GB2317394A - Detergent compositions - Google Patents

Abstract

Granular detergent compositions or component thereof, containing one or more carboxylate-containing polyelectrolyte compounds, having builder or dispersant properties, and one or more cationic compounds, which are cationic, (partially) quaternized ethoxylated (poly)amine compounds with clay-soil removal / anti-redeposition properties, for use in laundry and dish washing processes.

Description

Detergent Compositions Technical Field The present invention relates to granular detergent compositions or components thereof containing cationic compounds with clay-soil/ particulate soil removal/anti-redeposition properties and one or more carboxylate- containing polyelectrolyte compounds, with builder or dispersant properties, for use in laundry and dish washing processes.

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.

A variety of models can be proposed for compounds which would have clay soil removal properties. One model requires that the compound have two distinct characteristics. The first is the ability of the compound to adsorb onto the negatively charged layers of the clay particle. The second is the ability of the compound, once adsorbed, to push apart (swell) the negatively charged layers so that the clay particle loses its cohesive force and can be removed in the wash water.

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 effect which is especially noticeable on white fabrics. To minimise this problem, anti-redeposition agents can be included in the detergent composition.

Other detergent components traditionally employed in detergents are carboxylate-containing polyelectrolyte compounds, which are also known in detergent compositions as soil dispersants and anti-encrustation agents.

For example EP-B-1 11 965 disclose 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.

A model proposed for the anti-redeposition action of these compounds is as follows. Adsorption of the positively charged molecule on the surface of clay particles in the wash water gives the particles the dispersancy properties of the molecule. As more and more of these compounds adsorb onto the suspended clay soil particles, the latter become encased within a hydrophilic layer provided by the attached ethoxy units. As such the hydrophilically encased soil is prevented from redepositing on fabrics, in particular hydrophobic fabrics such as polyester, during the laundering or dish washing cycle.

It has been found that the known cationic clay-soil removal compounds do not always remove the clay particles rapidly and efficiently from the fabric surface into the washing water, because they can encounter problems when trying to push apart (swell) the negatively charged layers of the clay (and thereby preventing the clay particles losing their cohesive force). These problems can be due to clay and particulate soils being held together by calcium bridges.

It has also been found that the anti-redeposition properties of these known cationic clay-soil removal compounds can be deminished under hard-water conditions during the laundry or dishwashing process, i.e when high levels of free calcium (and/ or magnesium) is present in the wash water.

The Applicants have now found that these problems can be ameliorated by inclusion of specific amounts of carboxylate-containing polyelectrolyte compounds, which have builder or dispersant properties, in a granular detergent composition (or a component thereof), comprising cationic, (partially) quaternized ethoxylated (poly) amines which have clay-soil removal/anti-redeposition properties. Detergent compositions (or components thereof) employing both cationic quaternized ethoxylated (poly) arnines and carboxylate-containing polyelectrolyte compounds have been shown to deliver a surprisingly better clayl soil removal and cleaning performance than that of detergent compositions employing either of the two components individually.

The cleaning performance benefits of the detergent compositions containing both carboxylate-containing polyelectrolyte compounds and cationic, (partially) quaternized ethoxylated (poly) amines are found to depend both on the amount of carboxylate-containing polyelectrolyte compound used and its properties (e.g. the molecular weight of the polymeric compound and the monomeric segments comprised in the polymeric compound). For example, in built conditions it has been found that co-polymeric polycarboxylic compounds, for example maleic acrylic co-polymers, have a better (calcium) builder/ dispersant performance than homo-polymeric polycarboxylic compounds of a similar molecular weight. Thus, lower levels of certain, preferred polymeric compounds are as effective as higher levels of others.

A further advantage of the present invention is that the clayl soil removal benefits can even be observed after the completion of only one wash cycle.

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

Summary of the invention The present invention relates to granular detergent compositions or components thereof, which comprise a carboxylate-containing polyelectrolyte compound, having builder or dispersant properties, and one or more cationic compounds, which are (partially) quaternized ethoxylated (poly) amine compounds with clay-soil removal I anti-redeposition properties.

In more detail, the present invention relates to a granular detergent composition or component thereof which comprises: (a) a carboxylate-containing polyelectrolyte compound; and (b) a water-soluble cationic compound having clay soil removaVanti-redeposition properties, which is selected from the group consisting of: 1) ethoxylated cationic monoamines having the formula:

2) ethoxylated cationic diamines having the formula:

wherein M1 is an N+ or N group; each M2 is an N+ or N group, and at least one M2 is an N+ group; 3) ethoxylated cationic polyamines having the formula:

4) mixtures thereof; wherein Al is

R is H or Cl-C4 alkyl or hydroxyalkyl, R1 is C2-C12 alkylene, hydroxyalkylene, alkenylene, 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 R2 is Cl-C4 alkyl or hydroxyalkyl, the moiety -L X, or two R2 together form the moiety -(CH2)rA2-(CH2)s-, wherein A2 is O- or -CH2-, r is l or2, s is l or2 and r- s is 3 or4; each R3 is Cl-Cg alkyl or hydroxyalkyl, benzyl, the moiety L-X, or two R3 or one R2 and one R3 together form the moiety -(CH2)rA2-(CH2)s-; R4 is a substituted C3 C 12 alkyl, hydroxyalkyl, alkenyl, aryl or alkaryl group having p substitution sites; R5 is Cl-Cl 2 alkenyl, hydroxyalkylene, alkenylene, arylene or alkarylene, or a C2-C3 oxyalkylene moiety having from 2 to about 20 oxvalkylene units provided that no 0-0 or O-N bonds are formed; X is a nonionic group selected from the group consisting of H, C 1 -C4 alkyl or hydroxyalkyl ester or ether groups, and mixtures thereof; L is a hydrophilic chain which contains the polyoxyalkylene moiety -[(R60)m(CH2CH20)n]-; wherein R6 is C3-C4 alkylene or hydroxyalkylene and m and n are numbers such that the moiety -(CH2CH2O)n- comprises at least about 50% by weight of said polyoxyalkylene moiety; d is 1 when M2 is N+ and is 0 when M2 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 1; andwhewinthe Iatio of wDd (a)to (b) is fian 1:95 to 95:1.

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

The ratio of the water-soluble cationic compound to the carboxylatecontaining polyelectrolyte compound is from 1:95 to 95:1, more preferably from 1:25 to 25:1, most preferably from 1:5 to 5:1 If present in a detergent composition in accord with the present invention the water-soluble cationic compound is preferably present 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.

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

In the preceding formulas for the cationic gamines, R1 can be branched (e.g.

cyclic

or most preferably linear (e.g. CH2CH2 , CH2cH2cH2 ) alkylene, hydroxyalkylene, alkenylene, alkarylene or oxyalkylene. R1 is preferably C2-C6 alkylene for the ethoxylated cationic diamines. Each R2 is preferably methyl or the moiety -L-X; each R3 is preferably C1-C4 alkyl or hydroxyalkyl, and most preferably methyl.

The positive charge of the N+ groups is offset by the appropriate number of counter amnions. Suitable counter anions include Cl-, Br-, S03-2, PO4-2, MeOSO3- and the like. Particularly preferred counter anions are C 1 - and Br-.

X can be a nonioinic 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 formulas, hydrophilic chain L usually consists entirely of the polyoxyalkylene moiety -[(R6O)m(CH2CH2-On)-]. The moieties -(R60)m- and XCH2CH2O)n- of the polyoxyalkylene moiety can be mixed together or preferably form blocks Of6O)rn and XCH2CH2O)"- moieties. R6 is preferably C3H (propylene); m is preferably from 0 to about 5 and is most preferably 0, i.e. the polyoxyalkylene moiety consists entirely ofthe moiety (CH2CH20)n-. The moiety -(CH2CH2O)n- 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, M1 and each M2 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

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 R4 is a substituted aryl or alkaryl group, q is preferably 1 and R5 is preferably C2-C3 alkylene. When R4 is a substituted alkyl, hydroxyalkyl, or alkenyl group, and when q is 0, R5 is preferably a C2-C3 oxyalkylene moiety; when q is 1, R5 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: -(OC3H6)c-NH2 CH3 (OC3H6)c NH2 -(OC3H6)c-NH2 wherein each c is a number from 2 to about 20.

Carboxvlate-containing polvelectrolvte compounds An essential component of the invention is one or more carboxylatecontaining polyelectrolyte compounds, which have builder or dispersant properties.

The ratio of the water-soluble cationic compound (which has clay-soil removal/anti-redeposition properties) to the carboxylate-containing polyelectrolyte compounds is from 1:95 to 95:1, more preferably from 1:25 to 25:1, most preferably from 1:5 to 5:1.

Preferably these compounds are homo- or co-polymeric polycarboxylic compounds and most preferably co-polymeric polycarboxylic compounds in which the acid monomer of said polycarboxylic compound comprises at least two carboxyl groups separated by not more than two carbon atoms.

Salts of these polycarboxylic compounds are also considered herein.

If present in detergent compositions in accord with the present invention, the carboxylate-containing polyelectrolyte compounds are preferably present at a level of 0.01% to 40%, more preferably from 0.1% to 10% and most preferably from 0.2% to 6% by weight of the detergent composition.

The carboxylate-containing polyelectrodyte materials can be prepared by polymerising or copolymerizing suitable unsaturated monomers, preferably in their acid forrn. Unsaturated monomeric acids that can be polymerised to form suitable polymeric polycarboxylates are selected from acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid and methylenemalonic acid. The presence in these carboxylate-containing polyelectrolyte compounds herein of monomeric segments, containing no carboxylate radicals such as vinylmethyl ether, styrene, ethylene, etc. is suitable provided that such segments do not constitute more than 40% by weight.

Carboxylate-containing materials can also optionally include further monomeric units such as nonionic spacing units. For example, suitable nonionic spacing units may include vinyl alcohol or vinyl acetate.

Particular preferred carboxylate-containing polyelectrolyte compounds are acrylic/maleic-based co-polymers. Such materials include the water-soluble salts of copolymers of acrylic acid and maleic acid/ maleic anhydride. The average molecular weight of such copolymers in the acid form preferably can range from 1,000 to 100,000, more preferably from 2,000 to 75,000, but most preferred are the co-polymers with a average molecular weight of from 2,500 to 20.000 and from 60,000 to 75,000. The ratio of acrylate to maleate segments in such copolymers will generally range from 30:1 to 1:30, more preferably from 10:1 to 1:1. Water-soluble salts of such acrylic acid/maleic acid copolymers can include, for example, the alkali metal, ammonium and substituted ammonium salts. Soluble acrylate/maleate copolymers of this type are known materials which are described in European Patent Application No. 66915, published December 15, 1982, as well as in EP 193,360, published September 3, 1986.

Other suitable carboxylate-containing polyelectrolyte compounds can be derived from acrylic acid. Such acrylic acid-based polymers which are useful herein are for example the water-soluble salts of polymerized acrylic acid. The average molecular weight of such homo-polymers in the acid form preferably ranges from 1,800 to 100,000, more preferably from 2,000 to 10,000, most preferably from 3,000 to 5,000. Water-soluble salts of such acrylic acid polymers or can include, for example, the alkali metal, ammonium and substituted ammonium salts. Soluble polymers of this type are known materials. Use of polyacrylates of this type in detergent compositions has been disclosed, for example, in Diehl, U.S. Patent 3,308,067, issued March 7, 1967.

Also polyarnino-based compounds are useful herein including those derived from aspartic acid such as those disclosed in EP-A-30528? EP-A-305283 and EP-A-351629.

A further example of carboxylate-containing polyelectrolyte compounds suitable for the purpose of the invention include the maleic/acrylic/vinyl alcohol terpolymers. Such materials are also disclosed in EP 193,360, including, for example, the 45/45/10 terpolymer of acrylic/maleic/vinyl alcohol.

Terpolymers containing monomer units selected from maleic acid, acrylic acid and polyaspartic acid, particularly those having an average molecular weight of from 5,000 to 2 0,000, are also suitable herein.

Further useful carboxylate-containing polyelectrolyte compounds are the polyelectrodyte-containing glycols, particularly those of molecular weight 1000-10000, more particularly 2000 to 8000 and most preferably about 4000.

Other preferred carboxylate-containing polyelectrolyte compounds are those which typically have a hydrophilic backbone and at least one hydrophobic side chain.

Preferably this type of carboxylate-containing polyelectrolyte compounds have a molecular weight of between 500 and 100,000, more preferred from 1,000 to 20,000, especially preferred from 1,500 to 10,000 most preferred from 2,800 to 6,000. Carboxylate-containing polyelectrolyte compounds for use herein may for example be prepared by using conventional aqueous polymerisation procedures, suitable methods are for example described in GB 89 24477, GB 89 24478 and GB 89 24479.

Generally the hydrophilic backbone of the polymer is predominantly linear (the main chain of the backbone constitutes at least 50%, preferably more than 75%, most preferred more than 90% by weight of the backbone), suitable monomer constituents of the hydrophilic backbone are for example unsaturated C l-c6 acids, ethers, alcohols, aldehydes, ketones or esters, sugar units, alkoxy units, maleic anhydride and saturated polyalcohols such as glycerol. Preferably the hydrophobic sidegroups are composed of alkoxy groups for example butylene oxide and/or propylene oxide and/or alkyl or alkenyl chains having from 5 to 24 carbon atoms. The hydrophobic groups may be connected to the hydrophilic backbone via relatively hydrophilic bonds for example a poly ethoxy linkage.

Preferred carboxylate-containing polyelectrolyte compounds of this type are the polymers descibed in WO 91/ 08281.

Preferred counterions for the carboxylate-containing polyelectrolyte compounds are for example sodium, magnesium ans calcium ions.

Cationic polvmers The detergent composition or component thereof can comprise additional polymeric cationic ethoxylated amine compounds with particulate soil/claysoil removal/ anti-redeposition, selected from the group consisting of watersoluble cationic polymers. These polymers comprise a polymer backbone, at least 2M groups and at least one 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, C1 -C4 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:

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:

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 polyarmdes, the polyimides and the like, the polyacrylates, the polyacrylamides, the polyvinylethers, the polyethylenes, the polypropylenes and like polyalkylenes, the polystyrenes and like polyalkarylenes, the polyalkylenearnines, 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 (quartemary), positively charged center. The quarternary positively charged center can be represented by the following general structures E and F:

Particularly preferred M groups are those containing a quarternary 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, S032-, S042-, PO42-, MeOSO3~ and the like. Particularly preferred counter anions are C1-andBr.

X can be a nonionic group selected from hydrogen (H), C1-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 or components thereof 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 catiomc, 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 cationc/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 (M1) 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 M1 -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 -[(R'O)m(CH2CH2O)n]-. The moieties (R'O)rn and -(CH2CH20)n- of the polyoxyalkylene moiety can be mixed together, or preferably form blocks Of-(RO)m- and -(CH2CH20)n- 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)n-. The moiety -(CH2CH2O)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-, 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:

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 A1 is

Xis O or 1; R is H or Cl-C4 alkyl or hydroxyalkyl; R1 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 0-0 or O-N bonds are formed with A1: when xis 1, R2 is -R5except when A1 is

or is -(OR8)y- or -OR5- provided that no 0-0 or N-O bonds are formed with Al, and R3 is -R5- except when A1 is

or is -(R8O)-y or -R5O- provided that no 0-0 or O-N bonds are formed with A1; whenxis 0, R2 is

and R3 is -R5-; R4 is C1-C4 alkyl or hydroxyalkyl, or the moiety -(R5)k- [(C3H6O)m(CH2CH2O)n]-X; R5 is C1-C12 alkylene, hydroxyalkylene, alkenylene, arylene, or alkarylene; each R6 is C1 C4 alkyl or hydroxyalkyl, or the moiety -(CH2)r-A-(CH2)s-, wherein A2 is -O- or -CH2-; R7 is H or R4; R8 is C2-C3 alkylene or hydroxyalkylene; X is H,

-R9 or a mixture thereof, wherein R9 is C 1 -C4 alkyl or hydoxyalkyl; k is 0 or 1; m and n are numbers such that the moiety -(CH2CH2O)n- comprises at least about 85% by weight of the moiety -[(C3H6O)m(CH2CH2O)n]-; m is from 0 to about 5; n is at least about 3; ris 1 or 2, s is 1 or2, and r + s is 3 or 4; y is from 2 to about 20; the number of u, v and ware such that there are at least 2 N+ centers and at least 2 X groups.

In the above formulas, A1 is preferably

A2 is preferably -0-; x is preferably 1; and R is preferably H. R1 can be linear (e.g. -CH2-CH2-CH2-,

or branched

alkylene, hydroxyalkylene, alkenylene, cycloalkylene, alkarylene or oxyalkylene; when R1 is a C2-C3 oxyalkylene moiety, the number of oxyalkylene units is preferably from about 2 to about 12; R1 is preferably C2-C6 alkylene or phenylene, and most preferably C2 -C6 alkylene (e.g.

ethylene, propylene, hexamethylene). R2 is preferably -OR5- or R3 is preferably -R50- or -(0R8)y-; R4 and R6 are preferably methyl. Like Rl, R5 can be linear or branched, and is preferably C2-C3 alkylene; R7 is preferably H or C1-C3 alkyl; R8 is preferably ethylene; R9 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, Polyvinyl ether 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.

wherein

R is H or Cl-C4 alkyl or hydroxyalkyl; R1 is substituted C2-C12 alkylene, hydroxyalkylene, alkenylene, arylene or alkarylene, or C2-C3 oxyalkylene; each R2 is C1-C12 alkylene, hydroxyalkylene, alkenylene, arylene or alkarylene; each R3 is C1 -C4 alkyl or hydroxyalkyl, the moiety -(R2)k [(C3H6O)m(CH2CH2O)n]-X, or together form the moiety -(CH2)r-A2- (CH2)s-, wherein A2 is -O- or -CH2-; each R4 is Cl-C4 alkyl or hydroxyalkyl, or two R4 together form the moiety -(CH2)r-A2-(CH2)s-; X is H,

-R5 or mixture thereof, wherein R5 is C1-C4 alkyl or hydroxalkyl; j is 1 or O; k is 1 or 0; m and n are numbers such that the moiety -(CH2CH20)n- comprises at least about 85% by weight of the moiety [(C3H6O)m(CH2CH2O)n]-; m is from 0 to about 5; n is at least about 3; r is 1 or2,sis ior2andr+sis3or4; thenumberofu,vandwaresuch that there are at least 2N+ centres and at least 2 X groups.

In the above formulas, A1 is preferably

A2 is preferably -0-; R is preferably H. R1 can be linear

branched

substituted alkylene, hydroxyalkylene, alkenylene, alkarylene or oxyalkylene; R1 is preferably substituted C2-C6 alkylene or substituted C- C3 oxyalkylene, and most preferably

Each R2 is preferably C2-C3 alkylene, each R3 and R4 are preferably methyl; R5 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 polyalkylenearnines, polyalkyleneimines and the like. These polymers comprise units selected from those having formulas VII and VIII and IX.

wherein R1 is C2-C12 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 R2 is C1-C4 alkyl or hydroxyalkyl, or the moiety -(R3)k [(C3H6O)m(CH2CH2O)n]-X; R3 is Cl-C12 alkylene, hydroxyalkylene, alkenylene, arylene or alkarylene; M' is an N+ or N centre; X is H,

-R4 or mixture thereof, wherein R4 is C1-C4 alkyl or hydroxyalkyl; d is 1 when M' is N+ and is 0 when Mis N; e is 2 when M' is N+ and is 1 when Mis N; k is 1 or 0; m and n are numbers such that the moiety (CH2CH2O)n- comprises at least about 85% by weight of the moiety [(C3H6O)rn(CH2CH2O)n]; 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, R1 can be varied like R1 of the polyurethene and like polymers; each R2 is preferably methyl or the moiety -(R3)k [(C3H6O)rn(CH2CH2O)nJX; R3 is preferably C2-C3 alkylene; R4 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 11 X groups. For long chain length polymers, x T y + z 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 R2 (preferably methyl), M', X, d, x, y, z and n are defined as before; a is 1 or 0.

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

wherein x + y + z is from 2 to 9, and a is 0 or 1 (molecular weight offrom 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 tetraethylenepentanime (TEPA). Above the pentarmnes, 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:

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: CH2CH2 NH2 CH2CH2 NH 40% CH2CH2 N 30% 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 th PEI increases, especially much beyond about 1800. Also, the degree of ethoxyalation 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:

wherein R1 is C1 -C4 alkyl or hydroxyalkyl, or the moiety -(R2)k- [(C3H6O)m(CH2CH2O)n]-X; R is C1-C12 alkylene, hydroxyalkylene, alkylene, arylene or alkarylene; each R3 is C1-C4 alkyl or hydroxyalkyl, or together form the moiety -(CH2)r-A-(CH2)s-, wherein A is -O- or -CH2-; X is H,

-R4 or mixture thereof, wherein R4 is C1-C4 alkyl or hydroxyalkyl; k is 1 or O; m and n are numbers such that the moiety -(CH2CH2O)n- comprises at least about 85% by weight of the moiety -[(C3H6O)m(CH2CH2O)n]-; 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 3or4; xis 1 orO; y is 1 when x is 0 and 0 when x is 1; thenumberofu and v are such that there are at least 2N+ centres and at least 2 X groups.

In the above formulas, A is preferably -0-; R1 is preferably methyl; each R2 is preferably C2-C3 alkylene; each R3 is preferably methyl; R4 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 detergent components The detergent compositions or components thereof in accord with the invention may also contain additional detergent components. The precise nature of these additional components, and levels of incorporation thereof will depend on the physical form of the composition or component thereof, and the precise nature of the washing operation for which it is to be used.

The compositions or components thereof in accord with the invention preferably contain one or more additional detergent components selected from surfactants, additional builders, sequestrants, bleach, bleach precursors, bleach catalysts, additional organic polymeric compounds, enzymes, suds suppressors, additional 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 in accord with the invention 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 in aacord with the present invention 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 C1 2-C18 monoesters) diesters of sulfosuccinate (especially saturated and unsaturated C6-C14 diesters), N-acyl sarcosinates.

Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tallow oil.

Anionic 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 C- C17 acyl-N-(C 1 -C4 alkyl) and -N-(C1-C2 hydroxyalkyl) glucamine sulfates, and sulfates of alkylpolysaccharides such as the sulfates of alkylpolyglucoside (the nonionic nonsulfated compounds being described herein).

Alkyl sulfate surfactants are preferably selected from the linear and branched primary C10-C18 alkyl sulfates, more preferably the C 11-Cl S branched chain alkyl sulfates and the C12-Cl4 linear chain alkyl sulfates.

Alkyl ethoxysulfate surfactants are preferably selected from the group consisting of the C l o-C 18 alkyl sulfates which have been ethoxylated with from 0.5 to 20 moles of ethylene oxide per molecule. More preferably, the alkyl ethoxysulfate surfactant is a C11-C18 most preferably C11-C15 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 C- C20 linear alkylbenzene sulfonates, alkyl ester sulfonates, C6-C22 primary or secondary alkane sulfonates, C6-C24 olefin sulfonates, sulfonated polycarboxylic acids, alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfonates, and any mixtures thereof.

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

Suitable alkyl ethoxy carboxylates include those with the formula RO(CH2CH20)X CH2COO-M+ wherein R is a C6 to C18 alkyl group, x ranges from 0 to 10, and the ethoxylate distribution is such that, on a weight basis, the amount of material where x is O is less than 20 % and M is a cation. Suitable alkyl polyethoxy polycarboxylate surfactants include those having the formula RO-(CHRl-CHR2-O)-R3 wherein R is a C6 to C18 alkyl group, x is from 1 to 25, R1 and R2 are selected from the group consisting of hydrogen, methyl acid radical, succinic acid radical, hydroxysuccinic acid radical, and mixtures thereof, and R3 is selected from the group consisting of hydrogen, substituted or unsubstituted hydrocarbon having between 1 and 8 carbon atoms, and mixtures thereof.

Suitable soap surfactants include the secondary soap surfactants which contain a carboxyl unit connected to a secondary carbon. Preferred secondary soap surfactants for use herein are water-soluble members selected from the group consisting of the water-soluble salts of 2-methyl- 1 - undecanoic acid, 2-ethyl-1-decanoic acid, 2-propyl-1-nonanoic acid, 2 butyl-1 -octanoic acid and 2-pentyl-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 (R1) CH2 COOM, wherein R is a Cs-Cl7 linear or branched alkyl or alkenyl group, R1 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.

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

Preferred alkoxylated surfactants can be selected from the classes of the nonionic condensates of alkyl phenols, nonionic ethoxylated alcohols, nonionic ethoxylated/propoxylated fatty alcohols, nonionic ethoxylate/propoxylate condensates with propylene glycol, and the nonionic ethoxylate condensation products with propylene oxide/ethylene diarnine adducts.

Nonionic alkoxvlated 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 polvhvdroxv fattv acid amide surfactant Polyhydroxy fatty acid amides suitable for use herein are those having the structural formula R2CONR1Z wherein : R1 is H, C1-C4 hydrocarbyl, 2hydroxy ethyl, 2-hydroxy propyl, ethoxy, propoxy, or a mixture thereof; preferable C1-C4 alkyl, more preferably C1 or C2 alkyl, most preferably C1 alkyl (i.e., methyl); and R2 is a C5-C31 hydrocarbyl, preferably straightchain Cs-C19 alkyl or alkenyl, more preferably straight-chain Cg-C17 alkyl or alkenyl, most preferably straight-chain C11-C17 alkyl or alkenyl, or mixture thereof; and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof. Z preferably will be derived from a reducing sugar in a reductive amination reaction; more preferably Z is a glycityl.

Nonionic fattv acid amide surfactant Suitable fatty acid amide surfactants include those having the formula: R6CON(R7)2 wherein R6 is an alkyl group containing from 7 to 21, preferably from 9 to 17 carbon atoms and each R7 is selected from the group consisting of hydrogen, Cl -C4 alkyl, C1 -C4 hydroxyalkyl, and (C2H40)XH, where x is in the range of from 1 to 3.

Nonionic alkvlpolvsaccharide 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 R20(CnH2nO)t(glycosyl)x wherein R2 is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups contain from 10 to 18 carbon atoms; n is 2 or 3; t is from O to 10, and x is from 1.3 to 8. The glycosyl is preferably derived from glucose.

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

Suitable amine oxides include those compounds having the formula R3(0R4)XN0(R5)2 wherein R3 is selected from an alkyl, hydroxyalkyl, acylamidopropoyl and alkyl phenyl group, or mixtures thereof, containing from 8 to 26 carbon atoms; R4 is an alkylene or hydroxyalkylene group containing from 2 to 3 carbon atoms, or mixtures thereof; x is from 0 to 5, preferably from 0 to 3; and each 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 Clo-C18 alkyl dimethylamine oxide, and C 10-18 acylamido alkyl dimethylamine oxide.

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

Zwitterionic surfactant Zwitterionic surfactants can also be incorporated into the detergent compositions or components thereof in accord with the present invention.

These surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. Betaine and sultaine surfactants are exemplary zwitterionic surfactants for use herein.

Suitable betaines are those compounds having the formula R(R')2N+R2COO- wherein R is a C6-C18 hydrocarbyl group, each R1 is typically C1 -C3 alkyl, and R2 is a C1 -Cg hydrocarbyl group. Preferred betaines are C 12-18 dimethyl-ammonio hexanoate and the C 10-18 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 herein include the quaternary ammonium surfactants selected from mono C6-Cl6, preferably C6-C 10 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 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 No.s 4228042, 4239660 and 4260529.

In one preferred aspect the ester linkage and cationically charged group are separated from each other in the surfactant molecule by a spacer group consisting of a chain comprising at least three atoms (i.e. of three atoms chain length), preferably from three to eight atoms, more preferably from three to five atoms, most preferably three atoms. The atoms forming the spacer group chain are selected from the group consisting of carbon, nitrogen and oxygen atoms and any mixtures 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, -0-0- (i.e. peroxide), -N-N-, and -N-O- linkages are excluded, whilst spacer groups having, for example -CH2-O- CH2- and -CH2-NH-CH2- linkages are included. In a preferred aspect the spacer group chain comprises only carbon atoms, most preferably the chain is a hydrocarbyl chain.

Water-soluble builder compound The detergent compositions or components thereof in accord with the present invention can contain additional water-soluble builder compounds.

Suitable water-soluble builder compounds include carboxylate materials, borates, phosphates, and mixtures of any of the foregoing.

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 polymeta/phosphate in which the degree of polymerization ranges from about 6 to 21, and salts of phytic acid.

The carboxylate builder suitable for use in the detergant composition or components thereof can be momomeric or oligomeric (containing upto four carboxylate groups) in type although monomeric polycarboxylates are generally preferred for reasons of cost and performance.

Suitable, additional carboxylates containing one carboxy group include the water soluble salts of lactic acid, glycolic acid and ether derivatives thereof.

Carboxylates 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. Carboxylates 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 tricarboxylates described in British Patent No. 1,387,447.

Carboxylates 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.

Carboxylates 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 additional carboxylates 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.

Partially soluble or insoluble builder compound The detergent compositions or component thereof in accord with 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.

Examples of largely water insoluble builders include the sodium aluminosilicates.

Suitable aluminosilicate zeolites have the unit cell formula Naz[(A102)z(SiO2)y]. xH20 wherein z and y are at least 6; the molar ratio of z toy is from 1.0 to 0.5 and xis at least 5, preferably from 7.5 to 276, more preferably from 10 to 264. The aluminosilicate material are in hydrated form and are preferably crystalline, containing from 10% to 28%, more preferably from 18% to 2 Zeolite P, Zeolite X, Zeolite HS and mixtures thereof. Zeolite A has the formula Na 12 [A102) 12 (SiO2)12j. xH20 wherein x is from 20 to 30, especially 27. Zeolite X has the formula Na86 [(AlO2)86(SiO2)106]. 276 H20.

Another preferred aluminosilicate zeolite is zeolite MAP builder.

The zeolite MAP can be present at a level of from 1% to 80%, more preferably from 15% to 40% by weight of the compositions.

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 zeolite MAP detergent builder has a particle size, expressed as a d50 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 d50 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 scarining electron microscope or by means of a laser granulometer. Other methods of establishing d50 values are disclosed in EP 384070A.

Heavv metal ion sequestrant The detergent compositions or components thereof in accord with the invention preferably contain as an optional component a heavy metal ion sequestrant. By heavy metal ion sequestrant it is meant herein components which act to sequester (chelate) heavy metal ions. These components may also have calcium and 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 ethylenediamine-N.N'Misuccinic acid (EDDS) or the alkali metal, alkaline earth metal, ammonium, or substituted ammonium salts thereof, or mixtures thereof.

Other suitable heavy metal ion sequestrants for use herein are iminodiacetic acid derivatives such as 2-hydroxyethyl diacetic acid or glyceryl imino diacetic acid, described in EP-A-317,542 and EP-A-399,133. The iminodiacetic acid-N-2-hydroxypropyl sulfonic acid and aspartic acid N carboxymethyl N-2-hydroxypropyl-3-sulfonic acid sequestrants described in EP-A-516,102 are also suitable herein. The f3-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-5 10,331 describes suitable sequestrants derived from collagen, keratin or casein. EP A-528,859 describes a suitable alkyl iminodiacetic acid sequestrant.

Dipicolinic acid and 2-phosphonobutane- 1 ,2,4-tricarboxylic acid are alos suitable. Glycinamide-N,N'-disuccinic acid (GADS), ethylenediamine-N-N'diglutaric acid (EDDG) and 2-hydroxypropylenediamine-N-N'-disuccinic acid (HPDDS) are also suitable.

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

Inorganic perhvdrate 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 NaB02H202 or the tetrahydrate NaB02H202.3H20.

Alkali metal percarbonates, particularly sodium percarbonate are preferred perhydrates herein. Sodium percarbonate is an addition compound having a formula corresponding to 2Na2C03.3H202, and is available commercially as a crystalline solid.

Potassium peroxymonopersulfate is another inorganic perhydrate salt of use in the detergent compositions or components thereof.

Peroxvacid 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

where L is a leaving group and X is essentially any functionality, such that on perhydroloysis the structure of the peroxyacid produced is

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-1 586789. 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:

and mixtures thereof, wherein R1 is an alkyl, aryl, or alkaryl group containing from 1 to 14 carbon atoms, R3 is an alkyl chain containing from 1 to 8 carbon atoms, R4 is H or R3, R5 is an alkenyl chain containing from 1 to 8 carbon atoms and Y is H or a solubilizing group. Any of R1, R3 and R4 may be substituted by essentially any functional group including, for example alkyl, hydroxy, alkoxy, halogen, amine, nitrosyl, amide and ammonium or alkyl ammmonium groups The preferred solubilizing groups are SO3+, -C02M+, -S04M+, -N+(R3)4X and O < --N(R )3 and most preferably -SO3M and wherein R3 is an alkyl chain containing from 1 to 4 carbon atoms, M is a cation which provides solubility to the bleach activator and X is an anion which provides solubility to the bleach activator. Preferably, M is an alkali metal, ammonium or substituted ammonium cation, with sodium and potassium being most preferred, and X is a halide, hydroxide, methylsulfate or acetate anion.

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

Preferred alkyl percarboxylic precursor compounds of the imide type include the N-,N,N1N1 tetra acetylated alkylene diamines wherein the alkylene group contains from 1 to 6 carbon atoms, particularly those compounds in which the alkylene group contains 1, 2 and 6 carbon atoms. Tetraacetyl ethylene diamine (TAED) is particularly preferred.

Other preferred alkyl percarboxylic acid precursors mclude sodium 3,5,5-trimethyl hexanoyloxybenzene sulfonate (iso-NOBS), sodium nonanoyloxybenzene sulfonate (NOBS), sodium acetoxybenzene sulfonate (ABS) and pentaacetyl glucose.

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

wherein R1 is an alkyl group with from 1 to 14 carbon atoms, R2 is an alkylene group containing from 1 to 14 carbon atoms, and R5 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 succimmide, 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 groupcontaining perbenzoic acid precursors include N-benzoyl pyrrolidone, dibenzoyl taurine and benzoyl pyroglutamic acid.

Cationic peroxvacid 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, Nacylated 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 peroxvacid 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 R1 is H, alkyl, alkaryl, aryl, or arylalkyl.

Preformed organic peroxvacid 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:

wherein R1 is an alkyl, aryl or alkaryl group with from 1 to 14 carbon atoms, R2 is an alkylene, arylene, and alkarylene group containing from 1 to 14 carbon atoms, and R5 is H or an alkyl, aryl, or alkaryl group containing 1 to 10 carbon atoms. Arnide 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-phthaloylarninoperoxicaproic 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, lipases, amylases, 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, 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.

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

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

Another preferred lipase herein is obtained by cloning the gene from Humicola lanuginosa and expressing the gene in Aspergillus oryza, as host, as described in European Patent Application, EP-A-0258 068, which is commercially available from Novo Industri A/S, Bagsvaerd, Denmark, under the trade name Lipolase. This lipase is also described in U.S. Patent 4,810,414, Huge-Jensen et al, issued March 7, 1989.

Organic polvmeric compound Additional organic polymeric compounds can be used in the detergent compositions or components thereof in accord with the invention, and are preferably present as components of any particulate components where they may act such as to bind the particulate component together. By organic polymeric compound it is meant herein essentially any polymeric organic compound commonly used as dispersants, and anti-redeposition and soil suspension agents in detergent compositions, including any of the high molecular weight organic polymeric compounds described as clay flocculating agents herein, not being an quaternised ethoxylated (poly) anmie clay-soil removal/ anti-redeposition agent or anionic water-soluble polymeric polycarboxylic compound in accord with the invention, as described herein.

The additional organic polymeric compound is typically incorporated in the detergent compositions of the invention at a level of from 0.1% to 10%, preferably from 0.2% to 5%, most preferably from o.5% to 3% by weight of the compositions.

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

Suds suppressing system The detergent compositions of the invention, when formulated for use in machine washing compositions, preferably comprise a suds suppressing system present at a level of from 0.01% to 15%, preferably from 0.05% to 10%, most preferably from 0. 1% to 5% by weight of the composition.

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

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

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

Other suitable antifoam compounds include the monocarboxylic fatty acids and soluble salts thereof. These materials are described in US Patent 2,954,347, issued September 27, 1960 to Wayne St. John. The monocarboxylic fatty acids, and salts thereof, for use as suds suppressor typically have hydrocarbyl chains of 10 to 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 Ci 8-C40 ketones (e.g. stearone) N-alkylated amino triazines such as tri- to hexa-alkylinelamines or di- to tetra alkyldiarnine 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 DC0544, commercially available from DOW Corning under the tradename Do544; (c) an inert carrier fluid compound, most preferably comprising a C 16 C 18 ethoxylated alcohol with a degree of ethoxylation of from 5 to 50, preferably 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-A0210721 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 800C.

Polvmeric dve 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 polyarnine N-oxide polymers, copolymers of N-vinylpyrrolidone and Nvinylimidazole, polyvinylpyrrolidonepolymers or combinations thereof, whereby these polymers can be cross-linked polymers..

a) Polvamine 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 00 0 A is NC, CO, C, -O-, -S-, -N-; x is O or 1; R are aliphatic, ethoxylated aliphatics, aromatic, heterocyclic or alicyclic groups or any combination thereof 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

wherein R1, R2, and R3 are aliphatic groups, aromatic, heterocyclic or alicyclic groups or combinations thereof, x or/and y or/and z is O or 1 and wherein the nitrogen of the N-O group can be attached or wherein the nitrogen of the N-O group forms part of these groups. The N-O group can be part of the polymerisable unit (P) or can be attached to the polymeric backbone or a combination of both.

Suitable polyamine N-oxides wherein the N-O group forms part of the polymerisable unit comprise polyamine N-oxides wherein R is selected from aliphatic, aromatic, alicyclic or heterocyclic groups. One class of said polyamine N-oxides comprises the group of polyamine N-oxides wherein the nitrogen of the N-O group forms part of the R-group. Preferred polyamine N-oxides are those wherein R is a heterocyclic group such as pyrridine, pyrrole, Imidazole, pyrrolidine, piperidine, quinoline, acridine and derivatives thereof.

Other suitable polyamine N-oxides are the polyamine oxides whereto the N O group is attached to the polymerisable unit. A preferred class of these polyamine N-oxides comprises the polyamine N-oxides having the general formula (I) wherein R is an aromatic,heterocyclic or alicyclic groups wherein the nitrogen of the N-O functional group is part of said R group.

Examples of these classes are polyamine oxides wherein R is a heterocyclic compound such as pyrndine, 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-vinylpvrrolidone and N-vinvlimidazole 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 Nvinylpyrrolidone from 1 to 0.2.

c) Polvvinvlpvrrolidone The detergent compositions herein may also utilize polyvinylpyrrolidone ("PVP") having an average molecular weight of from 2,500 to 400,000.

Suitable polyvinylpyrrolidones are commercially vailable from ISP Corporation, New York, NY and Montreal, Canada under the product names PVP K-15 (viscosity molecular weight of 10,000), PVP K-30 (average molecular weight of 40,000), PVP K-60 (average molecular weight of 160,000), and PVP K-90 (average molecular weight of 360,000). PVP K15 is also available from ISP Corporation. Other suitable polywinylpyrrolidones which are commercially available from BASF Cooperation include Sokalan HP 165 and Sokalan HP 12.

d) Polvvinvloxazolidone 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) Polyvinvlimidazole 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 R1 is selected from anilino, N-2-bis-hydroxyethyl and NH-2hydroxyethyl; R2 is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl N-methylarmno, morphilino, chloro and amino; and M is a salt-fonning cat

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

Polvmeric 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 incorporated 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. Gosselink. Such ester oligomers can be prepared by: (a) ethoxylating allyl alcohol; (b) reacting the product of (a) with dimethyl terephthalate ("DMT") and 1,2propylene 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 1,2propylene/polyoxyethylene terephthalate polyesters of U.S. 4,711,730, December 8, 1987 to Gosselink 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 Gosselink, 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 Gosselink, 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, Gosselink 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 C1-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 200C as a 2% aqueous solution. Such materials are available as METOLOSE SM100 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 tenninals 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 terephthalatebased SRA's of the urethane-linked variety, see U.S. 4,201,824, Violland et al.; Other optional ingredients Other optional ingredients suitable for inclusion in the compositions of the invention include perfumes, colours and filler salts, with sodium sulfate being a preferred filler salt.

Near neutral wash pH detergent formulation While the detergent compositions of the present invention are operative within a wide range of wash pHs (e.g. from about 5 to about 12), they are particularly suitable when fonnulated to provide a near neutral wash pH, i.e.

an initial pH of from about 7.0 to about 10.5 at a concentration of from about 0.1 to about 2% by weight in water at 200C. Near neutral wash pH formulations are better for enzyme stability and for preventing stains from setting. In such formulations, the wash pH is preferably from about 7.0 to about 10.5, more preferably from about 8.0 to about 10.5, most preferably from 8.0 to 9.0.

Preferred near neutral wash pH detergent formulations are disclosed to European Patent Application 83.200688.6, filed May 16, 1983, J.H.M.

Wertz and P.C.E. Goffinet.

Highly preferred compositions of this type also preferably contain from about 2 to about 10% by weight of citric acid and minor amounts (e.g., less than about 20% by weight) of neutralizing agents, buffering agents, phase regulants, hydrotropes, enzymes, enzyme stabilizing agents, polyacids, suds regulants, opacifiers, anti-oxidants, bactericides, dyes, periumes and brighteners, such as those described in US Patent 4,285,841 to Barrat et al., issued August 25, 1981 (herein incorporated by reference).

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

The detergent component preferably forms part of a detergent composiiton.

The compositions in accordance with the invention can take 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 compositions in accord with the present invention can also be used in or in combination with bleach additive compositions, for example comprising chlorine bleach.

In general, granular detergent compositions in accordance with the present invention can be made via a variety of methods including dry mixing, spray drying, agglomeration and granulation. The quaternised clay-soil removal/ anti-redeposition agent in accord with the present invention can be added to the other detergent components by dry-mixing, agglomeration (preferably combined with a carrier material) or as a spray-dried component.

The mean particle size of the components of granular compositions in accordance with the invention, comprising the water-soluble cationic claysoil removal/anti-redeposition compounds, should preferably be such that no more that 15% of the particles are greater than 1 .8mm in diameter and not more than 15% of the particles are less than 0.25mm in diameter. Preferably the mean particle size is such that from 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.

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 fimnel 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/cm2, more preferably from 5 to 11KN!cm2 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 syrnmetrical to ensure the uniform dissolution of the tablet in the wash solution.

Laundry washing method Machine laundry methods herein typically comprise treating soiled laundry with an aqueous wash solution in a washing machine having dissolved or dispensed therein an effective amount of a machine laundry detergent composition in accord with the invention. By an effective amount of the detergent composition it is meant from lOg to 300g of product dissolved or dispersed in a wash solution of volume from 5 to 65 litres, as are typical product dosages and wash solution volumes commonly employed in conventional machine laundry methods.

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

The dispensing device containing the detergent product is placed inside the drum before the commencement of the wash, either before, or simultaneously with or after the washing machine has been loaded with laundry. At the commencement of the wash cycle of the washing machine water is introduced into the drum and the drum periodically rotates. The design of the dispensing device should be such that it permits containinent of the dry detergent product but then allows release of this product during the wash cycle in response to its agitation as the drum rotates and also as a result of its contact with the wash water.

To allow for release of the detergent product during the wash the device may possess a number of openings through which the product may pass.

Alternatively, the device may be made of a material which is permeable to liquid but impermeable to the solid product, which will allow release of dissolved product. Preferably, the detergent product will be rapidly released at the start of the wash cycle thereby providing transient localised high concentrations of product in the drum of the washing machine at this stage of the wash cycle.

Preferred dispensing devices are reusable and are designed in such a way that container integrity is maintained in both the dry state and during the wash cycle. Especially preferred dispensing devices for use with the composition of the invention have been described in the following patents; GB-B-2, 157, 717, GB-B-2, 157, 718, EP-A-0201376, EP-A-0288345 and EP-A-0288346. An article by J.Bland published in Manufacturing Chemist, November 1989, pages 41-46 also describes especially preferred dispensing devices for use with granular laundry products which are of a type commonly know as the "granulette". Another preferred dispensing device for use with the compositions of this invention is disclosed in PCT Patent Application No. WO94/11562.

Especially preferred dispensing devices are disclosed in European Patent Application Publication Nos. 0343069 & 0343070. The latter Application discloses a device comprising a flexible sheath in the form of a bag extending from a support ring defining an orifice, the orifice being adapted to admit to the bag sufficient product for one washing cycle in a washing process. A portion of the washing medium flows through the orifice into the bag, dissolves the product, and the solution then passes outwardly through the orifice into the washing medium. The support ring is provided with a masking arrangemnt to prevent egress of wetted, undissolved, product, this arrangement typically comprising radially extending walls extending from a central boss in a spoked wheel configuration, or a similar structure in which the walls have a helical form.

Alternatively, the dispensing device may be a flexible container, such as a bag or pouch. The bag may be of fibrous construction coated with a water impermeable protective material so as to retain the contents, such as is disclosed in European published Patent Application No. 0018678.

Alternatively it may be formed of a water-insoluble synthetic polymeric material provided with an edge seal or closure designed to rupture in aqueous media as disclosed in European published Patent Application Nos.

0011500,0011501,0011502,and0011968. Aconvenientformofwater frangible closure comprises a water soluble adhesive disposed along and sealing one edge of a pouch formed of a water impermeable polymeric film such as polyethylene or polypropylene.

Machine dishwashing method Any suitable methods for machine dishwashing or cleaning soiled tableware, particularly soiled silverware are envisaged.

A preferred machine dishwashing method comprises treating soiled articles selected from crockery, glassware, hollowware, silverware and cutlery and mixtures thereof, with an aqueous liquid having dissolved or dispensed therein an effective amount of a machine dishwashing composition in accord with the invention. By an effective amount of the machine dishwashing composition it is meant from 8g to 60g of product dissolved or dispersed in a wash solution of volume from 3 to 10 litres, as are typical product dosages and wash solution volumes commonly employed in conventional machine dishwashing methods.

Packagin for the compositions Commercially marketed executions of the bleaching compositions can be packaged in any suitable container including those constructed from paper, cardboard, plastic materials and any suitable laminates. A preferred packaging execution is described in European Application No. 94921505.7.

Abbreviations used in Examples In the detergent compositions, the abbreviated component identifications have the following meanings: LAS Sodium linear C 12 alkyl benzene sulfonate TAS Sodium tallow allcyl sulfate CxyAS Sodium Clx - Cly alkyl sulfate C46SAS Sodium C14 - C16 secondary (2,3) alkyl sulfate CxyEzS Sodium Clx-Cly alkyl sulfate condensed with z moles of ethylene oxide CxyEz C1 x-C 1 y predominantly linear primary alcohol condensed with an average of z moles of ethylene oxide QAS R2 N+(CH3)2(C2H4OH) with R2 = C12- C14 Soap Sodium linear alkyl carboxylate derived from an 80/20 mixture of tallow and coconut oils CFAA C12-C14 (coco) alkyl N-methyl glucamide TFAA C16-C18 alkyl N-methyl glucamide TPKFA C 12 C 14 topped whole cut fatty acids STPP Anhydrous sodium tripolyphosphate TSPP Tetrasodium pyrophosphate Zeolite A Hydrated Sodium Aluminosilicate of formula Nal2(A102SiO2)12.27H20 having a primary particle size in the range from 0.1 to 10 micrometers Zeolite MAP Hydrated sodium aluminosilicate zeolite MAP having a silicon to aluminium ratio of 1.07 NaSKS-6 Crystalline layered silicate of formula 6 Na2Si205 Citric acid Anhydrous citric acid Borate Sodium borate Carbonate Anydrous sodium carbonate with a particle size between 200 m and 900Rm Bicarbonate Anhydrous sodium bicarbonate with a particle size distribution between 400m and 1200,um Silicate Amorphous 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 425 m and 8501lm MA/AA 1 Copolymer of 1:2.3 maleic/acrylic acid, average molecular weight about 70,000 MA/AA 2 Copolymer of 4:6 maleic/acrylic acid, average molecular weight about 3,000 MA/AA 3 Copolymer of 4:6 maleic/acrylic acid, average molecular weight about 12,000 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 bv 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 100KLU/g sold by NOVO Industries A/S under the tradename Lipolase Endolase . Endoglucanase enzyme of activity 3000 CEVUIg sold by NOVO Industries A/S PB4 Sodium perborate tetrahydrate of nominal formula NaB02 .3H20.H202 PB 1 Anhudrous sodium perborate bleach of nominal formula NaB02.H202 Percarbonate Sodium percarbonate of nominal formula 2Na2C03 .3H202 NOBS Nonanoyloxybenzene sulfonate in the form of the sodium salt TAED Tetraacetylethylenediamine Mn catalyst MnIV2(m-0)3(1 ,4,7-trimethyl-l ,4,7- triazacyclononane)2 (PFg)2, as described in U.S.

Pat. Nos. 5,246,621 and 5,244,594.

DTPA Diethylene triarmne 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 Di sodium 4 ,4'-bis(2-sulphostyry)biphenyl Brightener 2 Disodium 4,4'-bis(4-anilino-6-morpholino-1.3.5- triazin-2-yl)amino) stilbene-2:2'-disulfonate HEDP l,l-hydroxyethane diphosphonic acid EDDS Ethylenediamine-N, N'-disuccinic acid QEA1 bis((C2H50)(C2H40)n) (CH3) -N±C6H1 2-N± (CH3) bis((C2HsO)-(C2H4O)n), wherein n=from 20 to 30 QEA2 bis((C2HsO)-(C2H4O)n) (CH3) N+ R1, wherein R1 is C4-C12 alkyl group and n=from 20 to 30 QEA 3 tri{(bis((C2H5O)-(C2H4O)n)(CH3)-N+) (CONC3H6)}-C3H6O, wherein n=from 20to26 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 SRP 1 Sulfobenzoyl and capped esters with oxyethylene oxy and terephtaloyl backbone SRP 2 Diethoxylated poly (1, 2 propylene terephtalate) short block polymer Silicone antifoam Polydimethylsiloxane foam controller with siloxane-oxyalkylene copolymer as dispersing agent with a ratio of said foam controller to said dispersing agent of 10:1 to 100:1 Wax Paraffin wax In the following examples all levels are quoted as % by weight of the composition: Example 1 The following high density granular laundry detergent compositions A to F of particular utility under European machine wash conditions were prepared in accord with the invention:

A B C D E F LAS 8.0 8.0 8.0 8.0 8.0 8.0 C25E3 3.4 3.4 3.4 3.4 3.4 3.4 C46AS 1.0 2.0 2.5 - 3.0 4.0 C68AS 3.0 2.0 5.0 7.0 1.0 0.5 QAS - - 0.8 - - 0.8 Zeolite A 18.1 18.1 16.1 18.1 18.1 18.1 Zeolite MAP 4.0 3.5 - - Carbonate 13.0 13.0 13.0 27.0 27.0 27.0 Silicate 1.4 1.4 1.4 3.0 3.0 3.0 Sodium Sulfate 26.1 26.1 26.1 26.1 26.1 26.1 MA/AA 1 0.6 0.8 0.3 1.0 0.5 0.3 CMC 0.2 | 0.2 0.2 0.2 0.2 0.2 PB4 9.0 9.0 9.0 9.0 9.0 9.0 TAED 1.5 1.5. 1.0 | 1.5 - 1.5 Mn Catalyst - 0.03 0.07 - - DTPMP 0.25 0.25 0.25 0.25 0.25 0.25 HEDP 0.3 0.3 0.2 0.2 | 0.3 I 0.3

EDDS | - | - | 0.4 | 0.2 | - | QEA 1 1.0 0.8 0.7 1.2 - 0.5 QEA2 2 - - - - 1.0 0.5 Protease 0.26 0.26 0.26 0.26 0.26 0.26 Amylase 0.1 0.1 0.4 0.3 0.1 0.1 Photoactivated 15 15 15 15 15 15 bleach (ppm) ppm ppm ppm ppm ppm ppm Brightener 1 0.09 0.09 0.09 0.09 0.09 0.09 Perfine 0.3 0.3 0.3 0.3 0.3 0.3 Silicone antifoam 0.5 0.5 0.5 0.5 0.5 0.5 Misc/minors to 100% Density in g/litre 850 850 850 850 850 850 Example 2 The following granular laundry detergent compositions G to I of particular utility under European machine wash conditions were prepared in accord with the invention:

G H I LAS 5.25 5.61 4.76 TAS 1.25 1.86 1.57 C45AS 2.24 3.89 C25E3S 0.76 1.18 C45E7 3.25 - 5.0 C25E3 5.5 QAS 0.8 2.0 2.0 STPP 19.7 1 Zeolite A - 19.5 19.5 Zeolite MAP 2.0 1 NaSKS6/citric acid (79:21) 10.6 10.6 Carbonate 6.1 21.4 21.4 Bicarbonate 2.0 2.0 Silicate 6.8 - Sodium Sulfate 39.8 - 14.3 MA/AA 1 0.8 1.6 1.6 MA/AA2 0.4 -

CMC 0.2 0.4 0.4 PB4 5.0 12.7 Percarbonate 5.0 - 12.7 TAED 0.5 3.1 DTPMP 0.25 0.2 0.2 HEDP 0.3 0.3 QEA1 0.9 1.2 QEA 2 1.0 Protease 0.26 0.85 0.85 Lipase 0.15 0.15 0.15 Cellulase 0.28 0.28 0.28 Amylase 0.4 0.1 0.1 PVP 0.9 1.3 0.8 Photoactivated bleach (ppm) 15 ppm 27 ppm 27 ppm Brightener I 0.08 0.19 0.19 Brightener 2 0.04 0.04 Perfume 0.3 0.3 0.3 Silicone antifoam 0.5 2.4 2.4 Minors!misc to 100% Example 3 The following detergent formulations of particular utility under European machine wash conditions were prepared in accord with the invention.

J K L M Blown powder LAS 6.0 5.0 | 11.0 6.0 TAS 2.0 - - 2.0 Zeolite A 27.0 - 20.0 STPP 24.0 - 24.0 Sulfate 9.0 6.0 13.0 MA/AA 2 2.0 - - 4.0 MA/AA 1 - 4.0 6.0 Silicate 7.0 3.0 3.0 3.0 CMC 1.0 1.0 0.5 0.6 QEA 1 0.8 1.0 1.4 0.5 QEA 2 - - - 0.5 Brightener 0.2 0.2 0.2 0.2 Silicone antifoam 1.0 1.0 1.0 0.3 DTPMP 0.4 0.4 0.2 0.4 Spray on C45E7 - - - 5.0 C45E2 2.5 2.5 2.0 C45E3 2.6 2.5 2.0 Perfume 0.3 0.3 0.3 0.2 Silicone antifoam 0.3 0.3 0.3 Dry additives Sulfate 3.0 3.0 5.0 10.0 Carbonate 6.0 13.0 15.0 14.0 PB1 - - - 1.5 PB4 18.0 18.0 10.0 18.5 <S

Amylase 0.2 0.2 0.2 0.4 Photoactivated bleach - - - 0.15 Total 100.0 100.0 100.0 100.0 Example 4 The following granular detergent formulations were prepared in accord with the invention. Formulation N is particularly suitable for usage under Japanese machine wash conditions. Formulations O to S are particularly suitable for use under US machine wash conditions.

N O P Q R S Blown powder LAS 22.0 5.0 4.0 9.0 8.0 7.0 C45AS 7.0 7.0 6.0 - - C46AS - 4.0 3.0 - - C45E35 - 3.0 2.0 8.0 5.0 4.0 Zeolite A 6.0 16.0 14.0 19.0 16.0 14.0 MA/AA 1 6.0 3.0 3.0 - - MA/AA2 - 3.0 - 2.0 3.0 5.0 AA - - 3.0 2.0 3.0 Sodium Sulfate 7.0 18.3 11.3 24.0 19.3 19.3 Silicate 5.0 1.0 1.0 - 2.0 1.0 1.0 Carbonate 28.3 9.0 7.0 | 25.7 8.0 6.0 QEA 1 0.9 0.9 - - 0.5 1.1 QEA 2 - 0.8 1.0 - QEA 3 - - 0.4 - - PEG 4000 0.5 1.5 1.5 1.0 1.5 1.0 Sodium oleate 2.0 - - - - - DTPA 0.4 - 0.5 - - 0.5 Brightener 0.2 0.3 0.3 0.3 0.3 0.3 Spray on C25E9 1.0 - - - - C45E7 - 2.0 2.0 0.5 2.0 2.0 Perfume 1.0 0.3 0.3 1.0 0.3 0.3 Agglomerates C45AS - 5.0 5.0 - 5.0 5.0 LAS - 2.0 2.0 - | 2.0 2.0 Zeolite A 7.5 7.5 - 7.5 7.5 HEDP - 1.0 | - | - 2.0

Carbonate - 4.0 4.0 - 4.0 4.0 PEG 4000 - 0.5 0.5 - 0.5 0.5 Misc (water etc) - 2.0 2.0 - 2.0 2.0 Dry additives TEAD 1.0 2.0 3.0 1.0 3.0 2.0 PB4 - 1.0 4.0 - 5.0 0.5 PB1 6.0 - - - - Percarbonate - 5.0 12.5 - | - | - Carbonate - 5.3 1.8 - 4.0 4.0 NOBS 4.5 - 6.0 - - 0.6 Cumeme sulfonic acid - 2.0 2.0 - 2.0 2.0 Lipase 0.4 0.4 0.4 - 0.4 0.4 Cellulase 0.1 0.2 0.2 - 0.2 0.2 Amylase 0.1 0.3 0.3 - - - Protease 1.0 0.5 0.5 0.5 0.5 0.5 PVPVI - 0.5 0.5 - - PVP 0.5 0.5 0.5 - | - | - PVNO - 0.5 0.5 - - SRP1 - 0.5 0.5 - - Silicone antifoam - 0.2 0.2 - 0.2 0.2 Total 100.0 100.0 100.0 100.0 100.0 100.0 Example 5 The following granular detergent formulations were prepared in accord with the invention. Formulations W and X are of particular utility under US machine wash conditions. Y is of particular utility under Japanese machine wash conditions

T U V Blown Powder Zeolite A 30.0 22.0 6.0 Sodium Sulfate 190 5.0 7.0 MA/AA - 3.0 6.0 MA/AA 3 3.0 - - LAS 14.0 12.0 22.0 C45AS 8.0 7.0 7.0 Silicate r 1.0 5.0 Soap - - 2.0 Brightener 1 0.2 0.2 0.2 QEA 1 0.6 2.0 1.0 Carbonate 8.0 16.0 20.0 DTPMP - 0.4 0.4 Spray On - 1.0 5.0 C45E7 1.0 1.0 1.0 Dry additives HEDP 1.0 - PVPVI/PVNO 0.5 0.5 0.5 Protease 1.0 | 1.0 1.0 Lipase 0.4 0.4 0.4 Amylase 0.1 | 0.1 0.1 Cellulase 0.1 0.1 0.1 TEAD - 6.1 4.5 PB1 11.0 5.0 6.0 Sodium Sulfate - 6.0 Balance (Moisture and Misc.) Example 6 The following granular detergent compositions of particular utility under European wash conditions were prepared in accord with the invention.

w x Blown powder Zeolite A 20.0 STPP - 20.0 LAS 6.0 6.0 C68AS 2.0 2.0 Silicate 3.0 8.0 MA/AA 1 4.0 2.0 MA/AA 2 2.0 CMC 0.6 0.6 QEA 1 0.9 0.6 QEA 3 0.1 Brightener 1 0.2 0.2 DTPMP 0.4 0.4 Spray on C45E7 5.0 5.0 Silicone antifoam 0.3 0.3 Perfume 0.2 0.2 Dry additives Carbonate 14.0 9.0 PB1 1.5 2.0 PB4 18.5 13.0 TAED 2.0 2.0 Photoactivated bleach 15 ppm 15 ppm Protease 1.0 1.0 Lipase 0.2 0.2 Amylase 0.4 0.4 Cellulase 0.1 0.1 Sulfate 10.0 20.0 Balance (Moisture and Misc.)

Density (g/litre) 700 700 Example 7 The following detergent compositions, according to the present invention were prepared:

Y Z AA Blown Powder Zeolite A 15.0 15.0 15.0 Sodium Sulfate 0.0 5.0 0.0 LAS 3.0 3.0 3.0 QAS - 1.5 1.5 DTPMP 0.4 0.2 0.4 CMC 0.4 0.4 0.4 MA/AA 1 - 2.0 MA/AA 2 2.0 AA - 4.0 Agglomerates LAS 5.0 5.0 5.0 TAS 2.0 2.0 1.0 Silicate 3.0 3.0 4.0 QEA 1 1.0 2.5 0.6 Mn Catalyst 0.03 Zeolite A 8.0 8.0 8.0 Carbonate 8.0 8.0 4.0 Spray On Perfume 0.3 0.3 0.3 C45E7 2.0 2.0 2.0 C25E3 2.0 - Dry additives Citrate 5.0 - 2.0 Bicarbonate - 3.0 Carbonate 8.0 - 15.0 10.0 Percarbonate - 7.0 10.0 TAED 6.0 2.0 5.0 PB1 14.0 7.0 10.0 EDDS - 2.0 Polyethylene oxide of MW 5,000,000 - - 0.2

Bentoniteclay 10.0 Protease 1.0 1.0 1.0 Lipase 0.4 0.4 0.4 Amylase 0.6 0.6 0.6 Cellulase 0.6 0.6 0.6 Silicone antifoam 5.0 5.0 5.0 Dry additives Sodium sulfate 0.0 3.0 0.0 Balance (Moisture and Misc.) 100.0 100.0 100.0 Density (litre) 850 850 850 Example 8 The following detergent formulations, according to the present invention were prepared:

BB CC DD EE LAS 20.0 14.0 24.0 22.0 QAS 0.7 1.0 - 0.7 TFAA - 1.0 C25E5/C45E7 - 2.0 - 0.5 C45E3S - 2.5 STPP 30.0 18.0 30.0 22.0 Silicate 9.0 5.0 10.0 8.0 Carbonate 13.0 7.5 - 5.0 Bicarbonate - 7.5 Percarbonate - 5.0 9.0 15.0 DTPMP 0.7 1.0 - QEA 1 0.4 1.2 0.5 2.0 QEA 2 0.4 - - SRP 1 0.3 0.2 - 0.1 MA/AA 1 2.0 1.5 - 1.0 MA/AA 2 - 1.5 - AA 2.0 1.0 CMC 0.8 0.4 0.4 0.2 Protease 0.8 1.0 0.5 0.5 Amylase 0.8 0.4 1 0.25 Lipase 0.2 0.1 0.2 0.1 Cellulase 0.15 0.05 Photoactivated 70ppm 45ppm 1 Oppm bleach (ppm) Brightener 1 0.2 0.2 0.08 0.2 PB1 6.0 2.0 l - HEDP - - 2.3 TEAD 2.0 1.0 - Balance (Moisture and Miscellaneous) Example 9 The following laundry bar detergent compositions were prepared in accord with the invention.

FF GG HH II JJ KK LL MM LAS - - 19.0 15.0 21.0 6.75 8.8 C28AS 30.0 13.5 - - - 15.75 11.2 22.5 Sodium laurate 2.5 9.0 - - - - - Zeolite A 2.0 1.25 - - - 1.25 1.25 1.25 Carbonate 20.0 3.0 13.0 8.0 10.0 15.0 15.0 10.0 Calcium 21.5 - - - - - - carbonate Sulfate 5.0 - - - - - - TSPP 5.0 - 5.0 - 5.0 5.0 2.5 5.0 STPP 5.0 15.0 - - - 5.0 8.0 10.0 Bentonite clay - 10.0 - - 5.0 - - DTPMP - 0.7 0.6 - 0.6 0.7 0.7 0.7 MA/AA 1 0.4 1.0 - - 0.2 0.4 0.5 0.4 MA/AA 2 - 0.9 1.2 0.8 0.8 - SRP1 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Protease - 0.12 - 0.08 0.08 - - 0.1 Lipase - 0.1 - 0.1 - - - Amylase - - 0.8 - - - 0.1 Cellulase - 0.15 - - 0.15 - - PEO - 0.2 - 0.2 0.3 - - 0.3 Perfume 1.6 - - - - - - Example 10 The following compact high density (0.96Kg/l) dishwashing detergent compositions NN to SS were prepared in accord with the invention and the abbreviated component identifications, used in the dish washing detergent compositions, have the following meanings: Metasilicate : Sodium metasilicate (SiO2:Na2O ratio = 1.0) Nonionic C1 3-C 15 mixed ethoxylated/propoxylated fatty alcohol with an average degree of ethoxylation of 3.8 and an average degree of propoxylation of 4.5 sold under the tradename Plurafac LF404 by BASF GmbH (low foaming) PAAC . Pentaamine acetate cobalt (III) salt BzP Benzoyl Peroxide Paraffin Paraffin oil sold under the tradename Winog 70 by Wintershall.

BTA Benzotriazole Bismuth nitrate . Bismuth nitrate salt Terpolymer Terpolymer of average molecular weight approx. 7,000, comprising acrylic: maleic : ethylacrylic acid monomer units at a weight ratio of 60:20:20 480N Random copolymer of 3:7 acrylic/methacrylic acid, average molecular weight about 3,500

NN OO PP QQ RR SS STPP 24.80 24.80 25.00 28.39 28.50 20.00 Citrate - - - - 10.00 10.00 Carbonate - - 17.50 17.50 - - QEA 1 0.5 1.5 2.0 1.0 1.3 0.8 Silicate 20.36 20.36 14.81 14.81 14.81 Metasilicate 2.50 2.50 2.50 - - - PB1 7.79 7.79 9.74 14.28 9.74 PB4 - - - - 10.4 Percarbonate - - - - - 6.70 Non-ionic 1.50 1.50 2.00 1.50 2.00 2.60 TAED 2.39 2.00 2.70 2.00 3.60 4.00 HEDP 0.46 0.46 1.00 - 0.83 DETPMP - - 0.65 - - PAAC - - - 0.20 - BzP - - - 4.44 - Paraffin 0.50 0.50 0.50 0.50 - 0.20 Protease 2.20 2.20 2.20 2.20 2.00 0.50 Amylase 1.50 1.50 1.20 1.50 1.00 1.10 BTA 0.30 0.30 0.30 0.30 - Bismuth Nitrate - - 0.30 - - Terpolymer - - - 4.00 - MA/AA 2 2.77 | 2.77 6.00 4.50 6.67 3.85 Sulphate 8.44 8.44 20.77 - 23.24 1.00 Misc inc moisture to balance pH (1 % solution) 10.90 10.90 11.00 10.80 10.90 9.60

Claims (23)

Claims 1. A granular detergent composition or component thereof, comprising (a) a carboxylate-containing polyelectrolyte compound; and (b) 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:

2) ethoxylated cationic diamines having the formula:

wherein M1 is an N+ or N group; each M2 is an Nr or N group, and at least one M2 is an N+ group; 3) ethoxylated cationic polyamines having the formula:

4) mixtures thereof; wherein A is

R is H or C1-C4 alkyl or hydroxyalkyl, R1 is C2-C12 alkylene, hydroxyalkylene, alkenylene, 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 R2 is C1 -C4 alkyl or hydroxyalkyl, the moiety -L X, or two R2 together form the moiety -(CH2)rA2-(CH2)s-, wherein A2 is O- or -CH2-, r is 1 or2, sis 1 or2 andr+sis3 or4; eachR3 isC1-C8 alkyl or hydroxyalkyl, benzyl, the moiety L-X, or two R3 or one R2 and one R3 together form the moiety -(CH2)r-A-(CH2)s-; R4 is a substituted C3 C 12 alkyl, hydroxyalkyl, alkenyl, aryl or alkaryl group having p substitution sites; R5 is C1-C 12 alkenyl, hydroxyalkylene, alkenylene, arylene or alkarylene, or a C2-C3 oxyalkylene moiety having from 2 to about 20 oxyalkylene units provided that no 0-0 or O-N bonds are formed; X is a nonionic group selected from the group consisting of H, Cl-C4 alkyl or hydroxyalkyl ester or ether groups, and mixtures thereof; L is a hydrophilic chain which contains the polyoxyalkylene moiety -{(R60)m(CH2CH20)n]-; wherein R6 is C3-C4 alkylene or hydroxyalkylene and m and n are numbers such that the moiety -(CH2CH2O)n- comprises at least about 50% by weight of said polyoxyalkylene moiety; d is 1 when M2 is N+ and is 0 when M2 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 wherein the ratio of compound (a) to (b) is from 1:95 to 95:1 2. A granular detergent composition or component thereof; according to Claim 1 wherein said ratio is from 1:25 to 25:1.

3. A granular detergent composition according to Claims 1 or 2 wherein said cationic compound is present at a level of from 0.01% to 30% by weight of the detergent composition.

4. A granular detergent composition according to any of Claims 1 to 3 wherein the cationic compound is present at a level of from 0.2% to 3% by weight.

5. A granular detergent composition or component thereof; according to any of Claims 1 to 4 wherein said cationic compound is an ethoxylated cationic monoamine and is characterised in that one R2 is methyl, two R2 are the moiety L-X, m is 0 and n is at least about 20.

6. A granular detergent composition or component thereof; according to any of Claims 1 to 4 wherein said cationic compound is an ethoxylated cationic diamine and is characterised in that R1 is a C2 C6 alkylene.

7. A granular detergent composition or component thereof; according to any of Claims 1 to 4 or 6 wherein said ethoxylated cationic diamine is characterised in that R1 is hexamethylene.

8. A detergent composition or component thereof; according to any of Claims 1 to 4 wherein said cationic compound is an ethoxylated cationic polyamine and is characterised in that R4 is a substituted C3 C6 alkyl, hydroxyalkyl or aryl group; Al is

and pisfrom3to6.

9. A granular detergent composition or component thereof, according to any of Claims 6 to 8, wherein the cationic compounds is characterised in that each R2 is methyl or the moiety -L-X, each R3 is methyl and M1 and each M2 are an N+ group.

10. A granular detergent composition or component thereof, according to any of Claims 6 to 9 wherein mis 0 and n is at least 12.

11. A granular detergent composition or component thereof, according to Claims 6 or 7 wherein m is 0 and n is at least 20.

12. A granular detergent composition according to any of Claims 1 to 11 wherein said carboxylate-containing polyelectrolyte compound is present at a level of from 0.01% to 40% by weight of the detergent composition.

13. A granular detergent composition according to any of Claims 1 to 12 wherein the carboxylate-containing polyelectrolyte compound is present at a level of from 0.2% to 6 % by weight of the composition.

14. A granular detergent composition or component thereof, according to any of Claims 1 to 13 wherein the carboxylate-containing polyelectrolyte compound is a maleic/ acrylic co-polymer.

15 A granular detergent composition or component thereof according to any of Claims 1 to 14 wherein the carboxylate-containing polyelectrolyte compound comprises acrylate segrnents and has a molecular weight of from 2000 to 10000.

16. A granular detergent composition or component thereof, according to any of Claims 1 to 15 wherein a cationic clay-soil removal/ anti redeposition polymer is present, characterised in that it has a backbone, at least 2M groups and at least one L-X group, wherein M is a cationic group attached to or integral with the backbone and contains an N+ positively charged centre; and L connects groups M and X or connects group X to the polymer backbone; X is a nonionic group selected from the group consisting of H, C l-C4 alkyl or hydroxyalkyl ester or ether groups, and mixtures thereof; and L is a hydrophilic chain which contains the polyoxyalkylene moiety [(R60)m(CH2CH20)n]-;

17. A granular detergent composition or component thereof, according to Claim 16 wherein said cationic compound is an ethoxylated cationic polymer which has a backbone, selected from the group consisting of the polyurethanes, the polyesters, the polyethers, the polyimides, the polyalkyleneimines and mixtures thereof.

18. A granular detergent composition, according to any of Claims 1 to 17 wherein the composition is formulated in such a manner as to provide a wash pH of from 8.0 to 10.5.

19. A granular detergent composition or component thereof according to any of Claims 1 to 18 wherein a heavy metal ion sequestrant is present at a level of from 0.1 % to 10% by weight of the detergent composition.

20. A granular detergent composition or component thereof according to any of Claims 1 to 19 wherein an organic peroxyacid bleaching system is present, containing a hydrogen peroxide source and an organic peroxyacid bleach precursor compound.

21. A granular detergent composition or component thereof according to any of Claims 1 to 20 wherein a surfactant is present, selected from the group consisting of anionic, nonionic, cationic, ampholytic, amphoteric and zwitterionic surfactants and mixtures thereof.

22. A method of washing laundry in a domestic washing machine wherein an effective amount of a granular detergent composition according to any of Claims 1 to 21 is introduced into the drum of the washing machine, preferably before the commencement of the wash by use of a dispensing device which permits progressive release of said granular detergent composition into the wash liquor during the wash.

23. The use of a detergent composition or component thereof according to any of Claims 1 to 22 in a dish washing process.