkylene, alkenylene, cycloalkylene, alkarylene or oxyalkylene; when Ri is a C2-C3 oxyalkylene moiety, the number of oxyalkylene units is preferably from about 2 to about 12; R ¹ is preferably C2-C6 alkylene or phenylene, and most preferably C2-C6 alkylene (e.g. ethylene, propylene, hexamethylene). R ² is preferably -OR ⁵ - or -(OR ⁸ )y-; R3 is preferably -R ⁵ O- or -(OR ⁸ )^-; R ⁴ and R ⁶ are preferably methyl. Like R* , R ⁵ can be linear or branched, and is preferably C2- C3 alkylene; R ⁷ is preferably H or C1-C3 alkyl; R ⁸ is preferably ethylene; R^ is preferably methyl; X is preferably H or methyl; k is preferably 0; m is preferably 0, r and s are each preferably 2; y is preferably from 2 to about 12.

In the above formulas, n is preferably at least about 6 when the number of N ⁺ centers and X groups is 2 or 3; n is most preferably at least about 12, with a typical range of about 12 to about 42 for all ranges of u + v + w. For homopolymers (v and w are 0), u is preferably from about 3 to about 20. For random compolymers (u is at least 1 or preferably 0), v and w are each preferably from about 3 to about 40.

B. Polyacrylate, Polyacrylamide, Polyvinylether or Like Polymers

Another class of suitable cationic polymers are derived from polyacrylates, polyacrylamides, polyvinylethers and the like. These polymers comprise units selected from those having formulas IV, V and VI.

[(C3H ₆ O) _πl (CH ₂ CH2θ) _n ] — X

IV

[(C ₃ H ₆ O) _m (CH ₂ CH ₂ O) _n ] — X

VI

R is H or C1-C4 alkyl or hydroxyalkyl; R* is substituted C2-C12 alkylene, hydroxyalkylene, alkenylene, arylene or alkarylene, or C2-C3 oxyalkylene; each R ² is C1-C12 alkylene, hydroxyalkylene, alkenylene, arylene or alkarylene; each R^ is C1-C4 alkyl or hydroxyalkyl, the moiety -(R ² )A-[(C3H6θ) _OT (CH ₂ CH2θ) _n ]-X, or together form the moiety -(CH2) _r -A ² -(CH2 , wherein A ² is -O- or -CH2-; each R ⁴ is C1-C4 alkyl or hydroxyalkyl, or two R ⁴ together form the moiety -(CH2V-A ² - (CH2) _r ; X is H,

0

CR ^:

-R ⁵ or mixture thereof, wherein R ⁵ is C1-C4 alkyl or hydroxalkyl; j is 1 or 0; k is 1 or 0; m and n are numbers such that the moiety -(CH2CH2θ) _π - comprises at least about 85% by weight of the moiety -[(C3HgO),„(CH ₂ CH2θ)„]-; m is from 0 to about 5; n is at least about 3; r is 1 or 2, s is 1 or 2 and r + s is 3 or 4; the number of u, v and w are such that there are at least 2N+ centres and at least 2 X groups.

In the above formulas, A Ms preferably

O o

CN- CO or O

R

A ² is preferably -O-; R is preferably H. R^ can be linear

(e.g. — CH ₂ — CH— CH ₂ — , — C ) or

branched (e.g. — CH ₂ — C — , — CH ₂ CH-

substituted alkylene, hydroxyalkylene, alkenylene, alkarylene or oxyalkylene; R* is preferably substituted C2-Cg alkylene or substituted C2-C3 oxyalkylene, and most preferably

Cft

Each R ² is preferably C2-C3 alkylene, each R^ and R ⁴ are preferably methyl; R ⁵ is preferably methyl; X is preferably H or methyl; j is preferably 1 ; k is preferably 0; m is preferably 0; r and s are each preferably 2.

In the above formulas, n, u, v and w can be varied according to the n, u, v and w for the polyurethane and like polymers.

C. Polyalkyleneamine, Polyalkyleneimine or like polymers.

Another class of suitable cationic polymers are derived from polyalkyleneamines, polyalkyleneimines and the like. These polymers comprise units selected from those having formulas VII and VIII and IX.

(R ³ ) _k — [(C ₃ H ₆ 0) _m (CH ₂ CH ₂ 0) _n ) — X

(R ³ ) _k — [(C ₃ H ₆ 0) _m (CH ₂ CH ₂ 0) _n ] — X

wherein R^ is C ₂ -C]2 alkylene, hydroxyalkylene, alkenylene, cycloalkylene, arylene or alkarylene, or a C2-C3 oxyalkylene moiety having from 2 to about 20 oxyalkylene units provided that no O-N bonds are formed; each R ² is C1-C4 alkyl or hydroxyalkyl, or the moiety -(R ³ )H(C3H6θ) (CH2CH2θ)„]-X; R ³ is 1-C12 alkylene, hydroxyalkylene, alkenylene, arylene or alkarylene; M' is an N+ or N centre; X is H,

-R ⁴ or mixture thereof, wherein R ⁴ is C1-C4 alkyl or hydroxyalkyl; d is 1 when M' is N+ and is 0 when M' is N; e is 2 when M' is N+ and is 1 when M' is N; k is 1 or

0; m and n are numbers such that the moiety -(CH2CH2θ)„- comprises at least about 85%) by weight of the moiety -[^HβO^C^CHoO),,]-; m is from 0 to about 5; n is at least about 3; the number of x, y and z are such that there are at least 2M' groups, at least 2N+ centres and at least 2 X groups.

In the above formulas, R' can be varied like R^ of the polyurethene and like polymers; each R ² is preferably methyl or the moiety -(R ³ )jfc- [(C ₃ H ₆ O) _OT (CH2CH ₂ O)„]-X; R ³ is preferably C ₂ -C ₃ alkylene; R ⁴ is preferably methyl; X is preferably H; k is preferably 0; m is preferably 0.

In the above formulas, n is preferably at least about 6 when the number of M' and X groups is 2 or 3; n is most preferably at least about 12, with a typical range of from about 12 to about 42 for all ranges of x + y + z. Typically, x + y + z is from 2 to about 40 and preferably from 2 to about 20. For short chain length polymers, x + y + z can range from 2 to 9 with from 2 to 9 N+ centres and from 2 to 1 1 X groups. For long chain length polymers, x + y + 7. is at least 10, with a preferred range of from 10 to about 42. For the short and long chain length polymers, the M' groups are typically a mixture of from about 50 to 100%) N+ centres and from 0 to about 50% N centres.

Preferred cationic polymers within this class are derived from the C2-C3 polyalkyleneamines (x + y + z is from 2 to 9) and polyalkyleneimines (x + y + z is at least 10. preferably from 10 to about 42). Particularly preferred cationic polyalkyleneamines and polyalkyleneimines are the cationic polyethyleneamines (PEA's) and polyethyleneimines (PEI's). These preferred cationic polymers comprise units having the general formula:

wherein R ² (preferably methyl), M', X, d, x, y, z and n are defined as before; a is 1 or O.

Prior to ethoxylation, the PEAs used in preparing cationic polymers of the present invention have the following general formula:

CHzNJ CH ₂ NH ₂ ] ₂ ⁱ a ^■ l∞PVflx- [CH ₂ CH ₂ N]y- -{CH ₂

H wherein x + y + z is from 2 to 9, and a is 0 or 1 (molecular weight of from about 100 to about 400). Each hydrogen atom attached to each nitrogen atom represents an active site for subsequent ethoxylation. For preferred PEAs, x + y + z is from about 3 to about 7 (molecular weight is from about 140 to about 310). These PEA's can be obtained by reactions involving ammonia and ethylene dichloride, followed by fractional distillation. The common PEA's obtained are triethylenetetramine (TETA) and tetraethylenepentamine (TEPA). Above the pentamines, i.e., the hexamines, heptamines, octamines and possibly nonamines, the cogenerically derived mixture does not appear to separate by distillation and can include other materials such as cyclic amines and particularly piperazines. There can also be present cyclic amines with side chains in which nitrogen atoms appear. See US Pat. No. 2,792,372 to Dickson, issues May 14, 1957, which describes the preparation of PEAs.

The minimum degree of ethoxylation required for preferred clay soil removal/anti- redeposition performance can vary depending upon the number of units in the PEA.

Where y + z is 2 or 3, n is preferably at least about 6. Where y + z is from 4 to 9, suitable benefits are achieved when n is at least about 3. For preferred cationic PEAs, n is at least about 12, with a typical range of about 12 to about 42.

The PEIs used in preparing the polymers of the present invention have a molecular weight of at least about 440 prior to ethoxylation, which represents at least about 10 units. Preferred PEIs used in preparing these polymers have a molecular weight of from about 600 to about 1800. The polymer backbone of these PEIs can be represented by the general formula:

H

H ₂ N CH ₂ CH ₂ N -[ CH ₂ CH ₂ N -] - [- CH ₂ CH ₂ NH ₂ ] _Z

wherein the sum of x, y, and z represents a number of sufficient magnitude to yield a polymer having the molecular weights previously specified. Although linear polymer backbones are possible, branch chains can also occur. The relative proportions of primary, secondary and tertiary amine groups present in the polymer can vary, depending on the manner of preparation. The distribution of amine groups is typically as follows:

Each hydrogen atom attached to each nitrogen atom of the PEI represents an active site for subsequent ethoxylation. These PEIs can be prepared, for example, by polymerizing ethyleneimine in the presence of a catalyst such as carbon dioxide, sodium bisulfite, sulfuric acid, hydrogen peroxide, hydrochloric acid, acetic acid, etc. Specific methods for preparing PEIs are disclosed in US Pat. No. 2,182,306 to Ulrich

et al., issued Dec. 5, 1939; US Pat No. 3,033,746 to Mayle et al., issued May 8, 1962; US Pat. No. 2,208,095 to Esselmann et al., issued July 16, 1940; US Pat. No. 2,806,839 to Crowther, issued Sept. 17, 1957; and US Pat. No. 2,533,696 to Wilson, issued May 21, 1951 (all herein incorporated by reference).

As defined in the preceding formulas, n is at least about 3 for the cationic PEIs. However, it should be noted that the minimum degree of ethoxylation required for suitable clay soil removal/anti-redeposition performance can increase as the molecular weight of the PEI increases, especially much beyond about 1800. Also, the degree of ethoxylation for preferred polymers increases as the molecular weight of the PEI increases. For PEIs having a molecular weight of at least about 600, n is preferably at least about 12, with a typical range of from about 12 to about 42. For PEIs having a molecular weight of at least 1800, n is preferably at least about 24, with a typical range of from about 24 to about 42.

D. Diallylamine Polymers

Another class of suitable cationic polymers are those derived from the diallylamines. These polymers comprise units selected from those having formulas X and XI:

(R ³ )

wherein R^ is C1-C4 alkyl or hydroxyalkyl, or the moiety -(R ² ) - [(C ₃ H6θ),„(CH2CH2θ)„]-X; R ² is C1-C12 alkylene, hydroxyalkylene. alkylene, arylene or alkarylene; each R3 is C1-C4 alkyl or hydroxyalkyl. or together form the moiety -(CH2 - A-(CH2) , wherein A is -O- or -CH2-; X is H.

CR ⁴ ,

O

-R ⁴ or mixture thereof, wherein R ⁴ is C1-C4 alkyl or hydroxyalkyl; k is 1 or 0; m and n are numbers such that the moiety -(C^C^O),,- comprises at least about 85% by weight of the moiety -[(C3H6θ) _w (CH2CH2θ) _rt ]-; m is from 0 to about 5; n is at least about 3; r is 1 or 2, s is 1 or 2, and r + s is 3 or 4; x is 1 or 0; y is 1 when x is 0 and 0 when x is 1 ; the number of u and v are such that there are at least 2N+ centres and at least 2 X groups.

In the above formulas, A is preferably -O-; R^ is preferably methyl; each R- is preferably C2-C3 alkylene; each R ³ is preferably methyl; R ⁴ is preferably methyl; X is preferably H; k is preferably 0; m is preferably 0; r and s are each preferably 2.

In the above formulas, n is preferably at least about 6 when the number of N+ centres and X groups are each 2 or 3, n is preferably at least 12, with a typical range of from about 12 to about 42 for all range of u + v. Typically, v is 0, and u is from 2 to about 40. and preferably from 2 to about 20.

(Additional) Water-soluble builder compound

The detergent compositions or components thereof preferably contain a water-soluble builder compound, typically present in detergent compositions 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 momomeric 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, maleic acid, diglycolic acid, tartaric acid, tartronic acid and fumaric 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 Netherlands Application 7205873, and the oxypolycarboxylate materials such as 2-oxa- 1,1, 3 -propane tri carboxylates 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.

The parent acids of the monomeric or oligomeric polycarboxylate chelating agents or mixtures thereof with their salts, e.g. citric acid or citrate/citric acid mixtures are also contemplated as useful builder components.

Borate builders, as well as builders 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 poiymeta/phosphate in which the degree of polymerization ranges from about 6 to 21 , and salts of phytic acid.

Partially soluble or insoluble builder compound

The detergent compositions or components thereof, of the present invention may contain a partially soluble or insoluble builder compound, typically present in detergent compositions 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.

Preferred largely insoluble builder compounds are aluminosilicate ion exchange materials, preferably zeolite A and zeolite MAP, as described above.

Heavy metal ion sequestrant

The detergent compositions or components thereof preferably contain as an optional component a heavy metal ion sequestrant. By heavy metal ion sequestrant it is meant herein components which act to sequester (chelate) heavy metal ions. These components may also have calcium and magnesium chelation capacity, but preferentially they show selectivity to binding heavy metal ions such as iron, manganese and copper.

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

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

Preferred among the above species are diethylene 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 ethyienediamine-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 -hydroxy ethyl 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 β-alanine-N,N'-diacetic acid, aspartic acid-N.N'-diacetic acid, aspartic acid-N- monoacetic acid and iminodisuccinic acid sequestrants described in EP-A-509,382 are also suitable.

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 also suitable. Glycinamide-N,N'- disuccinic acid (GADS), ethylenediamine-N-N'-diglutaric acid (EDDG) and 2- hydroxypropylenediamine-N-N'-disuccinic acid (HPDDS) are also suitable.

Organic peroxyacid bleaching system

A preferred feature of detergent compositions or component thereof is an organic peroxyacid bleaching system. In one preferred execution the bleaching system contains a hydrogen peroxide source and an organic peroxyacid bleach precursor compound. The production of the organic peroxyacid occurs by an in situ reaction of the precursor with a source of hydrogen peroxide. Preferred sources of hydrogen peroxide include inorganic perhydrate bleaches. In an alternative preferred execution a preformed organic peroxyacid is incorporated directly into the composition. Compositions containing mixtures of a hydrogen peroxide source and organic peroxyacid precursor in combination with a preformed organic peroxyacid are also envisaged.

Inorganic perhydrate bleaches

Inorganic perhydrate salts are a preferred source of hydrogen peroxide. These salts are normally incorporated in the form of the alkali metal, preferably sodium salt at a level of from 1% to 40% by weight, more preferably from 2% to 30% by weight and most preferably from 5% to 25% by weight of the compositions.

Examples of inorganic perhydrate salts include perborate, percarbonate, perphosphate, persulfate and persilicate salts. The inorganic perhydrate salts are normally the alkali metal salts. The inorganic perhydrate salt may be included as the crystalline solid without additional protection. For certain perhydrate salts however, the preferred executions of such granular compositions utilize a coated form of the material which provides better storage stability for the perhydrate salt in the granular product. Suitable coatings comprise inorganic salts such as alkali metal silicate, carbonate or borate salts or mixtures thereof, or organic materials such as waxes, oils, or fatty soaps.

Sodium perborate is a preferred perhydrate salt and can be in the form of the monohydrate of nominal formula NaBθ2H2θ2 or the tetrahydrate NaBO ₂ H2θ2.3H O.

Alkali metal percarbonates, particularly sodium percarbonate are preferred perhydrates herein. Sodium percarbonate is an addition compound having a formula corresponding to 2Na2CO3.3H2O2, and is available commercially as a crystalline solid.

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

Peroxyacid bleach precursor

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

O li

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

II

X-C -OOH

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

Suitable peroxyacid bleach precursor compounds typically contain one 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 groups

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:

υ

-N— C— R ¹ -N Λ N -N— C— CH— R ⁴ R ⁵ R ^J

I

Y

R ³ Y

I I

-O-CH=C-CH=CH ₂ -O-CH=C-CH=CH ₂

and mixtures thereof, wherein R is an alkyl, aryl, or alkaryl group containing from 1 to 14 carbon atoms, R 3 is an alkyl chain contai •ning from 1 to 8 carbon atoms. R 4 is

H or R , R ⁵ is an alkenyl chain containing from 1 to 8 carbon atoms and Y is H or a solubilizing group. Any of R 1 , R 3 and R 4 may be substituted by essentially any functional group including, for example alkyl, hydroxy, alkoxy, halogen, amine, nitrosyl, amide and ammonium or alkyl ammmonium groups

chain containing from 1 to 4 carbon atoms, M is a cation which provides solubility to the bleach activator and X is an anion which provides solubility to the bleach activator. Preferably, M is an alkali metal, ammonium or substituted ammonium cation, with sodium and potassium being most preferred, and X is a halide, hydroxide, methylsulfate or acetate anion.

Alkyl percarboxylic acid bleach precursors

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

Preferred alkyl percarboxylic precursor compounds of the imide type include the N- ,N,N*Nl tetra acetylated alkylene diamines wherein the alkylene group contains from 1 to 6 carbon atoms, particularly those compounds in which the alkylene group contains 1 , 2 and 6 carbon atoms. Tetraacetyl ethylene diamine (TAED) is particularly preferred.

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

Amide substituted alkyl peroxyacid precursors

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

1 1 R1 N — C — R ² — C

or R ⁵ O O

wherein R^ is an alkyl group with from 1 to 14 carbon atoms, R ² is an alkylene group containing from 1 to 14 carbon atoms, and R ⁵ 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-0170386.

Perbenzoic acid precursor

Perbenzoic acid precursor 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 ureas. Suitable imidazole type perbenzoic acid precursors include N-benzoyl imidazole and N-benzoyl benzimidazole. Other useful N-acyl group- containing perbenzoic acid precursors include N-benzoyl pyrrolidone, dibenzoyl taurine and benzoyl pyroglutamic acid.

Cationic peroxyacid precursors

Cationic peroxyacid precursor compounds produce cationic peroxyacids on perhydrolysis.

Typically, cationic peroxyacid precursors are formed by 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 precursor compound to be so cationically substituted may be a perbenzoic acid, or substituted derivative thereof, precursor compound as described hereinbefore. Alternatively, the peroxyacid precursor compound may be an alkyl percarboxylic acid precursor compound or an amide substituted alkyl peroxyacid precursor as described hereinafter

Cationic peroxyacid precursors are described in U.S. Patents 4,904,406; 4,751.015; 4,988,451 ; 4,397,757; 5,269,962; 5,127,852; 5,093,022; 5,106,528; U.K. 1,382.594; EP 475,512, 458.396 and 284,292; and in JP 87-318,332.

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

Suitable cationic peroxyacid precursors include any of the ammonium or alkyl ammonium substituted alkyl or benzoyl oxybenzene sulfonates, N-acylated caprolactams, and monobenzoyltetraacetyl glucose benzoyl peroxides. Preferred cationic peroxyacid precursors of the N-acylated caprolactam class include the trialkyl ammonium methylene benzoyl caprolactams and the trialkyl ammonium methylene alkyl caprolactams.

Benzoxazin organic peroxyacid precursors

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

wherein R. 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 1 — _c _ _N _ _R 2 ..._ _c _ OOH

wherein R is an alkyl, aryl or alkaryl group with from 1 to 14 carbon atoms. R ² is an alkylene, arylene, and alkarylene group containing from 1 to 14 carbon atoms, and R ⁵ 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- 0170386.

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.

Enzyme

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

Preferred additional enzymatic materials include the commercially available cellulases, endolases, cutinases, amylases, lipases, neutral and alkaline proteases, esterases, pectinases, lactases and peroxidases conventionally incorporated into 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 tradenames Alcalase, Savinase, Primase, Durazym, and Esperase by Novo Industries A/S (Denmark), those sold under the tradename Maxatase, Maxacal and Maxapem by Gist-Brocades, those sold by Genencor International, and those sold under the tradename Opticlean and Optimase by Solvay Enzymes. Protease enzyme may be incorporated into the compositions in accordance with the invention at a level of from 0.0001% to 4% active enzyme by weight of the composition.

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

(Additional) Organic polymeric compound

Organic polymeric compounds are preferred additional components of the detergent compositions or components thereof 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, not being an quatemised ethoxylated (poly) amine clay-soil removal/ anti- redeposition agent in accord with the invention.

Organic polymeric compound is typically incorporated in the detergent compositions of the invention at a level 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 1000-5000 and their copolymers with maleic anhydride, such copolymers having a molecular weight of from 2000 to 100.000, especially 40,000 to 80,000.

The polyamino compounds are useful herein including those derived from aspartic acid such as those disclosed in EP-A-305282, EP-A-305283 and EP-A-351629.

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

Other organic polymeric compounds suitable for incorporation in the detergent compositions herein include cellulose derivatives such as methylcellulose, carboxymethylcellulose, hydroxypropylmethylcellulose and hydroxyethylcellulose.

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

Suds suppressing system

The detergent compositions, 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 24 carbon atoms, preferably 12 to 18 carbon atoms. Suitable salts include the alkali metal salts such as sodium, potassium, and lithium salts, and ammonium and alkanolammonium salts.

Other suitable antifoam compounds include, for example, high molecular weight fatty esters (e.g. fatty acid triglycerides), fatty acid esters of monovalent alcohols, aliphatic C i g-C4Q 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-alkali metal (e.g. sodium, potassium, lithium) phosphates and phosphate esters.

A preferred suds suppressing system comprises

(a) antifoam compound, preferably silicone antifoam compound, most preferably a silicone antifoam compound comprising in combination

(i) polydimethyl siloxane, at a level of from 50% to 99%, preferably 75% to 95% by weight of the silicone antifoam compound; and

(ii) silica, at a level of from 1 % to 50%, preferably 5% to 25% by weight of the silicone/silica antifoam compound;

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

(b) a dispersant compound, most preferably comprising a silicone glycol rake copolymer with a polyoxyalkylene content of 72-78% and an ethylene oxide to propylene oxide ratio of from 1 :0.9 to 1 : 1.1 , at a level of from 0.5% to 10%, preferably 1% to 10% by weight; a particularly preferred silicone glycol rake copolymer of this type is DCO544, commercially available from DOW

Coming under the tradename DCO544;

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

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

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, whereby these polymers can be cross-linked polymers.

a) Polyamine N-oxide polymers

Polyamine N-oxide polymers suitable for use herein contain units having the following structure formula :

P

(I) 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, heterocychc 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

O

(R.,) x -N-(R ₂ )y ▲

( ^R 3)z or N-(R-,)x

wherein RI, R2, and R3 are aliphatic groups, aromatic, heterocychc 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 heterocychc 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 heterocychc 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 aromaticheterocyclic 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 heterocychc compound such as pyrridine, pyrrole, imidazole and derivatives thereof.

The polyamine N-oxides can be obtained in almost any degree of polymerisation. The degree of polymerisation is not critical provided the material has the desired water-solubility and dye-suspending power. Typically, the average molecular weight is within the range of 500 to 1000,000.

b) Copolymers of N-vinylpyrrolidone and N-vinylimidazole

Suitable herein are coploymers of N-vinylimidazole and N-vinylpyrrolidone having an average molecular weight range of from 5,000 to 50,000. The preferred copolymers have a molar ratio of N-vinylimidazole to N-vinylpyrrolidone from 1 to 0.2.

c) Polyvinylpyrrolidone

The detergent compositions herein may also utilize polyvinylpyrrolidone ("PVP") having an average molecular weight of from 2,500 to 400,000. Suitable polyvinylpyrrolidones are commercially available from ISP Corporation, New York, NY and Montreal, Canada under the product names PVP K-l 5 (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-l 5 is also available from ISP Corporation. Other suitable polyvinylpyrrolidones which are commercially available from BASF Cooperation include Sokalan HP 165 and Sokalan HP 12.

d) Polyvinyloxazolidone

The detergent compositions herein may also utilize polyvinyloxazolidones as polymeric dye transfer inhibiting agents. Said polyvinyloxazolidones have an average molecular weight of from 2,500 to 400,000.

e) Polyvinylimidazole

The detergent compositions herein may also utilize polyvinylimidazole as polymeric dye transfer inhibiting agent. Said polyvinylimidazoles preferably have an average molecular weight of from 2,500 to 400,000.

Optical brightener

The detergent compositions herein also optionally contain from about 0.005% to 5% by weight of certain types of hydrophilic optical brighteners.

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

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

When in the above formula, Rj is anilino, R2 is N-2-bis-hydroxyethyl and M is a cation such as sodium, the brightener is 4,4',-bis[(4-anilino-6-(N-2-bis- hydroxyethyl)-s-triazine-2-yl)amino]-2,2'-stilbenedisulfonic acid and disodium salt. This particular brightener species is commercially marketed under the tradename

Tinopal-UNPA-GX by Ciba-Geigy Coφoration. Tinopal-UNPA-GX is the preferred hydrophilic optical brightener useful in the detergent compositions herein.

When in the above formula, R] 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-aniiino-6-(N-2- hydroxyethyl-N-methylamino)-s-triazine-2-yl)amino]2,2'-stilb enedisulfonic acid

disodium salt. This particular brightener species is commercially marketed under the tradename Tinopal 5BM-GX by Ciba-Geigy Coφoration.

When in the above formula, R\ is anilino. R2 is moφhilino and M is a cation such as sodium, the brightener is 4,4'-bis[(4-aniIino-6-moφhilino-s-triazine-2-yl)amino]2,2'- stilbenedisulfonic acid, sodium salt. This particular brightener species is commercially marketed under the tradename Tinopal AMS-GX by Ciba Geigy Coφoration.

Polymeric Soil Release Agent

Known polymeric soil release agents, hereinafter "SRA", can optionally be employed in the present detergent compositions. If utilized, SRA's will generally comprise from 0.01% to 10.0%, typically from 0.1% to 5%, preferably from 0.2% to 3.0% by weight, of the compositions.

Preferred SRA's typically have hydrophilic segments to hydrophilize the surface of hydrophobic fibers such as polyester and nylon, and hydrophobic segments to deposit upon hydrophobic fibers and remain adhered thereto through completion of washing and rinsing cycles, thereby serving as an anchor for the hydrophilic segments. This can enable stains occurring subsequent to treatment with the SRA to be more easily cleaned in later washing procedures.

Preferred SRA's include oligomeric terephthalate esters, typically prepared by processes involving at least one transesterification/oligomerization, often with a metal catalyst such as a titanium(IV) alkoxide. Such esters may be made using additional monomers capable of being incoφorated into the ester structure through one, two, three, four or more positions, without, of course, forming a densely crosslinked overall structure.

Suitable SRA's include a sulfonated product of a substantially linear ester oligomer comprised of an oligomeric ester backbone of terephthaloyl and oxyalkyleneoxy repeat units and allyl-derived sulfonated terminal moieties covalently attached to the backbone, for example as described in U.S. 4,968,451, November 6, 1990 to J.J. Scheibel and E.P. Gosseiink. Such ester oligomers can be prepared by: (a)

ethoxylating allyl alcohol; (b) reacting the product of (a) with dimethyl terephthalate ("DMT") and 1,2-propylene glycol ("PG") in a two-stage transesterification/oligomerization procedure; and (c) reacting the product of (b) with sodium metabisulfite in water. Other SRA's include the nonionic end-capped 1,2- propylene/polyoxyethylene terephthalate polyesters of U.S. 4,711,730, December 8, 1987 to Gosseiink et al., for example those produced by transesterification/oligomerization of poly(ethyleneglycol) methyl ether, DMT, PG and poly(ethyleneglycol) ("PEG"). Other examples of SRA's include: the partly- and fully- anionic-end-capped oligomeric esters of U.S. 4,721,580, January 26, 1988 to Gosseiink, such as oligomers from ethylene glycol ("EG"), PG, DMT and Na-3,6- dioxa-8-hydroxyoctanesulfonate; the nonionic-capped block polyester oligomeric compounds of U.S. 4,702,857, October 27, 1987 to Gosseiink, for example produced from DMT, methyl (Me)-capped PEG and EG and/or PG, or a combination of DMT, EG and/or PG, Me-capped PEG and Na-dimethyl-5-sulfoisophthalate; and the anionic, especially sulfoaroyl, end-capped terephthalate esters of U.S. 4,877,896, October 31, 1989 to Maldonado, Gosseiink et al., the latter being typical of SRA's useful in both laundry and fabric conditioning products, an example being an ester composition made from m-sulfobenzoic acid monosodium salt, PG and DMT, optionally but preferably further comprising added PEG, e.g., PEG 3400.

SRA's also include: simple copolymeric blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate, see U.S. 3,959,230 to Hays, May 25, 1976 and U.S. 3.893.929 to Basadur, July 8, 1975; cellulosic derivatives such as the hydroxyether cellulosic polymers available as METHOCEL from Dow; the CJ-C4 alkyl celluloses and C4 hydroxyalkyl celluloses, see U.S. 4,000,093, December 28, 1976 to Nicol, et al.; and the methyl cellulose ethers having an average degree of substitution (methyl) per anhydroglucose unit from about 1.6 to about 2.3 and a solution viscosity of from about 80 to about 120 centipoise measured at 20°C as a 2% aqueous solution. Such materials are available as METOLOSE SMI 00 and METOLOSE SM200, which are the trade names of methyl cellulose ethers manufactured by Shin-etsu Kagaku Kogyo KK.

Additional classes of SRA's include: (I) nonionic terephthalates using diisocyanate coupling agents to link polymeric ester structures, see U.S. 4,201,824, Violland et al.

and U.S. 4,240.918 Lagasse et al.; and (II) SRA's with carboxylate terminal groups made by adding trimellitic anhydride to known SRA's to convert terminal hydroxyl groups to trimellitate esters. With the proper selection of catalyst, the trimellitic anhydride forms linkages to the terminals of the polymer through an ester of the isolated carboxylic acid of trimellitic anhydride rather than by opening of the anhydride linkage. Either nonionic or anionic SRA's may be used as starting materials as long as they have hydroxyl terminal groups which may be esterified. See U.S. 4,525,524 Tung et al.. Other classes include: (III) anionic terephthalate- based SRA's of the urethane-1 inked variety, see U.S. 4,201,824. Violland et al.;

Form of the compositions

The particle of the present invention can be introduced in the detergent component via a variety of methods, including dry-mixing and agglomerating of the various compounds comprised in the detergent component.

The detergent compositions or components thereof can have a variety of physical forms including granular, tablet, flake, pastille and bar 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 bulk density of granular detergent compositions in accordance with the present invention typically have a bulk density of at least 600 g/litre, more preferably from 650 g/litre to 1200 g/litre. Bulk density is measured by means of a simple funnel and cup device 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 90 mm. an internal height of 87 mm and an internal diameter of 84 mm. Its nominal volume is 500 ml.

To carry out a measurement, the funnel is filled with powder by hand pouring, the flap valve is opened and powder allowed to overfill the cup. The filled cup is removed from the frame and excess powder removed from the cup by passing a straight edged implement eg; a knife, across its upper edge. The filled cup is then weighed and the value obtained for the weight of powder doubled to provide a bulk density in g/litre. Replicate measurements are made as required.

Compacted solids may be manufactured using any suitable compacting process, such as tabletting, briquetting or extrusion, preferably tabletting. Preferably tablets for use in dish washing processes, are manufactured using a standard rotary tabletting press using compression forces of from 5 to 13 KN/cm ² , more preferably from 5 to 1 1 KN/cm-'- so that the compacted solid has a minimum hardness of 176N to 275N, preferably from 195N to 245N, measured by a C100 hardness test as supplied by I. Holland instruments. This process may be used to prepare homogeneous or layered tablets of any size or shape. Preferably tablets are symmetrical to ensure the uniform dissolution of the tablet in the wash solution.

Abbreviations used in Examples

In the detergent compositions, the abbreviated component identifications have the following meanings:

LAS Sodium linear C 2 alkyl benzene sulfonate TAS Sodium tallow alkyl sulfate CxyAS Sodium Cj _x - Cjy alkyl sulfate C46SAS Sodium C]4 - Cj6 secondary (2,3) alkyl sulfate CxyEzS Sodium Cj _x -Ciy alkyl sulfate condensed with z moles of ethylene oxide

CxyEz C ] _X -C i y predominantly linear primary alcohol condensed with an average of z moles of ethylene oxide

QAS R2.N ⁺ (CH3)2(C ₂ H OH) with R ₂ = C ₁₂ - Cj ₄ Soap Sodium linear alkyl carboxylate derived from an 80/20 mixture of tallow and coconut oils

CFAA Cl2"Ci4~(coco) alkyl N-methyl glucamide TFAA Cjg-Cj g alkyl N-methyl glucamide TPKFA Ci2-C _j 4 topped whole cut fatty acids STPP Anhydrous sodium tripoly phosphate TSPP Tetrasodium pyrophosphate Zeolite A Hydrated Sodium Aluminosilicate of formula

Nai2(A102SiO2)i2- ⁷ H2O having a primary particle size in the range from 0.1 to 10 micrometers Zeolite A (dry) Zeolite A with a moisture content of lee than 10% by weight

Zeolite MAP Hydrated sodium aluminosilicate zeolite MAPhaving a silicon to aluminium ratio of 1.07

NaSKS-6 Crystalline layered silicate of formula δ- Na2Si2θ5 Citric acid Anhydrous citric acid Borate Sodium borate Carbonate Anydrous sodium carbonate with a particle size between

200μm and 900μm

Bicarbonate Anhydrous sodium bicarbonate with a particle size distribution between 400μm and 1200μm

Silicate Amoφhous Sodium Silicate (SiO2:Na2O = 2.0:1)

Sodium sulfate Anhydrous sodium sulfate Citrate Tri-sodium citrate dihydrate of activity 86.4% with a particle size distribution between 425μm and 850μm

MA/AA Copolymer of 1 :4 maleic/acrylic acid, average molecular weight about 70,000

AA Sodium polyacrylate polymer of average molecular weight

4,500

CMC Sodium carboxymethyl cellulose Cellulose ether Methyl cellulose ether with a degree of polymerization of

650 available from Shin Etsu Chemicals

Protease Proteolytic enzyme of activity 4KNPU/g sold by NOVO

Industries A/S under the tradename Savinase

Alcalase Proteolytic enzyme of activity 3AU/g sold by NOVO

Industries A/S

Cellulase Cellulytic enzyme of activity 1000 CEVU/g sold by

NOVO Industries A/S under the tradename Carezyme

Amylase Amylolytic enzyme of activity 120KNU/g sold by NOVO

Industries A/S under the tradename Termamyl 120T

Lipase Lipolytic enzyme of activity lOOKLU/g sold by NOVO

Industries A/S under the tradename Lipolase

Endolase Endoglucanase enzyme of activity 3000 CEVU/g sold by

NOVO Industries A S

PB4 Sodium perborate tetrahydrate of nominal formula

NaBθ2.3H ₂ O.H ₂ θ2

PB1 Anhudrous sodium perborate bleach of nominal formula

NaBθ2-H2θ2

Percarbonate Sodium percarbonate of nominal formula

2Na ₂ CO ₃ .3H2θ2

NOBS Nonanoyloxy benzene sulfonate in the form of the sodium salt

TAED Tetraacetylethylenediamine Mn catalyst Mn ^IV ₂ (m-O)3( 1 ,4.7-trimethyl- 1 ,4,7- triazacyclononane)2(PF6)2, as described in U.S. Pat. Nos.

5,246,621 and 5.244,594.

DTPA Diethylene triamine pentaacetic acid DTPMP Diethylene triamine penta (methylene phosphonate), marketed by Monsanto under the Tradename Dequest

2060

Photoactivated Sulfonated Zinc Phthlocyanine encapsulated in bleach dextrin soluble polymer

Brightener 1 Disodium 4,4'-bis(2-sulphostyry)biphenyl Brightener 2 Disodium 4,4'-bis(4-anilino-6-moφholino-l .3.5-triazin-2- yl)amino) stilbene-2:2'-disulfonate HEDP 1 , 1 -hydroxyethane diphosphonic acid EDDS Ethylenediamine-N, N'-disuccinic acid QEA1 bis((C ₂ H5θ)(C ₂ H4θ) _n ) (CH ₃ ) -N+-C ₆ H ₁₂ -N ⁺ -(CH ₃ ) bis((C2H5O)-(C2H ₄ O) _n ), wherein n-from 20 to 30

QEA2 bis((C2H5θ)-(C2H ₄ O) _n ) (CH ₃ ) N+ R] , wherein R is

C4-C12 ^a lkyl group and n=from 20 to 30

QEA3 tri{(bis((C2H ₅ O)-(C2H ₄ O) _n )(CH3)-N ⁺ )-(CONC3H ₆ )}-

C3H5O, wherein n=from 20 to 26

PEGX Polyethylene glycol, with a molecular weight of x

PEO Polyethylene oxide, with a molecular weight of 50,000

TEPAE Tetraethylenepentaamine ethoxylate

PVP Polyvinylpyrolidone polymer

PVNO Polyvinylpyridine N-oxide

PVPVI Copolymer of polyvinylpyrolidone and vinylimidazole

SRP1 Sulfobenzoyl and capped esters with oxyethylene oxy and terephtaloyl backbone

SRP2 Diethoxylated poly (1, 2 propylene terephtalate) short block polymer

Silicone antifoam Polydimethylsiloxane foam controller with siloxane- oxyalkylene copolymer as dispersing agent with a ratio of said foam controller to said dispersing agent of 10:1 to

100:1

Wax Paraffin wax

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

Example 1

The following detergent formulations of particular utility under European machine wash conditions were prepared.

Example 2

The following granular detergent formulations were prepared.

Example 3

The following granular detergent formulations were prepared.

Example 4

The following granular detergent compositions.

Example 5

The following detergent compositions were prepared.