Bleaching Component Technical Field The present invention relates to bleaching components which contain a percarboxylic acid bleach or precursor thereto and a disintegrating agent. The invention also relates to detergent compositions, in particular nonaqueous liquid laundry compositions and solid laundry compositions such as tablets, bars and granules, comprising the bleaching component.

Background to the Invention Many detergent compositions comprise bleaching systems which contain a bleach activator, which is generally added to the detergent in the form of separate granules.

Widely known bleach activator or precursors are organic peroxyacid activators or precursors.

These bleach activators are highly reactive materials. On one hand, this is essential to obtain a good bleaching performance. On the other hand, this has as a disadvantage that they readily react with other ingredients present in the composition, thus resulting in a reduced performance of not only the bleach activators but also the other ingredients.

Therefore, bleach activators are often coated or compacted to improve their stability and reduce the occurrence of unwanted reactions.

However, it has been found that these coated or compacted bleach activators do not always dissolve satisfactorily in the wash water and thus not always deliver to their full

capacity. This is particularly a problem when the bleach activator is used in cold water conditions or when a fast dissolution is required because the washing operation is of very short duration.

As a solution it has been suggested, for example in EP 238341-A and EP299599-A to include in the bleach activator granule a water-soluble salt or acid of a sequestering agent, such as EDTA or aminoacids, which are said to aid the dissolution of the granule and the activator therein. However, to make these materials, high levels of binders are required.

The inventors have now found improved bleaching components, containing specific percarboxylic acids or percarboxylic acid precursors, which dissolve rapidly in water and which are stable upon storage. The inventors have found that when the bleaching components comprise a specific polymeric, preferably water-swellable material, the dissolution of the bleaching component is improved and an improved bleaching or cleaning performance is obtained. The specific polymeric disintegrating agents are believed to be capable of absorbing water rather than dissolving rapidly in water, thereby disturbing the structure of the component and dispersing the ingredients therein. The dispersed ingredients are of smaller particle size and dissolve faster in water. Thus, in use this results in a faster delivery of the bleach precursors to the wash water and a faster bleaching performance. Even in cold water conditions or in very short washing cycles, the bleaching component is delivered rapidly to the wash and a good bleaching performance can be achieved.

Furthermore, they have found that the specific polymeric materials can be combined with the specific bleach precursors without any problems and the resulting component has been found to be very stable, also upon storage.

Summary of the Invention The present invention provides a particulate bleaching component comprising a particulate percarboxylic acid bleach and/or a percarboxylic acid bleach precursors and a polymeric disintegrating agent which are mixed with one another, whereby the percarboxylic acids bleach and the percarboxylic acid bleach precursors are respectively of the formula

L being a leaving group, M being a counter ion, preferably hydrogen, X having at least 2 carbon atoms and R is a substituent group comprising at least 4 carbon atoms, provided that the polymeric disintegrating agent does not consist of non-modified sodium salt of carboxymethyl cellulose.

The invention also relates to a process for making a particulate bleaching component comprising the steps of a) mixing the disintegrating agent and the percarboxylic acid bleach or percarboxylic acid bleach precursor, and optionally a binder, to from a mixture; and b) granulation of the mixture to form the particulate bleaching component, preferably including the step of extrusion and/or agglomeration of the mixture.

The invention also relates to detergent compositions comprising the particulate bleaching component of the invention, preferably solid or nonaqueous liquid compositions, in particular laundry detergent compositions.

The invention also relates to the use of the component or the compositions comprising the component in a washing process for washing of fabrics at a wash water temperature of about 45°C or less.

Detailed Description of the Invention Bleaching Component The bleaching component of the invention is preferably in the form of a granule, preferably formed by extrusion or agglomeration of a mixture of the polymeric disintegrating agent and the percarboxylic acid bleach and/or percarboxylic acid bleach precursor.

The granule may be present as a separate granular component in compositions as described herein and/or the granule can be incorporated with other ingredients in another granule or in a tablet or bar.

The particulate bleaching component preferably has a weight average particle size of from 200 to 2500 microns, more preferably from 350 microns to 2000 microns or even from 450 microns to 1700 microns or even from 500 microns to 1500 microns. hereby it may be preferred that the percarboxylic acid bleach or the percarboxylic acid precursor have a weight average particle size of from 3 to 600 microns, or even form 5 to 500 microns or even from 10 to 300 microns, or even to 200 microns.

The weight average particle size can be determined by any method known in the art, in particular by sieving a sample of the particulate material herein through a series of sieves, typically 5, with meshes of various diameter or aperture size, obtaining a number of fraction (thus having a particle size of above, below or between the mesh sizes of the used sieves), whereof the weight is determined (weight fractions). The average particle size per fraction can be obtained and then the weight average particle size of the material can be calculated, taking in account the weight percentage per fraction (e. g. plotting the weight fractions against the aperture size of the sieves).

It may be preferred that the particulate component is'dry', which it is to be understood that the granules are substantially free of water, i. e., that no is present other than the moisture of or in the materials themselves. Typically, the level of water is below 5% by weight of the total granule, preferably below 3% and more preferably below 1.5%.

It may be highly preferred that the bleaching component comprises the percarboxylic acid or the precursor thereto, or mixtures thereof and the disintegrating agent are mixed such that they are in close proximity to one another. This means that they are in intimate mixture with one another in the bleaching component, typically a homogeneous mixture.

Such a granule may also be obtainable by a process whereby the ingredients are thoroughly mixed and subsequently granulated, preferably by a process comprising an agglomeration step or pressure agglomeration, a compaction step and/or an extrusion step.

The bleaching component preferably comprises a hydrophobic percarboxylic acid or more preferably a hydrophobic percarboxylic acid precursor. However, it may be preferred that the component comprises a mixture of hydrophilic and hydrophobic percarboxylic acids and/or, more preferably percarboxylic acid precursors.

The bleaching component comprises the percarboxylic acid and/or precursor thereto generally at a level of from 30% to 99% of the component, preferably at a level of from 50% to 95% or even from 60% to 90% by weight of the component.

The polymeric disintegrating agent is generally present at a level of from 1% to 40% by weight of the component, preferably from 3% to 20% or even from 5% to 15% by weight.

The bleaching component may comprise a binder material. The binder material is preferably a material which has a melting point above 40°C and which is thus solid at ambient storage temperatures. Preferably, the binder has a melting point below 150°C or even below 100°C or even below 80°C, so that the melt can be formed and added to the

percarboxylic acid bleach or precursor at a temperature which is not detrimental to the stability of the bleaching ingredient (s). Highly preferred binders include nonionic surfactants, as described herein after, in particular nonionic alkoxylated alcohol surfactant, and polyalkyleneglycols, whereby polyethyleneglycols are highly preferred binders.

The binder (s), when present, is preferably incorporated at a level of from 0.5% to 30% by weight of the component, more preferably at a level of 1% to 20% or even 5% to 15% by weight of the component.

The bleaching component is preferably free of anionic carboxymethyl cellulose ether. It has been found that this material tends to form gels upon contact with water. The gels not only hinders the delivery of the bleaching component to the wash but the gels also tend to deposit onto the fabric, causing other ingredients to get entrapped in the gel. This results in spotting of the fabric and even in damaging of the fabric.

Other ingredients which may be present in the component of the invention include anionic surfactant, as described herein, preferably present at a level of from 0.5% to 40% or even from 3% to 30% or even from 5% to 20% by weight of the component. Highly preferred are salts or acids of anionic alkylbenzene sulphonate surfactants. Also included as other ingredient may be fatty acids or salts thereof, preferably C12-C24 alkyl fatty acids or salts thereof.

It may be preferred that an effervescence system is present in the component of the invention, in particular an effervescence system comprising an acid source and an carbon dioxide source. Preferred acid sources include mono-or polycarboxylic acids preferably citric acid, adipic acid, glutaric acid, 3 cetoglutaric acid, citramalic acid, tartaric acid, maleic acid, fumaric acid, malic acid, succinic acid, malonic acid. Such acids are preferably used in their acidic forms, and it may be preferred that their anhydrous forms are used, or mixtures thereof. Other preferred acids include sulphonic acids such as

toluenesulphonic acid. Preferred carbon dioxide sources include sodium and potassium carbonate and bicarbonate and percarbonate. Such an effervesce system is then preferably present at a level of from 2% to 20% by weight of the component, preferably from 2 % to 10% or even from 3% to 8% by weight.

It may be preferred that the component is free of clay, in particularly because clays can be a source of heavy metal ions which can be detrimental tot he stability of the percarboxylic acid or precursor thereto.

Polvmeric Disintegrating Agent The bleaching component herein comprises a polymeric disintegrating agent which is capable of accelerating the dissolution of the bleach or precursor thereto. In a preferred embodiment, the desintegrating agent comprises a polymeric material which is a so called water-swellable polymer, capable of absorbing water and increasing thereby its volume.

It may thus be preferred that the disintegrating agent is only partially water soluble or substantially not water soluble.

However, selective water-soluble polymeric materials which agent which are capable of accelerating the dissolution of the bleach or precursor thereto, so called wicking agents, are also envisaged herein. Preferred examples thereof are compacted cellulose materials as described herein.

The disintegrating agent comprises preferably one or more polymers selected from the group comprising cross-linked polymers of polyvinyl pyrrolidone, cross-linked copolymers of polyvinyl pyrrolidone, starch, modified starch, including pregelatinised starch and sodium starch gluconate, gum, cellulose, modified cellulose, preferably cross- linked cellulose, cross-linked cellulose derivatives, hydroxyalkyl cellulose, microcrystalline cellulose, microcrystalline cellulose derivatives, microcrystalline crosslinked cellulose, compacted cellulose, compacted modified cellulose such as compacted cellulose derivatives or compacted cross-linked cellulose, or mixtures thereof.

Examples of preferred disintegrating agents include modified or pre-gelatinized starch (with less than 25% water soluble portion), low substituted hydroxyalkyl cellulose, having an average substitution degree of less than 3, crosslinked carboxy methyl cellulose (e. g., Nymcel or AcDiSol), microcrystalline cellulose (e. g., Avicel PH101 & PH102), crosslinked polyvinyl pyrrolidone (e. g., Kollidon CL), and mixtures thereof.

Highly preferred are water-swellable low substituted hydroxy propyl cellulose as available from Shin Etsu under the trade name L-HPC, preferably LH-11, LH-21, LH-31, LH-22, LH-32, LH-20, LH-30, most preferablyLH-31 or LH-11. Also preferred are more water- soluble wicking agents, including water soluble cellulose ethers such preferably methyl cellulose, hydroxy propyl methylcellulose, hydroxyethyl methyl cellulose, which are available from Shin Etsu under the trade name Metolose; mechanically compacted cellulose, such as available from Rettenmeier under the trade name Arbocel, or from Fibre Sales & Development Co under the trade name Solka Floc.

Hvdrophobic and Hydrophilic Percarboxylic Acid Bleach or Percarboxvlic Acid Bleach Precursors The hydrophilic percarboxylic acids or precursors thereto herein may be selected from those known in the art; a highly preferred hydrophilic precursor is TAED.

The bleaching component of the invention preferably comprises a hydrophobic percarboxylic acid bleach or precursor thereto.

Percarboxylic acid bleach precursor are compounds which react with hydrogen peroxide, preferably derived from a inorganic perhydrate salt, in a perhydrolysis reaction to produce a percarboxylic acid.

Preferably such hydrophobic percarboxylic acids or precursors thereto are those whose parent carboxylic acid has a critical micelle concentration less than 0.5 moles/liter and wherein said critical M'icelle concentration is measured in aqueous solution at 20°.

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 <BR> <BR> <BR> 14 carbon atoms, R³ is an alkyl chain containing from 1 to 8 carbon atoms, R4 is H or R3, and Y is H or a solubilizing group. Any of 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-SO'M,-CO'M,-SO.M,-N(R).X'and 0<--N (R3) 3 and most preferably-SOMand-COMwhereinR 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.

The bleaching component preferably comprises a hydrophobic percarboxylic acid and/or precursor thereto, having as leaving groups L, a benzoic acid or derivative thereof and especially benzene sulphonate or benzene sulphonic acid. The counterion M of the percarboxylic acid is preferably sodium, potassium or hydrogen.

The hydrophobic percarboxylic acid, preferably formed from the precursor, preferably comprise a R group containing at least 5 carbon atoms, or at least 6 or even 7 carbon atoms, and it may be preferred that it contains at least from 5 to 10 carbon atoms, more preferably from 6 to 9 carbon atoms. The R group may comprise any further substituent groups, provided that the percarboxylic acid is hydrophobic. In a preferred aspect the percarboxylic acid has a group R which is a linear, or optionally branched, alkyl chain comprising at least 6 or even 7 carbon atoms, and it may be preferred that it contains at least from 5 to 10 carbon atoms, more preferably from 6 to 9 carbon atoms.

Highly preferred hydrophobic alkyl percarboxylic acid precursors include decanoly oxy benzoic acid or salt thereof, dodecanoyloxy-benzenesulphonate sodium or potassium salt, decanoyloxy-benzenesulphonate sodium or potassium salt (DOBS), benzoyloxy- benzenesulphonate sodium or potassium salt (BOBS), more preferred sodium or potassium 3,5,5-tri-methyl hexanoyloxybenzene sulfonate (iso-NOBS) and even more preferred sodium or potassium nonanoyloxybenzene sulfonate (NOBS).

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

wherein RI is an aryl or alkaryl group with from about 1 to about 14 carbon atoms, R2 is an alkylene, arylene, and alkarylene group containing from about 2 to 14 carbon atoms, and R5 is H or an alkyl, aryl, or alkaryl group containing 1 to 10 carbon atoms and L can be essentially any leaving group. R1 preferably contains from about 6 to 12 carbon atoms. R2 preferably contains from about 4 to 8 carbon atoms. Rl may be straight chain or branched alkyl or alkenyl, optionally containing branching or substitution, or both and may be sourced from either synthetic sources or natural sources including for example, tallow fat. Analogous structural variations are permissible for R2. R2 can include alkyl, alkenyl, wherein said R2 may also contain halogen, nitrogen, sulphur and other typical substituent groups or organic compounds. R5 is preferably H or methyl. RI and R5 should not contain more than 18 carbon atoms total.

Preferred examples of bleach precursors of this type include amide substituted peroxyacid precursor compounds selected from (6-octanamido-caproyl) oxybenzenesulfonate, (6- decanamido-caproyl) oxybenzene-sulfonate, and the highly preferred (6- nonanamidocaproyl) oxy benzene sulfonate, and mixtures thereof as described in EP-A- 0170386.

Particularly preferred is (6-nonamidocaproyl) oxybenzene sulfonate.

A preferred class of organic peroxyacid compounds are the amide substituted compounds of the following general formulae: wherein Rl is an alkyl, aryl or alkaryl group with from 1 to 14 carbon atoms, R2 is an alkylene, arylene, and alkarylene group containing from 2 to 14 carbon atoms, and R5 is H or an alkyl, aryl, or alkaryl group containing 1 to 10 carbon atoms.

Suitable organic peroxyacids include diperoxyalkanedioc acids having more than 7 carbon atoms, such as diperoxydodecanedioc acid (DPDA), diperoxytetradecanedioc acid and diperoxyhexadecanedioc acid. Mono-and diperazelaic acid, mono-and diperbrassylic acid and N-phthaloylaminoperoxicaproic acid (PAP), nonanoylamido peroxo-adipic acid (NAPAA) and hexane sulphenoyl peroxypropionic acid and are also suitable herein.

Detergent Compositions In a preferred embodiment the bleaching component or preferably the bleaching granules herein are comprised in a compositions which require dissolution in water, in particular in a shorter period of time and/or in cold water and/or at lower total level of bleaching particular components.

The bleaching component is preferably present at a level such that the percarboxylic acid and/or the precursor thereto are present at a level of from 0.5% to 40% by weight of the detergent component, more preferably of from 1% to 25% or even from 1.5% to 15% or even from 3% to 15% by weight.

In particular the bleaching components herein are incorporated in cleaning compositions such as laundry detergent compositions, pre-treatment compositions, but they may also be useful in hard surface cleaning compositions and dish washing detergent compositions. In particular non-aqueous liquid compositions and solid compositions, in particular granular compositions, tablets, extrudates and bars, are envisaged herein.

The bleaching component may be present as a separate granular component of the granular detergent composition.

The granular compositions of the present invention can be prepared with different bulk densities, preferably being from 300 to 1500 g/1, preferably from 500 to 1200 g/1. These compositions can be made by a variety of methods well known in the art, including dry- mixing, spray drying, agglomeration and granulation and combinations thereof.

In a preferred embodiment, the composition comprises from 0.5% to 50% by weight of the total composition of an effervescent component or granule, preferably from 2% to 40%, or even from 3% to 25% by weight, comprising the ingredients as described above.

The compositions herein generally 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, and the precise nature of the washing operation for which it is to be used.

It is highly preferred that a inorganic peroxygen bleach or perhydrate bleach is present, whereby it is preferred that a percarbonate salt is present.

In one preferred embodiment, the solid detergent composition herein comprises detergent base granules, whereof at least one comprises at least one bleaching component, preferably in granular form. Then, the detergent base granules preferably have an weight average particle size of 500 microns to 4 mm, more preferably from 600 microns to 2.5 mm or even from 710 microns to 2 mm. The detergent granule may be made by any process and may comprise any detergent ingredient. Preferred may be that the detergent base granule is made in a process whereby different detergent granules comprising different mixtures of detergent ingredients (preferably granulated by agglomeration, spray-drying or extrusion) are mixed and subsequently compacted, agglomerated, spheronised, or marumerised or extruded, optionally with addition of a binder. Thus, preferred may be that the bleaching granule herein and other granular detergent components are mixed with a binder and subsequently submitted to a granulation step, such as agglomeration, spheronisation, or marumerisation.

In one embodiment of the invention, it may be preferred that the detergent composition herein comprise one or more anionic surfactants and an aluminosilicate builder, whereby it is preferred that only small amounts of the aluminosilicate builder and the anionic surfactant are in an intimate mixture, i. e. less than 50% or even less than 30% of the total amount of the anionic surfactant and less than 50% or even less than 30% of the total amount of aluminosilicate; it may even be preferred that substantially no anionic surfactant and aluminosilicate builder are in an intimate mixture. Thus, it may be preferred that the composition comprises at least two separate particles which comprise either anionic surfactant or aluminosilicate. Namely, it has been found that the solubility and/or dispensing of the composition is thereby improved.

In another embodiment of the invention, it may be preferred that the composition only comprises low levels of aluminosilicate builder, for example less than 10% or even less than 5% by weight of the composition, whereby it is preferred that the composition comprises highly soluble builders, for example sodium citrate or citric acid, carbonate, and/or crystalline layered silicate.

It may also be preferred that the composition comprises as builder system or as part of the builder system, an agglomerate comprising from 0.5% to 80% by weight a crystalline layered silicate, preferably, NaSKS-6, and from 10% to 70% by weight of a surfactant, preferably an anionic surfactant, whereby it may be preferred that less than 10% by weight of the agglomerate of free moisture, more preferably 30% to 60% by weight a crystalline layered silicate and 20% to 50% by weight of an anionic surfactant.

Peroxide Source Inorganic perhydrate salts are a preferred source of peroxide. Preferably these salts are present at a level of from 0.5% to 40% by weight, more preferably of from 3% to 25%, or even form5% to 20% by weight.

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 NaBO2H202 or the tetrahydrate NaBO2H202.3H20.

Alkali metal percarbonates, particularly sodium percarbonate are preferred perhydrates herein. Sodium percarbonate is an addition compound having a formula corresponding to 2Na2CO3.3H202, and is available commercially as a crystalline solid.

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

The perhydrate salt preferably is in the form of a granule. It may be preferred that the granule has about the particle size of the bleaching component herein. It may be preferred that the perhydrate granule has an weight average particle size of from 700 microns to 1000 microns, more preferably from 750 or even 800 microns to 950 microns or even from 820 to 920 microns. It may be preferred that at least 70% or even at least 80% and more preferably at least 90% or even at least 95% of the perhydrate granule has a particle size of from 600 or even 710 microns to about 1180 microns, preferably from 710 microns to 1000 microns.

Surfactant The components in accord with the invention and the compositions herein preferably contain one or more surfactants 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 fI 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 components in accord with the present invention and/or the detergent compositions herein 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 and sulfonate surfactants are preferred.

The anionic surfactants is preferably present at a level of from 0.1 % to 60%, more preferably from 1 to 40%, most preferably from 5% to 30% by weight.

Highly preferred are surfactants systems comprising a sulfonate and a sulfate surfactant, preferably a linear or branched alkyl benzene sulfonate and alkyl ethoxylsulfates, as described herein, preferably combined with a cationic surfactants as described herein.

Other anionic surfactants include the isethionates such as the acyl isethionates, N-acyl taurates, fatty acid amides of methyl tauride, alkyl succinates and sulfosuccinates, monoesters of sulfosuccinate (especially saturated and unsaturated C 12-C 18 monoesters) diesters of sulfosuccinate (especially saturated and unsaturated 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 C5-Cl7 acyl-N- (Cl-C4 alkyl) and-N- (Cl-C2 hydroxyalkyl) glucamine sulfates, and sulfates of alkylpolysaccharides such as the sulfates of alkylpolyglucoside (the nonionic nonsulfated compounds being described herein).

Alkyl sulfate surfactants are preferably selected from the linear and branched primary C 1 o-C 18 alkyl sulfates, more preferably the C 11-C 15 branched chain alkyl sulfates and the C l 2-C 14 linear chain alkyl sulfates.

Alkyl ethoxysulfate surfactants are preferably selected from the group consisting of the C 1 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 C 11 ~ C1g, most preferably C 1-Cls 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/or sulfonate and alkyl ethoxysulfate surfactants. Such mixtures have been disclosed in PCT Patent Application No. WO 93/18124.

Anionic Sulfate Surfactant

Anionic sulfonate surfactants suitable for use herein include the salts of Cs-C20 linear alkylbenzene sulfonates, alkyl ester sulfonates, C6-C22 primary or secondary alkane sulfonates, C6-C24 olefin sulfonates, sulfonated polycarboxylic acids, alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfonates, and any mixtures thereof.

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

Suitable alkyl ethoxy carboxylates include those with the formula RO (CH2CH20) X CH2C00-M+ wherein R is a C6 to C1g alkyl group, x ranges from O to 10, and the ethoxylate distribution is such that, on a weight basis, the amount of material where x is 0 is less than 20 % and M is a cation. Suitable alkyl polyethoxy polycarboxylate surfactants include those having the formula RO- (CHR1-CHR2-O)-R3 wherein R is a C6 to C1g alkyl group, x is from 1 to 25, R1 and R2 are selected from the group consisting of hydrogen, methyl acid radical, succinic acid radical, hydroxysuccinic acid radical, and mixtures thereof, and R3 is selected from the group consisting of hydrogen, substituted or unsubstituted hydrocarbon having between 1 and 8 carbon atoms, and mixtures thereof.

Suitable soap surfactants include the secondary soap surfactants which contain a carboxyl unit connected to a secondary carbon. Preferred secondary soap surfactants for use herein are water-soluble members selected from the group consisting of the water-soluble salts of 2-methyl-1-undecanoic acid, 2-ethyl-1-decanoic acid, 2-propyl-1-nonanoic acid, 2- butyl-1-octanoic acid and 2-pentyl-1-heptanoic acid.

Certain soaps may also be included as suds suppressors.

Alkali Metal Sarcosinate Surfactant Other suitable anionic surfactants are the alkali metal sarcosinates of formula R-CON (RI) CH2 COOM, wherein R is a Cs-C17 linear or branched alkyl or alkenyl group, RI is

a C 1-C4 alkyl group and M is an alkali metal ion. Preferred examples are the myristyl and oleoyl methyl sarcosinates in the form of their sodium salts.

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

Preferred alkoxylated surfactants can be selected from the classes of the nonionic condensates of alkyl phenols, nonionic ethoxylated alcohols, nonionic ethoxylated/propoxylated fatty alcohols, nonionic ethoxylate/propoxylate condensates with propylene glycol, and the nonionic ethoxylate condensation products with propylene oxide/ethylene diamine 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 Polyhvdroxy Fattv Acid Amide Surfactant Polyhydroxy fatty acid amides suitable for use herein are those having the structural formula R2CONR1Z wherein: RI is H, Cl-C4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy <BR> <BR> <BR> propyl, ethoxy, propoxy, or a mixture thereof, preferable C1-C4 alkyl, more preferably C I or C2 alkyl, most preferably Cl alkyl (i. e., methyl); and R2 is a Cs-C31 hydrocarbyl, preferably straight-chain Cs-C1g alkyl or alkenyl, more preferably straight-chain Cg-Cl7 alkyl or alkenyl, most preferably straight-chain C1 l-Cl7 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 Fatty Acid Amide Surfactant Suitable fatty acid amide surfactants include those having the formula: R6CON (R7) 2 wherein R6 is an alkyl group containing from 7 to 21, preferably from 9 to 17 carbon atoms and each R7 is selected from the group consisting of hydrogen, C 1-C4 alkyl, C 1-C4 hydroxyalkyl, and- (C2H40) xH, where x is in the range of from 1 to 3.

Nonionic 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 (glycol) 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 0 to 10, and x is from 1.3 to 8. The glycosyl is preferably derived from glucose.

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

Suitable amine oxides include those compounds having the formula R3 (OR4) xNO (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 C 1 o-C 18 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 in accord with the invention. These surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. Betaine and sultaine surfactants are exemplary zwitterionic surfactants for use herein.

Suitable betaines are those compounds having the formula R (R') 2N+R2COO-wherein R is a C6-C1g hydrocarbyl group, each RI is typically Cl-C3 alkyl, and R2 is a C1-Cs hydrocarbyl group. Preferred betaines are C12-18 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 herein include the quaternary ammonium surfactants. Preferably the quaternary ammonium surfactant is a mono C6-C 16, preferably C6-C1o N-alkyl or alkenyl ammonium surfactants wherein the remaining N positions are substituted by methyl, hydroxyethyl or hydroxypropyl groups. Preferred are also the mono-alkoxylated and bis-alkoxylated amine surfactants.

Another suitable group of cationic surfactants which can be used in the detergent compositions or components thereof herein are cationic ester surfactants. The cationic ester surfactant is a, preferably water dispersible, compound having surfactant properties comprising at least one ester (i. e.-COO-) linkage and at least one cationically charged group.

Suitable cationic ester surfactants, including choline ester surfactants, have for example been disclosed in US Patents 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,-O-O- (i. e. peroxide),-N-N-, and-N-O-linkages are excluded, whilst spacer groups having, for example-CH2-O-CH2-and-CH2-NH-CH2-linkages are included. In a preferred aspect the spacer group chain comprises only carbon atoms, most preferably the chain is a hydrocarbyl chain.

Cationic Mono-Alkoxylated Amine Surfactants Highly preferred herein are cationic mono-alkoxylated amine surfactant preferably of the general formula I:

wherein R1 is an alkyl or alkenyl moiety containing from about 6 to about 18 carbon atoms, preferably 6 to about 16 carbon atoms, most preferably from about 6 to about 14 carbon atoms; R2 and R3 are each independently alkyl groups containing from one to about three carbon atoms, preferably methyl, most preferably both R2 and R3 are methyl groups; R4 is selected from hydrogen (preferred), methyl and ethyl; X'is an anion such as chloride, bromide, methylsulfate, sulfate, or the like, to provide electrical neutrality; A is a alkoxy group, especially a ethoxy, propoxy or butoxy group; and p is from 0 to about 30, preferably 2 to about 15, most preferably 2 to about 8.

Preferably the ApR4 group in formula I has p=1 and is a hydroxyalkyl group, having no greater than 6 carbon atoms whereby the-OH group is separated from the quaternary ammonium nitrogen atom by no more than 3 carbon atoms. Particularly preferred ApR4 groups are-CH2CH20H,-CH2CH2CH20H,-CH2CH (CH3) OH and- CH (CH3) CH20H, with-CH2CH20H being particularly preferred. Preferred R1 groups are linear alkyl groups. Linear RI groups having from 8 to 14 carbon atoms are preferred.

Another highly preferred cationic mono-alkoxylated amine surfactants for use herein are of the formula

wherein R1 is C1g-Cl8 hydrocarbyl and mixtures thereof, especially C10-Cl4 alkyl, preferably C 10 and C 12 alkyl, and X is any convenient anion to provide charge balance, preferably chloride or bromide.

As noted, compounds of the foregoing type include those wherein the ethoxy (CH2CH2O) units (EO) are replaced by butoxy, isopropoxy [CH (CH3) CH20] and [CH2CH (CH3O] units (i-Pr) or n-propoxy units (Pr), or mixtures of EO and/or Pr and/or i-Pr units.

The levels of the cationic mono-alkoxylated amine surfactants is preferably from 0.1 % to 20%, more preferably from 0.2% to 7%, most preferably from 0.3% to 3.0% by weight.

Cationic Bis-Alkoxylated Amine Surfactant The cationic bis-alkoxylated amine surfactant preferably has the general formula II: wherein R1 is an alkyl or alkenyl moiety containing from about 8 to about 18 carbon atoms, preferably 10 to about 16 carbon atoms, most preferably from about 10 to about 14 carbon atoms; R2 is an alkyl group containing from one to three carbon atoms, preferably methyl; R3 and R4 can vary independently and are selected from hydrogen (preferred), methyl and ethyl, X'is an anion such as chloride, bromide, methylsulfate, sulfate, or the like, sufficient to provide electrical neutrality. A and A'can vary independently and are each selected from C1-C4 alkoxy, especially ethoxy, (i. e.,-CH2CH2O-), propoxy, butoxy and mixtures thereof ; p is from 1 to about 30, preferably 1 to about 4 and q is from 1 to about 30, preferably 1 to about 4, and most preferably both p and q are 1.

Highly preferred cationic bis-alkoxylated amine surfactants for use herein are of the formula

wherein R l is C 10-C l 8 hydrocarbyl and mixtures thereof, preferably C 1 o, C 12, C 14 alkyl and mixtures thereof. X is any convenient anion to provide charge balance, preferably chloride. With reference to the general cationic bis-alkoxylated amine structure noted above, since in a preferred compound R 1 is derived from (coconut) C 12-C 14 alkyl fraction fatty acids, R2 is methyl and ApR3 and A'qR4 are each monoethoxy.

Other cationic bis-alkoxylated amine surfactants useful herein include compounds of the formula: wherein RI is CiQ-Cis hydrocarbyl, preferably C 1 p-C 14 alkyl, independently p is 1 to about 3 and q is 1 to about 3, R2 is C 1-C3 alkyl, preferably methyl, and X is an anion, especially chloride or bromide.

Other compounds of the foregoing type include those wherein the ethoxy (CH2CH2O) units (EO) are replaced by butoxy (Bu) isopropoxy [CH (CH3) CH20] and [CH2CH (CH30] units (i-Pr) or n-propoxy units (Pr), or mixtures of EO and/or Pr and/or i-Pr units.

Perfumes Another preferred ingredient of the component of the invention or the compositios herein is a perfume or perfume composition. Any perfume composition can be used herein. The perfumes may also be encapsulated.

Preferred perfumes containing at least one component with a low molecular weight volatile component, e. g. having a molecular weight of from 150 to 450 or preferably 350.

Preferably, the perfume component comprises an oxygen-containing functional group.

Preferred functional groups are aldehyde, ketone, alcohol or ether functional groups or mixtures thereof.

Heavy Metal Ion Sequestrant The components in accord with the present invention and/or the detergent compositions herein preferably contain as an optional component a heavy metal ion sequestrant or chelant or chelating agent. 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 10%, preferably from 0.1% to 5%, more preferably from 0.25% to 7.5% and most preferably from 0.3% to 2% by weight of the compositions or component 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, 1,1 hydroxyethane diphosphonic acid and 1,1 hydroxyethane dimethylene phosphonic acid.

Other suitable heavy metal ion sequestrant for use herein include nitrilotriacetic acid and polyaminocarboxylic acids such as ethylenediaminotetracetic acid, ethylenediamine disuccinic acid, ethylenediamine diglutaric acid, 2-hydroxypropylenediamine disuccinic acid or any salts thereof.

Other suitable heavy metal ion sequestrants for use herein are iminodiacetic acid derivatives such as 2-hydroxyethyl diacetic acid or glyceryl imino diacetic acid, described in EP-A-317,542 and EP-A-399,133. The iminodiacetic acid-N-2-hydroxypropyl sulfonic acid and aspartic acid N-carboxymethyl N-2-hydroxypropyl-3-sulfonic acid sequestrants described in EP-A-516,102 are also suitable herein. The (3-alanine-N, N'-diacetic acid, aspartic acid-N, N'-diacetic acid, aspartic acid-N-monoacetic acid and iminodisuccinic acid sequestrants described in EP-A-509,382 are also suitable.

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

Especially preferred are diethylenetriamine pentacetic acid, ethylenediamine-N, N'- disuccinic acid (EDDS) and 1,1 hydroxyethane diphosphonic acid or the alkali metal, alkaline earth metal, ammonium, or substituted ammonium salts thereof, or mixtures thereof.

In particular the chelating agents comprising a amino or amine group can be bleach- sensitive and are suitable in the compositions of the invention.

Enzyme Another highly preferred ingredient useful in the components or compositions herein is one or more additional enzymes.

Preferred additional enzymatic materials include the commercially available lipases, cutinases, amylases, neutral and alkaline proteases, cellulases, endolases, 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, a-amylases obtained from a special strain of B licheniformis, described in more detail in GB-1,269,839 (Novo). Preferred commercially available amylases include for example, those sold under the tradename Rapidase by Gist- Brocades, and those sold under the tradename Termamyl, Duramyl and BAN by Novo Industries A/S. Highly preferred amylase enzymes maybe those described in PCT/US 9703635, and in W095/26397 and W096/23873.

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.

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.

The lipase may be fungal or bacterial in origin being obtained, for example, from a lipase producing strain of Humicola sp., Thermomyces sp. or Pseudomonas sp. including Pseudomonas pseudoalcaligenes or Pseudomas fluorescens. Lipase from chemically or genetically modified 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.

Optical Brightener The component or compositions herein also preferably contain from about 0.005% to 5% by weight of certain types of hydrophilic optical brighteners, as mentioned above.

Hydrophilic optical brighteners useful herein include those having the structural formula: wherein RI is selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl; R2 is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, morphilino, chloro and amino; and M is a salt-forming cation such as sodium or potassium.

When in the above formula, R1 is anilino, R2 is N-2-bis-hydroxyethyl and M is a cation such as sodium, the brightener is 4,4',-bis [ (4-anilino-6- (N-2-bis-hydroxyethyl)-s-triazine- 2-yl) amino]-2,2'-stilbenedisulfonic acid and disodium salt. This particular brightener species is commercially marketed under the tradename Tinopal-UNPA-GX by Ciba- Geigy Corporation. Tinopal-CBS-X and Tinopal-UNPA-GX is the preferred hydrophilic optical brightener useful in the detergent compositions herein.

When in the above formula, RI is anilino, R2 is N-2-hydroxyethyl-N-2-methylamino and M is a cation such as sodium, the brightener is 4,4'-bis [ (4-anilino-6- (N-2-hydroxyethyl-N-

methylamino)-s-triazine-2-yl) amino] 2,2'-stilbenedisulfonic acid disodium salt. This particular brightener species is commercially marketed under the tradename Tinopal SBM-GX by Ciba-Geigy Corporation.

When in the above formula, R I 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 are commercially marketed under the tradename Tinopal-DMS-X and Tinopal AMS-GX by Ciba Geigy Corporation.

Photo-Bleaching Agent Photo-bleaching agents are preferred ingredients of the compositions or components herein. Preferred photo-bleaching agent herein comprise a compounds having a porphin or porphyrin structure.

Porphin and porphyrin, in the literature, are used as synonyms, but conventionally porphin stands for the simplest porphyrin without any substituents; wherein porphyrin is a sub- class of porphin. The references to porphin in this application will include porphyrin.

The porphin structures preferably comprise a metal element or cation, preferably Ca, Mg, P, Ti, Cr, Zr, In, Sn or Hf, more preferably Ge, Si or Ga, or more preferably Al, most preferably Zn.

It can be preferred that the photo-bleaching compound or component is substituted with substituents selected from alkyl groups such as methyl, ethyl, propyl, t-butyl group and aromatic ring systems such as pyridyl, pyridyl-N-oxide, phenyl, naphthyl and anthracyl moieties.

The photo-bleaching compound or component can have solubilizing groups as substituents. Alternatively, or in addition hereto the photo-bleaching agent can comprise a

polymeric component capable of solubilizing the photo-bleaching compound, for example PVP, PVNP, PVI or co-polymers thereof or mixtures thereof.

Highly preferred photo-bleaching compounds are compounds having a phthalocyanine structure, which preferably have the metal elements or cations described above.

Metal phthalocyanines and their derivatives have the structure indicated in Figure 1 and/or Figure 2, wherein the atom positions of the phthalocyanine structure are numbered conventionally.

The phthalocyanines can be substituted for example the phthalocyanine structures which are substituted at one or more of the 1-4,6,8-11,13,15-18,20,22-25,27 atom positions.

Water-Soluble Builder Compound The component or compositions herein preferably contain a water-soluble builder compound, typically present in detergent compositions at a level of from 1 % to 80% by weight, preferably from 10% to 60% by weight, most preferably from 15% to 40% by weight.

The detergent compositions of the invention preferably comprise phosphate-containing builder material. Preferably present at a level of from 0.5% to 60%, more preferably from 5% to 50%, more preferably from 8% to 40%.

The phosphate-containing builder material preferably comprises tetrasodium pyrophosphate or even more preferably anhydrous sodium tripolyphosphate.

Suitable water-soluble builder compounds include the water soluble monomeric polycarboxylates, or their acid forms, homo or copolymeric polycarboxylic acids or their salts in which the polycarboxylic acid comprises at least two carboxylic radicals separated

from each other by not more that two carbon atoms, borates, and mixtures of any of the foregoing.

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

Suitable carboxylates containing one carboxy group include the water soluble salts of lactic acid, glycolic acid and ether derivatives thereof. Polycarboxylates containing two carboxy groups include the water-soluble salts of succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid and fumaric acid, as well as the ether carboxylates and the sulfinyl carboxylates.

Polycarboxylates or their acids 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.

The most preferred polycarboxylic acid containing three carboxy groups is citric acid, preferably present at a level of from 0.1 % to 15%, more preferably from 0.5% to 8% by weight.

Polycarboxylates containing four carboxy groups include oxydisuccinates disclosed in British Patent No. 1,261,829,1,1,2,2-ethane tetracarboxylates, 1,1,3,3-propane <BR> <BR> <BR> <BR> tetracarboxylates and 1,1,2,3-propane tetracarboxylates. Polycarboxylates containing sulfo substituents include the sulfosuccinate derivatives disclosed in British Patent Nos.

1,398,421 and 1,398,422 and in U. S. Patent No. 3,936,448, and the sulfonated pyrolysed citrates described in British Patent No. 1,439,000. Preferred polycarboxylates are hydroxycarboxylates containing up to three carboxy groups per molecule, more particularly citrates.

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

Borate builders, as well as builders containing borate-forming materials that can produce borate under detergent storage or wash conditions are useful water-soluble builders herein.

Suitable examples of water-soluble phosphate builders are the alkali metal tripolyphosphates, sodium, potassium and ammonium pyrophosphate, sodium and potassium and ammonium pyrophosphate, sodium and potassium orthophosphate, sodium polymeta/phosphate in which the degree of polymerization ranges from about 6 to 21, and salts of phytic acid.

Partially Soluble or Insoluble Builder Compound The component in accord with the present invention or the compositions herein may contain a partially soluble or insoluble builder compound, typically present in detergent compositions at a level of from 0.5% to 60% by weight, preferably from 5% to 50% by weight, most preferably from 8% to 40% weight.

Examples of largely water insoluble builders include the sodium aluminosilicates. As mentioned above, it may be preferred in one embodiment of the invention, that only small amounts of alumino silicate builder are present.

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

The aluminosilicate zeolites can be naturally occurring materials, but are preferably synthetically derived. Synthetic crystalline aluminosilicate ion exchange materials are available under the designations Zeolite A, Zeolite B, Zeolite P, Zeolite X, Zeolite HS and mixtures thereof. Zeolite A has the formula: Na 12 [A102) 12 (Sio2) l2]. xH2O wherein x is from 20 to 30, especially 27. Zeolite X has the formula Na86 [ (A102) 86 (Si02) io. 276H20.

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.

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 median particle size dso 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 dso value indicates that 50% by weight of the particles have a diameter smaller than that figure. The particle size may, in particular be determined by conventional analytical techniques such as microscopic determination using a scanning electron

microscope or by means of a laser granulometer, described herein. Other methods of establishing dso values are disclosed in EP 384070A.

Organic Polymeric Compound Organic polymeric compounds are preferred additional herein 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, including quaternised ethoxylated (poly) amine clay-soil removal/anti- redeposition agent in accord with the invention.

Organic polymeric compound is typically incorporated in the detergent compositions of the invention at a level of from 0.01% to 30%, preferably from 0.1% to 15%, most preferably from 0.5% to 10% by weight of the compositions or component.

Examples of organic polymeric compounds include the water soluble organic homo-or co-polymeric polycarboxylic acids or their salts in which the polycarboxylic acid comprises at least two carboxyl radicals separated from each other by not more than two carbon atoms. Polymers of the latter type are disclosed in GB-A-1,596,756. Examples of such salts are polyacrylates of MWt 1000-5000 and their copolymers with maleic anhydride, such copolymers having a molecular weight of from 2000 to 100,000, especially 40,000 to 80,000.

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

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

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

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

Highly preferred polymeric components herein are cotton and non-cotton soil release polymer according to U. S. Patent 4,968,451, Scheibel et al., and U. S. Patent 5,415,807, Gosselink et al., and in particular according to US application no. 60/051517.

Another organic compound, which is a preferred clay dispersant/anti-redeposition agent, for use herein, can be the ethoxylated cationic monoamines and diamines of the formula: wherein X is a nonionic group selected from the group consisting of H, C 1-C4 alkyl or hydroxyalkyl ester or ether groups, and mixtures thereof, a is from 0 to 20, preferably from 0 to 4 (e. g. ethylene, propylene, hexamethylene) b is 1 or 0; for cationic monoamines (b=0), n is at least 16, with a typical range of from 20 to 35; for cationic diamines (b=l), n is at least about 12 with a typical range of from about 12 to about 42.

Other dispersants/anti-redeposition agents for use herein are described in EP-B-011965 and US 4,659,802 and US 4,664,848.

Suds Suppression System The components and detergent compositions herein, when formulated for use in machine washing compositions, may comprise a suds suppressing system present at a level of from 0.01% to 15%, preferably from 0.02% to 10%, most preferably from 0.05% to 3% by weight of the composition or component.

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

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

Particularly preferred antifoam compounds for use herein are silicone antifoam compounds defined herein as any antifoam compound including a silicone component.

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

Other suitable antifoam compounds include the monocarboxylic fatty acids and soluble salts thereof. These materials are described in US Patent 2,954,347, issued September 27, 1960 to Wayne St. John. The monocarboxylic fatty acids, and salts thereof, for use as suds suppressor typically have hydrocarbyl chains of 10 to 24 carbon atoms, preferably 12 to 18 carbon atoms. Suitable salts include the alkali metal salts such as sodium, potassium, and lithium salts, and ammonium and alkanolammonium salts.

Other suitable antifoam compounds include, for example, high molecular weight fatty esters (e. g. fatty acid triglycerides), fatty acid esters of monovalent alcohols, aliphatic

C 1 g-C40 ketones (e. g. stearone) N-alkylated amino triazines such as tri-to hexa- alkylmelamines or di-to tetra alkyldiamine chlortriazines formed as products of cyanuric chloride with two or three moles of a primary or secondary amine containing 1 to 24 carbon atoms, propylene oxide, bis stearic acid amide and monostearyl di-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 DC0544; (c) an inert carrier fluid compound, most preferably comprising a C 16-C 18 ethoxylated alcohol with a degree of ethoxylation of from 5 to 50, preferably 8 to 15, at a level of from 5% to 80%, preferably 10% to 70%, by weight;

A highly preferred particulate suds suppressing system is described in EP-A-0210731 and comprises a silicone antifoam compound and an organic carrier material having a melting point in the range 50°C to 85°C, wherein the organic carrier material comprises a monoester of glycerol and a fatty acid having a carbon chain containing from 12 to 20 carbon atoms. EP-A-0210721 discloses other preferred particulate suds suppressing systems wherein the organic carrier material is a fatty acid or alcohol having a carbon chain containing from 12 to 20 carbon atoms, or a mixture thereof, with a melting point of from 45°C to 80°C.

Other highly preferred suds suppressing systems comprise polydimethylsiloxane or mixtures of silicone, such as polydimethylsiloxane, aluminosilicate and polycarboxylic polymers, such as copolymers of laic and acrylic acid.

Polymeric Dye Transfer Inhibiting Agents The component and/or compositions herein may also comprise from 0.01% to 10 %, preferably from 0.05% to 0.5% by weight of polymeric dye transfer inhibiting agents.

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

Polymeric Soil Release Agent Polymeric soil release agents, hereinafter"SRA", can optionally be employed in the present components or 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.

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 1,2-propylene glycol ("PG") in a two-stage transesterification/oligomerization procedure; and (c) reacting the product of (b) with sodium metabisulfite in water. Other SRA's include the nonionic end- capped 1,2-propylene/polyoxyethylene terephthalate polyesters of U. S. 4,711,730, December 8,1987 to 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 20°C 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 terminals of the polymer through an ester of the isolated carboxylic acid of trimellitic anhydride rather than by opening of the anhydride linkage. Either nonionic or anionic SRA's may be used as starting materials as long as they have hydroxyl terminal groups which may be esterified. See U. S. 4,525,524 Tung et al.. Other classes include: anionic terephthalate-based 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 colours and filler salts, with sodium sulfate being a preferred filler salt.

Highly preferred compositions contain from about 2% to about 10% by weight of an organic acid, preferably citric acid. Also, preferably combined with a carbonate salt, minor amounts (e. g., less than about 20% by weight) of neutralizing agents, buffering agents, phase regulants, hydrotropes, enzyme stabilizing agents, polyacids, suds regulants, opacifiers, anti-oxidants, bactericides and dyes, such as those described in US Patent 4,285,841 to Barrat et al., issued August 25,1981 (herein incorporated by reference), can be present.

Chlorine-Based Bleach The detergent compositions can include as an additional component a chlorine-based bleach. However, since the detergent compositions of the invention are solid, most liquid chlorine-based bleaching will not be suitable for these detergent compositions and only granular or powder chlorine-based bleaches will be suitable.

Alternatively, the detergent compositions can be formulated such that they are chlorine- based bleach-compatible, thus ensuring that a chlorine based bleach can be added to the detergent composition by the user at the beginning or during the washing process.

The chlorine-based bleachis such that a hypochlorite species is formed in aqueous solution. The hypochlorite ion is chemically represented by the formula OCI-.

Those bleaching agents which yield a hypochlorite species in aqueous solution include alkali metal and alkaline earth metal hypochlorites, hypochlorite addition products, chloramines, chlorimines, chloramides, and chlorimides. Specific examples of compounds of this type include sodium hypochlorite, potassium hypochlorite, monobasic calcium hypochlorite, dibasic magnesium hypochlorite, chlorinated trisodium phosphate dodecahydrate, potassium dichloroisocyanurate, sodium dichloroisocyanurate sodium dichloroisocyanurate dihydrate, trichlorocyanuric acid, 1,3-dichloro-5,5- dimethylhydantoin, N-chlorosulfamide, Chloramine T, Dichloramine T, chloramine B and Dichloramine B. A preferred bleaching agent for use in the compositions of the instant

invention is sodium hypochlorite, potassium hypochlorite, or a mixture thereof.. A preferred chlorine-based bleach can be Triclosan (trade name).

Most of the above-described hypochlorite-yielding bleaching agents are available in solid or concentrated form and are dissolved in water during preparation of the compositions of the instant invention. Some of the above materials are available as aqueous solutions.

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. Preferred washing machines may be the so- called low-fill machines.

In a preferred use aspect the composition is formulated such that it is suitable for hard- surface cleaning or hand washing. In another preferred aspect the detergent composition is a pre-treatment or soaking composition, to be used to pre-treat or soak soiled and stained fabrics.

Abbreviations used in the bleaching component and detergent composition examples LAS Sodium linear C11-13 alkyl benzene sulfonate LAS (I) Potassium linear or branched C11-13 alkyl benzene sulfonate TAS Sodium tallow alkyl 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 Clx-Cly predominantly linear primary alcohol condensed with an average of z moles of ethylene oxide QAS R2. N+ (CH3) 2 (C2H40H) with R2 = C12-C14 QAS 1 R2. N+ (CH3) 2 (C2H40H) with R2 = C8-C 11 APA C8-C10 amido propyl dimethyl amine Soap Sodium linear alkyl carboxylate derived from an 80/20 mixture of tallow and coconut fatty acids STS Sodium toluene sulphonate CFAA C12-C14 (coco) alkyl N-methyl glucamide TFAA C 16-C 18 alkyl N-methyl glucamide TPKFA C12-C14 topped whole cut fatty acids STPP Anhydrous sodium tripolyphosphate TSPP Tetrasodium pyrophosphate Zeolite A Hydrated sodium aluminosilicate of formula Nal2 (A102Si02) 12.27H20 having a primary particle size in the range from 0.1 to 10 micrometers (weight expressed on an anhydrous basis) NaSKS-6 Crystalline layered silicate of formula d-Na2Si205 Citric acid I Anhydrous citric acid, 80% having a particle size of from 40 microns to 70 microns, and having a volume median particle size of 55 microns

Citric acid II Anhydrous or monohydrate citric acid, 80% having a particle size of from 15 microns to 40 microns, having a volume average particle size of 25 microns Malic acid Anhydrous malic acid, 80% having a particle size of from 50 microns to 100 microns, having a volume median particle size of 75 microns Maleic acid Anhydrous maleic acid, 80% having a particle size of from 5 microns to 30 microns, having a volume median particle size of 15 microns Tartaric acid Anhydrous tartaric acid, 80% having a particle size of from 25 microns to 75 microns, having a volume median particle size of 50 microns Carbonate I Anydrous sodium carbonate having 80% by volume of particles with a particle size from 50 microns to 150 microns with a volume median particle size of 100 microns Carbonate n Anydrous sodium carbonate having 80% by volume of particles with a particle size from 35 microns to 75 microns, having a volume median particle size of 55 microns Bicarbonate II: Anhydrous sodium bicarbonate having 80% by volume of particles with a particle size from 100 microns to 200 microns with a volume median particle size of 150 microns Bicarbonate I Anydrous sodium bicarbonate having 80% by volume of particles with a particle size from 15 microns to 40 microns, having a volume median particle size of 25 microns Silicate:Amorphous sodium silicate (Si02: Na20 = 2.0: 1) Sulfate Anhydrous sodium sulfate Mg sulfate Anhydrous magnesium sulfate Citrate Tri-sodium citrate dihydrate of activity 86.4% with a particle size distribution between 425pm and 8501lu MA/AA Copolymer of 1: 4 maleic/acrylic acid, average molecular weight about 70,000

MA/AA (1) Copolymer of 4: 6 maleic/acrylic acid, average molecular weight about 10,000 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, having 3.3% by weight of active enzyme, sold by NOVO Industries A/S under the tradename Savinase Protease I Proteolytic enzyme, having 4% by weight of active enzyme, as described in WO 95/10591, sold by Genencor Int. Inc.

Alcalase Proteolytic enzyme, having 5.3% by weight of active enzyme, sold by NOVO Industries A/S Cellulase Cellulytic enzyme, having 0.23% by weight of active enzyme, sold by NOVO Industries A/S under the tradename Carezyme Amylase Amylolytic enzyme, having 1.6% by weight of active enzyme, sold by NOVO Industries A/S under the tradename Termamyl 120T Lipase Lipolytic enzyme, having 2.0% by weight of active enzyme, sold by NOVO Industries A/S under the tradename Lipolase Lipase (1) Lipolytic enzyme, having 2.0% by weight of active enzyme, sold by NOVO Industries A/S under the tradename Lipolase Ultra Endolase Endoglucanase enzyme, having 1.5% by weight of active enzyme, sold by NOVO Industries A/S PB4 Particle containing sodium perborate tetrahydrate of nominal formula NaB02.3H2 O, the particles having a weight average particle size of 950 microns, 85% particles having a particle size of from 850 microns to 950 microns PB1 Particle containing anhydrous sodium perborate bleach of nominal formula NaB02. H 202, the particles having a weight average particle size of 800 microns, 85% particles having a particle size of from 750 microns to 950 microns

Percarbonate Particle containing sodium percarbonate of nominal formula 2Na2CO3.3H202, the particles having a weight average particle size of 850 microns, 5% or less having a particle size of less than 600 microns and 2% or less having a particle size of more than 1180 microns NOBS Particle comprising nonanoyloxybenzene sulfonate in the form of the sodium salt, the particles having a weight average particle size of 10 microns to 150 microns NACA-OBS Particle comprising (6-nonamidocaproyl) oxybenzene sulfonate, the particles having a weight average particle size of from 10 microns to 150 microns DOBS Decanoyl oxybenzene sulfonate in the form of the sodium salt DPDA Diperoxydodecanedioc acid NOBS Nonanoyloxybenzene sulfonate in the form of the sodium salt NACA-OBS (6-nonamidocaproyl) oxybenzene sulfonate LOBS Dodecanoyloxybenzene sulfonate in the form of the sodium salt DOBS Decanoyloxybenzene sulfonate in the form of the sodium salt DOBA Decanoyl oxybenzoic acid TAED I Particle containing tetraacetylethylenediamine, the particles having a weight average particle size of from 10 microns to 100 microns TAED II Tetraacetylethylenediamine of a particle size from 50 microns to 120 microns DTPA Diethylene triamine pentaacetic acid DTPMP Diethylene triamine penta (methylene phosphonate), marketed by Monsanto under the Tradename Dequest 2060 Photoactivated: Sulfonated zinc phthlocyanine encapsulated in bleach (1) dextrin soluble polymer Photoactivated: Sulfonated alumino phthlocyanine encapsulated in bleach (2) dextrin soluble polymer

Brightener 1 Disodium 4,4'-bis (2-sulphostyryl) biphenyl Brightener 2 Disodium 4,4'-bis (4-anilino-6-morpholino-1.3.5-triazin-2- yl) amino) stilbene-2: 2'-disulfonate EDDS Ethylenediamine-N, N'-disuccinic acid, (S, S) isomer in the form of its sodium salt.

HEDP 1,1-hydroxyethane diphosphonic acid PEGx Polyethylene glycol, with a molecular weight of x (typically 4,000) PEO Polyethylene oxide, with an average molecular weight of 50,000 TEPAE Tetraethylenepentaamine ethoxylate PVI Polyvinyl imidosole, with an average molecular weight of 20,000 PVP Polyvinylpyrolidone polymer, with an average molecular weight of 60,000 PVNO Polyvinylpyridine N-oxide polymer, with an average molecular weight of 50,000 PVPVI Copolymer of polyvinylpyrolidone and vinylimidazole, with an average molecular weight of 20,000 QEA bis ( (C2H50) (C2H40) n) (CH3)-N+-C6H12-N+- (CH3) bis ((C2H50)-(C2H4 O)) n, wherein n = from 20 to 30 SRP 1 Anionically end capped poly esters SRP 2 Diethoxylated poly (1,2 propylene terephtalate) short block polymer PEI Polyethyleneimine with an average molecular weight of 1800 and an average ethoxylation degree of 7 ethyleneoxy residues per nitrogen 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 Opacifier Water based monostyrene latex mixture, sold by BASF Aktiengesellschaft under the tradename Lytron 621 Wax. Paraffin wax Bleaching granule: any of the bleaching granules I to Vm

The following bleaching granules I to VIII are in accord with the invention (ingredients in % by weight of bleaching granule). The granules can be prepared by mixing the ingredients and agglomerating the ingredients or by compacting the mixed ingredients, the later being the preferred process for preparing particle I, IV and VHI. PARTICLES I II III IV V VI VII VI II LAS 5 5 5 5 5 LH-31 5 10 15 Solka Floc *** 10 5 15 Arbocel 10 10 TAED 80 70 70 Desiccant2 2 2 NACOBS NOBS 75 70 65 70 70 CMC 5 10 10 Fatty acids 5 5 5 5 5 === Brightner 3 3 3 PEG 4000 10 10 10 10 10 5 5

* LH-31: Low substituted Hydroxy Propyl Cellulose from Shin Etsu.

** Arbocel: Mechanically compacted cellulose from Rettenmeier *** Solka Floc: Mechanically compacted cellulose from Fibre Sales & Development Co **** overdried or anhydrous salts/zeolite or overdried zeolite TABLE I The following compositions are in accordance with the invention. A FGHI Sprav-dried Granules LAS 10.0 10.0 15.0 5. 0 5.0 10. 0 TAS - 1.0 - - - - MBAS - - 5.0 5.0 - - - C45AS-1. 0 2. 0 2. 0 C45AE3S - - 1.0 - - - QAS 1. 0 1. 0 DTPA, HEDP and/or 0. 3 0. 3 0. 5 0. 3 EDDS MgSO4 0.5 0.5 0.1- - - - Sodium citrate 3.0 5.0 Sodium carbonate 10.0 7.0 15.0 10.0 Sodium sulphate 5.0 5.0 - - 5.0 3.0- -- Sodium silicate 1.6R - - - - 2.0 - - - Zeolite A 16.0 18.0 20.0 SKS-6 3. 0 5. 0 MA/AA or AA 1.0 2.0 11.0 - - 2.0 - - - PEG 4000 2. 0 1. 0 1.0 QEA 1. 0 1. 0 QEA 1.0 - - - 1.0 - - - - Brightener 0.05 0.05 0.05 - 0.05 - - - - Silicone oil 0.01 0.01 0.01- - 0.01 - - - bleaching granule I, III, 10 7.0 - - - - - -- IV or VIII lomerate LAS 2 0 2. 0 MBAS - - - - - - 1.0 C45AS - - - - 2.0 - - AE3 - - - - - 1.0 0.5 Carbonate. 0 1. 0 1. 0 1. 0 Sodium citrate 5.0 CFAAIIIII Citric acid. 0 1. 0 1. 0 QEA - - - 2.0 2.0 1.0 - SRP - - - 1.0 1.0 0.2 - Zeolite A - - - 15.0 26.0 15.0 16.0 Sodium silicate PEG - - - - - - 4.0 - - Builder Agglomerates SKS-6 6.0 - - - 6.0 3.0 - 7.0 10.0 LAS 4. 0 5. 0 5. 0 3. 0 10.0 12.0 Dry-add particulate components bleaching granule I-VIII - 4.0 10.0 4.0 25 8.0 12.0 2.0 4.0 or mixtures QEA 0. 2 0. 5 : BAS 8. 0 8. 0. 0 LAS (flake) 10.0 10.0 8. 0 Citric acid II Spray-on Brightener 0.2 0.2 0.3 0.1 0.2 0.1 - 0.6 0.3 Dye - - - 0.3 0.05 0.1 - - - AE7 - - - - - 0.5 - 0.7 - Perfume 1.0 0.5 1.1 0.8 0.3 0.5 0.3 0.5 - Dry-add Citrate - - 20.0 4.0 - 5.0 15.0- 5.0 Percarbonate 15.0 3.0. 6.0 10.0 - - 24.0 18.0 5.0 Perborate - - - - 6.0 18.0 - - - Photobleach 0.02 0. 1 0. 05 0. 3 0.03 Enzymes (cellulase, 1. 3 0. 3 0. 5 0. 5 0. 8 2. 0 0. 5 0.16 0. 2 amylase, protease, lipase) Carbonate 0. 0 10. 0 5. 0 8. 0 10. 0. 0 Perfume(encapsulated) - 0.5 0.5- 0.3 - 0.2 - - Suds suppressor 1.0 0.6 0.3 - 0.10 0.5 1.0 0.3 1.2 Soap 0.5 0.2 0.3 3.0 0.5 - - 0.3 - Citric acid (I or coarse)- - - 6.0 6.0 - - - 5.0 Dyed carbonate (blue, 0.5 0.5 1.0 2.0 - 0.5 0.5 0.5 1.0 green) SKS-6. 0 6. 0 Fillers up to 100% TABLE II The following compositions are in accordance with the invention. C F G Spray-Dried Granules LAS or LAS (I) 10.0 10.0 16.0 5. 0 5. 0 10.0- - - TAS - 1.0 - - - - MBAS - - - 5.0 5.0 - - - C45AS - - 1.0 2.0 2.0 - - - C45AE3S - - - 1.0 - - - C45AE3S - - - 1.0 - - - QAS 1. 0 1. 0 DTPA, HEDP and/or. 3 0. 3 0. 3 0. 3 EDDS MgSO4 0.5 0.4 0.1 - - - - Sodium citrate 10.0 12.0 17.0 3.0 5.0 Sodium carbonate 15.0 8.0 15.0 10.0 Sodium sulphate 5.0 5.0 5.0 3.0 - - - Sodium silicate 1.6R. 0 Zeolite A 2. 0 SKS-6 3. 0 5. 0 MA/AA or AA 1.0 2.0 10.0 - - 2.0 - - - PEG 4000 - 2.0 - 1.0 - 1.0 - - - QEA 1. 0 1. 0 Brightener 0. 05 0. 05 0. 05). 05 Silicone oil 0. 01 0. 01 0. 01). 01 Bleaching granule I, III, 6 2 - - - - - - - VII or VIII Agglomerate LAS - - - - - - 2.0 2.0 - MBAS - - - - - - - - 1.0 C45AS. 0 AE.0 0.5 Carbonate. 0 1.0 1.0 1.0 Sodium citrate 5.0 CFAA Citric acid. 0 1.0 1.0 QEA - - - - - 2.0 2.0 1.0 - SRP - - - - - 1.0 1.0 0.2 - Zeolite A - - - - - 15.0 26.0 15.0 16.0 Sodium silicate PEG - - - - - - 4.0 - - TAEDnToT5 Builder Agglomerate SKS-6 6. 0 5. 0. 0 3. 0 7. 0 10.0 LAS 4.0 5.0 - - 5.0 3.0 - 10.0 12.0 -add particulate components Bleaching granule I, IV, - 3.0 4.0 5 15 8.0 2.0 20 4.0 IV or VIII MBAS - - - 8.0 - - 8.0 - 4.0 LAS (flake) 8. 0 Spray-on Brightener 0. 2 0. 2 0. 3 0. 1 0. 2 0. 1 0. 6 Dye - - - 0.3 0.05 0.1 - - - AE7 7. 5. 7 Perfume 0. 8. 5 0. 8 0. 5 1.0 Dry-add QEA - - - 0.2 0.5 - - - - Citrate. 0 3. 0. 0 5.0 15.0 5.0 Percarbonate 15.0 3. 0 6. 0 10. 0 12.0 18.0 5. 0 Perborate - - - - 6.0 18.0 - - - Photobleach 0.02 0.02 0.02 0.1 0.05 - 0.3 - 0.03 Enzymes (cellulase, 1.5 0.3 0.5 0.5 0.8 2.0 0.5 0.16 0.2 amylase, protease, lipase) Carbonate II - --- - 5.0 8.0 10.0 5.0 Perfume(encapsulated) 0.6 0.5. 0.5 - 0.3 0.5 0.2 0.1 0.6 Suds suppressor 1.0 0.6 0.3- 0.10 0.5 1.0 0.3 1.2 Soap 0.5 0.2 0.3 3.0 0.5 - - 0.3 - Citric acid II 5.0 5. 0 Dyed carbonate (blue, 0.5 0.5 ? 2.0 - 0.5 0.5 0.5 1.0 green) SKS-6. 0 6. 0 Fillers up to 100%

Table m The following are high density and bleach-containing detergent formulations according to the present invention: ABC Blown Powder ZeoliteA--15.0 Sodiumsulfate 0. 0 5. 0 0. 0 LAS 3. 0-3. 0 C45AS 3.0 2.0 4.0 QAS - - 1.5 DTPMP 0. 4 0. 4 0. 4 CMC 0. 4 0. 4 0. 4 MA/AA 4. 0 2. 0 2. 0 bleaching granule I or Vin 7.0 TAED--3. 0 Agglomerates bleaching granule-5.0 2.0 I-VIII or mixtures QAS 1.0 - - LAS-11. 0 7.0 TAS 2.0 2.0 1.0 Silicate 3. 0-4. 0 Zeolite A 8.0 8.0 8.0 Carbonate 8. 0 8. 0 4.0 Agglomerate NaSKS-6 (n or (In 15. 0 12. 0 5. 0 NaSKS-6(I) or (II) 15.0 12.0 5.0 LAS 8.0 7.0 4.0 AS5. 0 Spray On Perfume 0. 3 0. 3 0. 3 C25E3 2. 0-2. 0 brightener 0.1 0.4 photobleach 0.03 0.05 Dry additives QEA 1.0 0.5 0.5 Citric acid I 5. 0-2. 0 Bicarbonate I-3. 0- CarbonateII 8. 0 15. 0 10.0 NAC OBS 2. 0-- Manganesecatalyst--0.3 Percarbonate 14.0 7. 0 10.0 Polyethylene oxide of MW 5,000,000--0.2 Bentonite clay--10.0 effervescence granule of maleic acid/5.5 7.5 carbonate/bicarbonate 2: 2: 1 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 Sodium sulfate 0. 0 3. 0 0. 0 Balance (Moisture and 100.0 100.0 100.0 Miscellaneous) Density (g/litre) 850 850 850 Table III V W X Y Z AA BB CC DD LAS 12.0 16.0 20.0 16.0 23.0 22.0 Sodium C 4-C 15 AS 4. 5---4.0 4.0- Ci4-Ci5 alcohol ethoxylate (0.5) sulfate C14-C15 alcohol - - 2.0 1.0 1.0 1.0- ethoxylate (3) sulfate Sodium C14-C15 2. 0 2. 0-1. 3--0.6 4.0 5.0 alcohol ethoxylate (3 or 9) cationic surfactant--1.0 0.5 2.0 0.5 1.0 Tallow fatty acid----1. 0 Tallow alcohol----0.2 ethoxylate (50) ZeoliteA-14. 0-20.3 11.0 5.0 SKS-6---11. 0--7.5 18.0 Sodium 23.0 25.0 24.0 22,0-20. 0--- tripolyphosphate Sodium carbonate 15.0 12.0 15.0 10.0 13.0 11.0 10.0 15.0 20.0 Sodium Polyacrylate 0.5 0.5 0.5 0.5 - - - 7.0 7.5 (45%) Sodium--1.0 1.0 1.0 2.0 0. 5-- polyacrylate/maleate polymer Sodium silicate (1: 6 3. 0 6. 0 9. 0 8.0 9. 0 6.0 8.0 12.0- ratio NaO/SiO2) (46%) Sodium sulfate 25.0 18.0 20.0 18.0 20.0 22.0 13.0 3.0- Sodium 5.0 5.0 10.0 8.0 3.0 1.0 2.0 3.5 3.0 perborate/percarbonate Poly (ethyleneglycol), 1.5 1.5 1.0 1.0 - - 0.5 0.3 0.1 MW-4000 (50%) CMC 1.0 1.0 0.5 0.5-- Citric acid - - - 4.0 2.0- -- effervescence particle 5.0 10.0 (malic acid/ bicarbonate/carbonate 2 : 1 : 2) Bleach granule I-VIII 5.5 10 0.5 2.5 1.0 3.7 1.3 4.0 3.0 or mixtures Soil release polymer 1. 5 1. 5 1. 0 1. 0-1. 0-0. 3 0.4 Moisture 7.5 7.5 6.0 7.0 5.0 3.0 5.0 2.5 3.5 Magnesium sulphate----1.0 0.5 1.5 Speckle 0. 5 3. 0 5.0 0.5- Chelants - - - - 0.8 0.6 1.0 - 0.3 Enzymes - 2.0 0.5 0.3 2.0 1.5 2.0 0.2 0.4 minors, e. g. perfume, 1. 0 1. 0 1. 0 1. 0 0. 5 1.5 1.0 0.2 0.8 brightener, photo- bleach, dye Table IV CC DD EE FF LAS 13.3 8.0 Sodium C 14-C 15 alcohol 3. 9 4. 0 4. 5 sulfate C14W15 alcohol ethoxylate 2.0 2.0- (O. 5) sulfate C14-C15 alcohol ethoxylate - - - - (3) sulfate Sodium C14-C15 alcohol 0.5 0.5 0.5 5.0 ethoxylate (6.5) QAS 1. 0--0. Tallow fatty acid 0.5 - - - Tallow alcohol ethoxylate--1.0 0.3 (50) Sodium tripolyphosphate-41-20.0 Zeolite A, 26.-21.3 1. 0 Sodium carbonate 23.9 12.25.2 17.0 4 Sodium Polyacrylate (45%) 3.4 0.0 2.7 Sodium polyacrylate/maleate--1.0 1.5 polymer Sodium silicate (1: 6 ratio 2.4 6.4 2.1 6.0 NaO/SiO2) (46%) Sodium sulfate 10.5 10.8.2 15.0 9 Sodium perborate/sodium 1.0 1.0 1.0 2.0 percarbonate Poly (ethyleneglycol), MW 1.7 0.4 1.0 -4000 (50%) CMC 1.0 - - 0.3 Citric acid--3. 0 TAED 0. 6--- bleach granule I, m, IV or 3. 0 2.0 6. 5 0. 8 vm Soil release polymer-1.5 1.0 1.0 Moisture 7. 5 3. 1 6. 1 7. 3 Magnesium sulphate---1.0 Chelants--0. 5 Enzymes-1. 0-1.5 minors, e. g. perfume, 1.0 1.0 1.0 1.0 brightener, photo-bleach, dye