BACKGROUND OF THE INVENTION Polyphosphates are known as cheating agents, chemical polishes for stainless steel, and catalysts or dehydrating agents in chemical reactions.

Generally, a common polyphosphate is sodium polyphosphate and is described as Nan+2PnO3n+1 (n=2, 3, 4,...). A typical sodium polyphosphate is sodium tripolyphosphate.

Sodium tripolyphosphate (STPP) is a builder commonly used in detergent compositions. However, during the crutching and/or spray-drying processing steps for making detergent products, STPP may revert or hydrolyze to form part pyrophosphate and part orthophosphate, the latter being a less-efficient builder and having among other disadvantages a detrimental effect on the softness of the fabrics being washed. In fully-built solid detergent compositions, the hydrolysis of some of the STPP is compensated for, by raising the level of STPP in the product. Moreover, a significant drawback in the elimination or reduction of tripolyphosphate builders from detergent products is a corresponding decrease in the whiteness maintenance of fabrics.

Based on the foregoing, there is a need for a builder which does not form orthophosphate nor decrease whiteness maintenance of fabrics.

SUMMARY OF THE INVENTION The present invention relates to detergent compositions having a polyphosphate salt. More particularly, it relates to detergent compositions having a mixed polyphosphate salt which includes an alkali metal ion and a magnesium counter ion, and has the formula : MxMg ((n-x+2)/2) PnO3n+1, wherein n is an integer from 3 to 25, x is an integer from 1 to n, and M is an alkali metal.

The present invention also relates to a process for making a mixed polyphosphate salt including the steps of mixing an alkali metal phosphate with a magnesium counter ion to form a mixture, and heating the mixture at about 700- 800 °C to form a mixed polyphosphate salt.

These and other features, aspects, and advantages of the present invention will become evident to those skilled in the art from a reading of the present disclosure.

DETAILED DESCRIPTION OF THE INVENTION While this specification concludes with claims distinctly pointing out and particularly claiming that which is regarded as the invention, it is believed that the invention can be better understood through a careful reading of the following detailed description of the invention.

All percentages and proportions are by weight, all temperatures are expressed in degrees Celsius (°C), and all molecular weights are in weight average molecular weight, unless otherwise indicated.

All ratios are weight ratios unless specifically stated otherwise.

As used herein,"comprising"means that other steps and other ingredients which do not affect the end result can be added. This term encompasses the terms"consisting of'and"consisting essentially of'.

All cited references are incorporated herein by reference in their entireties.

Citation of any reference is not an admission regarding any determination as to its availability as prior art to the claimed invention.

As used herein, the term"detergent composition"or"detergent"is intended to designate any of the agents conventionally used for removing soil, such as general household detergents or laundry detergents of the synthetic or soap type.

Mixed Polyphosphate Salt The present invention relates to a detergent composition containing a mixed polyphosphate salt which includes an alkali metal ion and a magnesium counter ion, and which has the formula : MxMg ((n-x+2)/2) PnO3n+1, wherein n is an integer from 3 to 25, x is an integer from 1 to n, and M is an alkali metal.

The detergent composition of the present invention shows less hydrolysis and retains more performance after treatment by a simulated tower process, as compared to a conventional polyphosphate. As noted above, conventional polyphosphates, such as Glass H, reverts or hydrolyzes during the crutching and/or spray-drying processing steps for making detergent products. The conventional polyphosphates form lower chain length polyphosphates including pyrophosphate and orthophosphate, which are less efficient builders and which may having, among other disadvantages, a detrimental effect on the softness and whiteness of the fabrics being washed. However, the mixed polyphosphate salt of the present invention show less hydrolysis and improved whiteness maintenance of fabrics than conventional polyphosphate. In addition, the detergent composition in the present invention provides a much better structurant which improves the hardness and wear rate when included into a laundry bar or a tablet.

The mixed polyphosphate salt of the present invention has the formula : MxMg ((n-x+2)/2) PnO3n+ 1, wherein n is an integer from 3 to 25, x is an integer from 1 to n, and M is an alkali metal. Preferably, x is from n-2 to n. M is preferably a sodium ion, or a potassium ion. More preferably, M is sodium and n is from 10 to 25.

The mixed polyphosphate salt may be formed by combining an alkali metal phosphate and a magnesium counter ion. A preferred magnesium counter ion is derived from a magnesium compound selected from the group consisting of magnesium chloride, magnesium sulfate, magnesium phosphate, magnesium hydroxide, and a mixture thereof. Magnesium chloride and magnesium hydroxide are more preferred. A preferred alkali metal phosphate is selected from the group consisting of sodium phosphate, potassium phosphate, sodium pyrophosphate, potassium pyrophosphate, and a mixture thereof. Sodium phosphate is more preferred.

The mixed polyphosphate salt is preferably formed by mixing the alkali metal phosphate with a magnesium counter ion to form a mixture, and heating the mixture at about 700-800 °C. The mixture may be maintained at this temperature for about 1-2 hours, and then quenched to form the mixed polyphosphate salt.

The detergent composition herein typically contains, by weight of the detergent composition, from about 0. 5% to about 15% of the mixed polyphosphate salt, preferably from about 2% to 8% of the mixed polyphosphate salt.

The detergent composition herein is formed by mixing the mixed polyphosphate salt and other detersive ingredients to make a slurry, and further processed according to methods known in the art, or by admixing the pre-formed mixed polyphosphate salt with the other detersive ingredients after, for example, a tower process.

This mixed polyphosphate salt may replace all or part of a conventional builder, preferably all or part of a conventional phosphate builder.

Other Detersive Ingredients The detergent composition of the present invention can optionally include one or more detersive ingredients or other materials for assisting or enhancing cleaning performance, treatment of the substrate to be cleaned, or to modify the aesthetics of the detergent composition (e. g., perfumes, colorants, dyes, etc.).

The following are illustrative examples of such optional detergent materials. The list of components is non-limiting.

1. Detersive Surfactant The detergent composition optionally comprises a detersive surfactant.

The detersive surfactant is selected from the group consisting of an anionic surfactant, a cationic surfactant, an amphoteric surfactant, a nonionic surfactant, and a mixture thereof. Preferably the detergent composition comprises at least about 0. 01% of a detersive surfactant ; more preferably at least about 0. 1% ; more preferably at least about 1 % ; more preferably still, from about 5% to about 60%.

In a preferred embodiment of the present invention, the fine surfactant containing particles have been removed from the composition. Preferably, fine particles below 75 microns, more preferably below 150 microns, even more preferably below 250 microns, have been removed from the composition.

(1) Anionic Surfactants : Nonlimiting examples of anionic surfactants useful herein, typically at levels from about 0. 1% to about 50%, by weight, include the conventional C11-C18 alkyl benzene sulfonate ("LAS") and primary, branched-chain and random C10-C20 alkyl sulfates ("AS"), the C10-C1g secondary (2, 3) alkyl sulfates of the formula CH3 (CH2) X (CHOS03-M+) CH3 and CH3 (CH2) y (CHOSO3~M) CH2CH3 where x and (y + 1) are integers of at least about 7, preferably at least about 9, and M is a water-solubilizing cation, especially sodium, unsaturated sulfates such as oleyl sulfate, the C10-C1g alpha-sulfonated fatty acid esters, the C1 0-C1 8 sulfated alkyl polyglycosides, the C1 0-C1 8 alkyl alkoxy sulfates ("AEXS" ; especially EO 1-7 ethoxy sulfates), and C1 0-C1 8 alkyl alkoxy carboxylates (especially the EO 1-5 ethoxycarboxylates). The Cl 2-Cl 8 betaines and sulfobetaines ("sultaines"), C10-C1g amine oxides, and the like, can also be included in the overall compositions. C10-C20 conventional soaps may also be used. If high sudsing is desired, the branched-chain C10-C16 soaps may be used. Other conventional useful anionic surfactants are listed in standard texts.

Other suitable anionic surfactants that can be used are alkyl ester sulfonate surfactants including linear esters of C8-C20 carboxylic acids (i. e., fatty

acids) which are sulfonate with gaseous SO3 according to"The Journal of the American Oil Chemists Society", 52 (1975), pp. 323-329. Suitable starting materials would include natural fatty substances as derived from tallow, palm oil, etc.

Other anionic surfactants useful for detersive purposes can also be included in the laundry detergent compositions. These can include salts (including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di-and triethanolamine salts) of soap, Cg-C22 primary of secondary alkanesulfonates, Cg-C24 olefinsulfonates, sulfonate polycarboxylic acids prepared by sulfonation of the pyrolyzed product of alkaline earth metal citrates, e. g., as described in British patent specification No.

1, 082, 179, Cg-C24 alkylpolyglycolethersulfates (containing up to 10 moles of ethylene oxide) ; alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleoyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, paraffin sulfonates, alkyl phosphates, isethionates such as the acyl isethionates, N-acyl taurates, alkyl succinamates and sulfosuccinates, monoesters of sulfosuccinates (especially saturated and unsaturated C12-C1g monoesters) and diesters of sulfosuccinates (especially saturated and unsaturated C6-C12 diesters), sulfates of alkylpolysaccharides such as the sulfates of alkylpolyglucoside (the nonionic nonsulfated compounds being described below), and alkyl polyethoxy carboxylates such as those of the formula RO (CH2CH20) k-CH2COO-M+ wherein R is a Cg-C22 alkyl, k is an integer from 0 to 10, and M is a soluble salt- forming cation. 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. Further examples are described in"Surface Active Agents and Detergents" (Vol. I and 11 by Schwartz, Perry and Berch). A variety of such surfactants are also generally disclosed in U. S. Patent 3, 929, 678, issued December 30, 1975 to Laughlin, et al. at Column 23, line 58 through Column 29, line 23 (herein incorporated by reference).

A preferred disulfate surfactant has the formula

where R is an alkyl, substituted alkyl, alkenyl, aryl, alkaryl, ether, ester, amine or amide group of chain length Cl to C2g, preferably C3 to C24, most preferably Cg to C20, or hydrogen ; A and B are independently selected from alkyl, substituted alkyl, and alkenyl groups of chain length Cl to C2g, preferably Cl to C5, most preferably Cl or C2, or a covalent bond, and A and B in total contain at least 2 atoms ; A, B, and R in total contain from 4 to about 31 carbon atoms ; X and Y are anionic groups selected from the group consisting of sulfate and sulfonate, provided that at least one of X or Y is a sulfate group ; and M is a cationic moiety, preferably a substituted or unsubstituted ammonium ion, or an alkali or alkaline earth metal ion.

The disulfate surfactant is typically present at levels of incorporation of from about 0. 1% to about 50%, preferably from about 0. 1% to about 35%, most preferably from about 0. 5% to about 15% by weight of the detergent composition.

When included therein, the laundry detergent compositions typically comprise from about 0. 1 % to about 50%, preferably from about 1 % to about 40% by weight of an anionic surfactant.

(2) Nonionic Surfactants : Nonlimiting examples of nonionic surfactants useful herein typically at levels from about 0. 1% to about 50%, by weight include the alkoxylated alcohol (AE's) and alkyl phenols, polyhydroxy fatty acid amides (PFAA's), alkyl polyglycosides (APG's), C10-C1g glycerol ethers, and the like.

More specifically, the condensation products of primary and secondary aliphatic alcohols with from about 1 to about 25 moles of ethylene oxide (AE) are suitable for use as the nonionic surfactant in the detergent composition. The alkyl chain of the aliphatic alcohol can either be straight or branched, primary or secondary, and generally contains from about 8 to about 22 carbon atoms.

Examples of commercially available nonionic surfactants of this type

include : TergitolTM 15-S-9 (the condensation product of C11-C15 linear alcohol with 9 moles ethylene oxide) and TergitolTM 24-L-6 NMW (the condensation product of C12-C14 primary alcohol with 6 moles ethylene oxide with a narrow molecular weight distribution), both marketed by Union Carbide Corporation ; NeodolTM 45-9 (the condensation product of C14-C1s linear alcohol with 9 moles of ethylene oxide), NeodolTM 23-3 (the condensation product of C12-C13 linear alcohol with 3 moles of ethylene oxide), NeodolTM 45-7 (the condensation product of C14-C1s linear alcohol with 7 moles of ethylene oxide) and NeodolTM 45-5 (the condensation product of C14-C1s linear alcohol with 5 moles of ethylene oxide) marketed by Shell Chemical Company ; KyroTM EOB (the condensation product of C13-C1s alcohol with 9 moles ethylene oxide), marketed by The Procter & Gamble Company ; and Genapol LA 030 or 050 (the condensation product of C12-C14 alcohol with 3 or 5 moles of ethylene oxide) marketed by Hoechst.

Another class of preferred nonionic surfactants for use herein are the polyhydroxy fatty acid amide surfactants of the formula. wherein R1 is H, or C1 4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl or a mixture thereof, R2 is C5-31 hydrocarbyl, and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative thereof. Typical examples include the C12-CI8 and C12-C14 N-methylglucamides. See U. S. 5, 194, 639 and 5, 298, 636. N-alkoxy polyhydroxy fatty acid amides can also be used ; see U. S.

5, 489, 393.

Also useful as a nonionic surfactant in the detergent composition are the alkylpolysaccharides such as those disclosed in U. S. Patent 4, 565, 647, Llenado, issued January 21, 1986, having a hydrophobic group containing from about 6 to about 30 carbon atoms, preferably from about 10 to about 16 carbon atoms, and a polysaccharide, e. g. a polyglycoside, hydrophilic group containing from about

1. 3 to about 10, preferably from about 1. 3 to about 3, most preferably from about 1. 3 to about 2. 7 saccharide units.

Polyethylene, polypropylene, and polybutylene oxide condensates of alkyl phenols are also suitable for use as the nonionic surfactant of the surfactant systems of the detergent composition, with the polyethylene oxide condensates being preferred. These compounds include the condensation products of alkyl phenols having an alkyl group containing from about 6 to about 14 carbon atoms, preferably from about 8 to about 14 carbon atoms, in either a straight-chain or branched-chain configuration with the alkylen oxide. Commercially available nonionic surfactants of this type include IgepalTM CO-630, marketed by the GAF Corporation ; and TritonTM X-45, X-114, X-100 and X-102, all marketed by the Rohm & Haas Company. These surfactants are commonly referred to as alkylphenol alkoxylates (e. g., alkyl phenol ethoxylates).

The condensation products of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol are also suitable for use as the additional nonionic surfactant in the detergent composition. The hydrophobic portion of these compounds will preferably have a molecular weight of from about 1500 to about 1800 and will exhibit water insolubility. Examples of compounds of this type include certain of the commercially-available PluronicTM surfactants, marketed by BASF.

Also suitable for use as a nonionic surfactant in the detergent composition, are the condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylenediamine. The hydrophobic moiety of these products consists of the reaction product of ethylenediamine and excess propylene oxide, and generally has a molecular weight of from about 2500 to about 3000. This hydrophobic moiety is condensed with ethylene oxide to the extent that the condensation product contains from about 40% to about 80% by weight of polyoxyethylene and has a molecular weight of from about 5, 000 to about 11, 000. Examples of this type of nonionic surfactant include certain of the commercially available TetronicTM compounds, marketed by BASF.

Also preferred nonionics are amine oxide surfactants. The detergent compositions may comprise amine oxide in accordance with the general formula 1 : Rl (EO) x (PO) y (BO) zN (0) (CH2R') 2. qH20 (t).

In general, it can be seen that the structure (I) provides one long-chain moiety Rl (EO) X (PO) y (BO) z and two short chain moieties, CH2R'. R'is preferably selected from hydrogen, methyl and-CH2OH. In general R1 is a primary or branched hydrocarbyl moiety which can be saturated or unsaturated, preferably, R1 is a primary alkyl moiety. When x+y+z = 0, R1 is a hydrocarbyl moiety having chainlength of from about 8 to about 18. When x+y+z is different from 0, R1 may be somewhat longer, having a chainlength in the range C12-C24.

The general formula also encompasses amine oxides wherein x+y+z = 0, Rl = Cg-Cig, R'= H and q = 0-2, preferably 2. These amine oxides are illustrated by C12-14 alkyldimethyl amine oxide, hexadecyl dimethylamine oxide, octadecylamine oxide and their hydrates, especially the dihydrates as disclosed in U. S. Patents 5, 075, 501 and 5, 071, 594, incorporated herein by reference.

(3) Cationic Surfactants : Nonlimiting examples of cationic surfactants useful herein typically at levels from about 0. 1% to about 50%, by weight include the choline ester-type quats and alkoxylated quaternary ammonium (AQA) surfactant compounds, and the like.

Cationic surfactants useful as a component of the surfactant system is a cationic choline ester-type quat surfactant which are preferably water dispersible compounds having surfactant properties and comprise at least one ester (i. e.

-COO-) linkage and at least one catatonically charged group. Suitable cationic ester surfactants, including choline ester surfactants, have for example been disclosed in U. S. Patents Nos. 4, 228, 042, 4, 239, 660 and 4, 260, 529.

2. Conventional Builders A conventional detergent builder can optionally be included in the detergent compositions herein to assist in controlling mineral hardness. The

conventional builder is selected from the group consisting of a pyrophosphate, an orthophosphate, a tripolyphosphate, a higher phosphate, an alkali metal carbonate or a bicarbonate, an alkali silicate, an aluminosilicate, a polycarboxylate, and a mixture thereof. Inorganic as well as organic builders can be used. Builders are typically used in fabric laundering compositions to assist in the removal of particulate soils.

The level of conventional builder can vary widely depending upon the end use of the composition and its desired physical form. When present, the compositions will typically comprise at least about 1% conventional builder, and preferably from about 5% to about 60% of a conventional builder. Granular formulations typically comprise from about 10% to about 80%, more typically from about 15% to about 50% by weight, of the conventional builder. Lower or higher levels of conventional builder, however, are not meant to be excluded.

Conventional inorganic detergent builders include, but are not limited to, the alkali metal, ammonium and alkanolammonium salts of polyphosphates (exemplified by the tripolyphosphates, pyrophosphates, and glassy polymeric meta-phosphates), phosphonates, phytic acid, silicates, carbonates (including bicarbonates and sesquicarbonates), sulphates, and aluminosilicates. However, non-phosphate builders are required in some locales. Importantly, the compositions herein function surprisingly well even in the presence of the so- called"weak"builders (as compared with phosphates) such as citrate, or in the so-called"underbuilt"situation that may occur with zeolite or layered silicate builders.

Examples of conventional silicate builders are the alkali metal silicates, particularly those having a Si02 : Na2O ratio in the range 1. 6 : 1 to 3. 2 : 1 and layered silicates, such as the layered sodium silicates described in U. S. Patent 4, 664, 839, issued May 12, 1987 to H. P. Rieck. NaSKS-6 is the trademark for a crystalline layered silicate marketed by Hoechst (commonly abbreviated herein as"SKS-6"). Unlike zeolite builders, the Na SKS-6 silicate builder does not contain aluminum. NaSKS-6 has the delta-Na2SiO5 morphology form of layered silicate. SKS-6 is a highly preferred layered silicate for use herein, but other

such layered silicates, such as those having the general formula NaMSix02x+l yH20 wherein M is sodium or hydrogen, x is a number from 1. 9 to 4, preferably 2, and y is a number from 0 to 20, preferably 0 can be used herein.

Other silicates may also be useful such as for example magnesium silicate, which can serve as a crispening agent in granular formulations, as a stabilizing agent for oxygen bleaches, and as a component of suds control systems.

Examples of conventional carbonate builders are the alkaline earth and alkali metal carbonates as disclosed in German Patent Application No. 2, 321, 001 published on November 15, 1973.

Conventional aluminosilicate builders are useful in the detergent composition. Aluminosilicate builders are of great importance in most currently marketed heavy duty granular detergent compositions. Aluminosilicate builders include those having the empirical formula : Mz (ZA102) y] xH20 wherein z and y are integers of at least 6, the molar ratio of z to y is in the range from 1. 0 to about 0. 5, and x is an integer from about 15 to about 264.

Useful aluminosilicate ion exchange materials are commercially available.

These aluminosilicates can be crystalline or amorphous in structure and can be naturally-occurring aluminosilicates or synthetically derived. Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite P (B), Zeolite MAP and Zeolite X. This material is known as Zeolite A. Dehydrated zeolites (x = 0-10) may also be used herein. Preferably, the aluminosilicate has a mean particle size of about 0. 1-10 microns in diameter.

Conventional organic builders suitable for the purposes of the detergent composition include, but are not restricted to, a wide variety of polycarboxylate compounds. As used herein,"polycarboxylate"refers to compounds having a plurality of carboxylate groups, preferably at least 3 carboxylates. Conventional polycarboxylate builder can generally be added to the composition in acid form, but can also be added in the form of a neutralized salt. When utilized in salt

form, alkali metals, such as sodium, potassium, and lithium, or alkanolammonium salts are preferred.

Conventional citrate builders, e. g., citric acid and soluble salts thereof (particularly sodium salt), are polycarboxylate builders of particular importance due to their availability from renewable resources and their biodegradability.

Citrates can also be used in granular compositions, especially in combination with zeolite and/or layered silicate builders. Oxydisuccinates are also especially useful in such compositions and combinations.

Also suitable in the detergent compositions are the 3, 3-dicarboxy-4-oxa- 1, 6-hexanedioates and the related compounds disclosed in U. S. Patent 4, 566, 984 to Bush, issued January 28, 1986. Useful conventional succinic acid builders include the C5-C20 alkyl and alkenyl succinic acids and salts thereof. A particularly preferred compound of this type is dodecenylsuccinic acid. Specific examples of conventional succinate builders include : laurylsuccinate, myristylsuccinate, palmitylsuccinate, 2-dodecenylsuccinate (preferred), 2- pentadecenylsuccinate, and the like.

Other suitable polycarboxylates are disclosed in U. S. Patent 4, 144, 226, Crutchfield et al, issued March 13, 1979 and in U. S. Patent 3, 308, 067, Diehl, issued March 7, 1967. See also U. S. Patent 3, 723, 322 to Diehl, issued March 27, 1973.

Fatty acids, e. g., C12-C1 g monocarboxylic acids, can also be incorporated into the compositions alone, or in combination with the aforesaid conventional builders, especially citrate and/or the succinate builders, to provide additional builder activity. Such use of fatty acids will generally result in a diminution of sudsing, which should be taken into account by the formulator.

The various conventional alkali metal phosphates such as the well-know sodium tripolyphosphates, sodium pyrophosphate and sodium orthophosphate can be used, especially in the formulation of solids used for hand-laundering operations. Conventional phosphonate builders such as ethane-1-hydroxy-1, 1- diphosphonate and other known phosphonates (see, for example, U. S. Patents 3, 159, 581 to Diehl, issued December 1, 1964 ; 3, 213, 030 to Diehl, issued

October 19, 1965 ; 3, 400, 148 to Quimby, issued September 3, 1968 ; 3, 422, 021 to Roy, issued January 14, 1969 ; and 3, 422, 137 to Quimby, issued January 14, 1969) can also be used.

3. Alkoxylated Polycarboxylates Alkoxylated polycarboxylates such as those prepared from polyacrylates are useful herein to provide additional grease removal performance. Such materials are described in WO 91/08281 and PCT 90/01815 at p. 4 et seq..

Chemically, these materials comprise polyacrylates having one ethoxy side-chain per every 7-8 acrylate units. The side-chains are of the formula - (CH2CH20) m (CH2) nCH3 wherein m is 2-3 and n is 6-12. The side-chains are ester-linked to the polyacrylate"backbone"to provide a"comb"polymer type structure. The molecular weight can vary, but is typically in the range of about 2000 to about 50, 000. Such alkoxylated polycarboxylates can comprise from about 0. 05% to about 10% of the compositions herein.

4. Bleaching Compounds-Bleaching Agents and Bleach Activators The detergent compositions herein may optionally contain bleaching agents or bleaching compositions containing a bleaching agent and one or more bleach activators. When present, bleaching agents will typically be at levels of from about 1 % to about 30%, more typically from about 5% to about 20%, of the detergent composition, especially for fabric laundering. If present, the amount of bleach activators will typically be from about 0. 1% to about 60%, more typically from about 0. 5% to about 40% of the bleaching composition comprising the bleaching agent-plus-bleach activator.

(1) Oxygen Bleaching Agents : Preferred detergent compositions comprise, as part or all of the laundry or cleaning adjunct materials, an oxygen bleaching agent. Oxygen bleaching agents useful in the detergent composition can be any of the oxidizing agents known for laundry, hard surface cleaning, automatic dishwashing or denture cleaning purposes. Oxygen bleaches or mixtures thereof are preferred, though other oxidant bleaches, such as oxygen, an enzymatic hydrogen peroxide

producing system, or hypohalites such as chlorine bleaches like hypochlorite, may also be used.

Oxygen bleaches deliver"available oxygen" (AvO) or"active oxygen" which is typically measurable by standard methods such as iodide/thiosulfate and/or ceric sulfate titration. See the well-know work by Swern, or Kirk Othmer's Encyclopedia of Chemical Technology under"Bleaching Agents".

When the oxygen bleach is a peroxygen compound, it contains-O-O-linkages with one O in each such linkage being"active". AvO content of such an oxygen bleach compound, usually expressed as a percent, is equal to 100 * the number of active oxygen atoms * (16/molecular weight of the oxygen bleach compound).

Preferably, an oxygen bleach will be used herein, since this benefits directly from combination with the transition-metal bleach catalyst. The oxygen bleach herein can have any physical form compatible with the intended application ; more particularly, solid-form oxygen bleaches as well as adjuncts, promoters or activators are included.

Common oxygen bleaches of the peroxygen type include hydrogen peroxide, inorganic peroxohydrates, organic peroxohydrates and the organic peroxyacids, including hydrophilic and hydrophobic mono-or di-peroxyacids.

These can be peroxycarboxylic acids, peroxyimidic acids, amidoperoxycarboxylic acids, or their salts including the calcium, magnesium, or mixed-cation salts.

Peracids of various kinds can be used both in free form and as precursors known as"bleach activators"or"bleach promoters"which, when combined with a source of hydrogen peroxide, perhydrolyze to release the corresponding peracid.

Also useful herein as oxygen bleaches are the inorganic peroxides such as Na202, superoxides such as K02, organic hydroperoxides such as cumene hydroperoxide and t-butyl hydroperoxide, and the inorganic peroxoacids and their salts such as the peroxosulfuric acid salts, especially the potassium salts of peroxodisulfuric acid and, more preferably, of peroxomonosulfuric acid including the commercial triple-salt form sold as OXONE by DuPont and also any equivalent commercially available forms such as CUROX from Akzo or CAROAT

from Degussa. Certain organic peroxides, such as dibenzoyl peroxide, may be useful, especially as additives rather than as primary oxygen bleach.

Mixed oxygen bleach systems are generally useful, as are mixtures of any oxygen bleaches with the known bleach activators, organic catalysts, enzymatic catalysts and mixtures thereof ; moreover such mixtures may further include brighteners, photobleaches and dye transfer inhibitors of types well-know in the art.

Preferred oxygen bleaches, as noted, include the peroxohydrates, sometimes known as peroxyhydrates or peroxohydrates. These are organic or, more commonly, inorganic salts capable of releasing hydrogen peroxide readily.

They include types in which hydrogen peroxide is present as a true crystal hydrate, and types in which hydrogen peroxide is incorporated covalently and is released chemically, for example by hydrolysis. Typically, peroxohydrates deliver hydrogen peroxide readily enough that it can be extracted in measurable amounts into the ether phase of an ether/water mixture. Peroxohydrates are characterized in that they fail to give the Riesenfeld reaction, in contrast to certain other oxygen bleach types described hereinafter. Peroxohydrates are the most common examples of"hydrogen peroxide source"materials and include the perborates, percarbonates, perphosphates, and persilicates. Other materials which serve to produce or release hydrogen peroxide are, of course, useful.

Mixtures of two or more peroxohydrates can be used, for example when it is desired to exploit differential solubility. Suitable peroxohydrates include sodium carbonate peroxyhydrate and equivalent commercial"percarbonate"bleaches, and any of the so-called sodium perborate hydrates, the"tetrahydrate"and "monohydrate"being preferred ; though sodium pyrophosphate peroxyhydrate can be used. Many such peroxohydrates are available in processed forms with coatings, such as of silicate and/or borate and/or waxy materials and/or surfactants, or have particle geometries, such as compact spheres, which improve storage stability. By way of organic peroxohydrates, urea peroxyhydrate can also be useful herein.

Percarbonate bleach includes, for example, dry particles having an mean particle size in the range from about 500 micrometers to about 1, 000 micrometers, not more than about 10% by weight of said particles being smaller than about 200 micrometers and not more than about 10% by weight of said particles being larger than about 1, 250 micrometers. Percarbonates and perborates are widely available in commerce, for example from FMC, Solvay and Tokai Denka.

Bleaching agents other than oxygen bleaching agents are also known in the art and can be utilized herein. One type of non-oxygen bleaching agent of particular interest includes photoactivated bleaching agents such as the sulfonate zinc and/or aluminum phthalocyanines. See U. S. Patent 4, 033, 718, issued July 5, 1977 to Holcombe et al. If used, detergent compositions will typically contain from about 0. 025% to about 1. 25%, by weight, of such bleaches, especially sulfonate zinc phthalocyanine.

(2) Bleach Activators Bleach activators useful herein include amides, imides, esters and anhydrides. Commonly at least one substituted or unsubstituted acyl moiety is present, covalently connected to a leaving group as in the structure R-C (O)-L. In one preferred mode of use, bleach activators are combined with a source of hydrogen peroxide, such as the perborates or percarbonates, in a single product.

Conveniently, the single product leads to in situ production in aqueous solution (i. e., during the washing process) of the percarboxylic acid corresponding to the bleach activator. The product itself can be hydrous, for example a powder, provided that water is controlled in amount and mobility such that storage stability is acceptable. Alternately, the product can be anhydrous. With respect to the above bleach activator structure RC (O) L, the atom in the leaving group connecting to the peracid-forming acyl moiety R (C) O- is most typically 0 or N.

Bleach activators can have non-charged, positively or negatively charged peracid-forming moieties and/or noncharged, positively or negatively charged leaving groups. One or more peracid-forming moieties or leaving-groups can be present. See, for example, U. S. 5, 595, 967, U. S. 5, 561, 235, U. S. 5, 560, 862 or

the bis- (peroxy-carbonic) system of U. S. 5, 534, 179. Bleach activators can be substituted with electron-donating or electron-releasing moieties either in the leaving-group or in the peracid-forming moiety or moieties, changing their reactivity and making them more or less suited to particular pH or wash conditions. For example, electron-withdrawing groups such as NO2 improve the efficacy of bleach activators intended for use in mild-pH (e. g., from about 7. 5- to about 9. 5) wash conditions.

Cationic bleach activators include quaternary carbamate-, quaternary carbonate-, quaternary ester-and quaternary amide-types, delivering a range of cationic peroxyimidic, peroxycarbonic or peroxycarboxylic acids to the wash. An analogous but non-cationic palette of bleach activators is available when quaternary derivatives are not desired. In more detail, cationic activators include quaternary ammonium-substituted activators of WO 96-06915, U. S. 4, 751, 015 and 4, 397, 757, EP-A-284292, EP-A-331, 229 and EP-A-03520 including 2- (N, N, N-trimethyl ammonium) ethyl-4-sulphophenyl carbonate- (SPCC) ; N- octyl, N, N-dimethyl-N 10-carbophenoxy decyl ammonium chloride- (ODC) ; 3- (N, N, N-trimethyl ammonium) propyl sodium-4-sulphophenyl carboxylate ; and N, N, N-trimethyl ammonium toluyloxy benzene sulfonate. Also useful are cationic nitriles as disclosed in EP-A-303, 520 and in European Patent Specification 458, 396 and 464, 880. Other nitrile types have electron-withdrawing substituents as described in U. S. 5, 591, 378 ; examples including 3, 5-dimethoxybenzonitrile and 3, 5-dinitrobenzonitrile.

Other bleach activator disclosures include GB 836, 988 ; 864, 798 ; 907, 356 ; 1, 003, 310 and 1, 519, 351 ; German Patent 3, 337, 921 ; EP-A-0185522 ; EP-A- 0174132 ; EP-A-0120591 ; U. S. Pat. Nos. 1, 246, 339 ; 3, 332, 882 ; 4, 128, 494 ; 4, 412, 934 and 4, 675, 393, and the phenol sulfonate ester of alkanoyl aminoacids disclosed in U. S. 5, 523, 434. Suitable bleach activators include any acetylated diamine types, whether hydrophilic or hydrophobic in character.

Preferred bleach activators include N, N, N'N'-tetraacetyl ethylene diamine (TAED) or any of its close relatives including the triacetyl or other unsymmetrical derivatives. TAED and the acetylated carbohydrates such as glucose

pentaacetate and tetraacetyl xylose are preferred hydrophilic bleach activators.

Depending on the application, acetyl triethyl citrate, a liquid, also has some utility, as does phenyl benzoate.

Preferred hydrophobic bleach activators include decyl oxybenzoic acid, sodium lauroyl oxybenzene sulfonate, sodium nonanoyloxybenzene sulfonate (NOBS or SNOBS), substituted amide types and activators related to certain imidoperacid bleaches, for example as described in U. S. Patent 5, 061, 807, issued October 29, 1991 and assigned to Hoechst Aktiengesellschaft of Frankfurt, Germany. Japanese Laid-Open Patent Application (Kokai) No. 4- 28799 for example describes a bleaching agent and a bleaching detergent composition comprising an organic peracid precursor described by a general formula and illustrated by compounds which may be summarized more particularly as conforming to the formula :

wherein L is sodium p-phenolsulfonate, R1 is CH3 or C12H25 and R2 is H.

Analogs of these compounds having any of the leaving-groups identified herein and/or having R1 being linear or branched C6-C16 are also useful.

Another group of peracids and bleach activators herein are those derivable from acyclic imidoperoxycarboxylic acids and salts thereof of the formula :

cyclic imidoperoxycarboxylic acids and salts thereof of the formula :

and (iii) mixtures of said compounds, (i) and (ii) ; wherein M is selected from hydrogen and bleach-compatible cations having charge q ; and y and z are integers such that said compound is electrically neutral ; E, A and X comprise hydrocarbyl groups ; and said terminal hydrocarbyl groups are contained within E and A. The structure of the corresponding bleach activators is obtained by deleting the peroxy moiety and the metal and replacing it with a leaving-group L, which can be any of the leaving-group moieties defined elsewhere herein. In preferred embodiments, there are encompassed detergent compositions wherein, in any of said compounds, X is linear C3-Cg alkyl ; A is selected from : wherein n is from 0 to about 4, and wherein R1 and E are said terminal hydrocarbyl groups, R2, R3 and R4 are independently selected from H, C1-C3 saturated alkyl, and C1-C3 unsaturated alkyl ; and wherein said terminal hydrocarbyl groups are alkyl groups comprising at least six carbon atoms, more typically linear or branched alkyl having from about 8 to about 16 carbon atoms.

Other suitable bleach activators include sodium-4-benzoyloxy benzene sulfonate (SBOBS) ; sodium-1-methyl-2-benzoyloxy benzene-4-sulphonate ; sodium-4-methyl-3-benzoyloxy benzoate (SPCC) ; trimethyl ammonium toluyloxy-benzene sulfonate ; or sodium 3, 5, 5-trimethyl hexanoyloxybenzene sulfonate (STHOBS).

Bleach activators may be used in an amount of up to 20%, preferably from 0. 1-10% by weight, of the composition, though higher levels, 40% or more, are acceptable, for example in highly concentrated bleach additive product forms or forms intended for appliance automated dosing.

Highly preferred bleach activators useful herein are amide-substituted and have either of the formulae : or mixtures thereof, wherein Ri is alkyl, aryl, or alkaryl containing from about 1 to about 14 carbon atoms including both hydrophilic types (short R1) and hydrophobic types (R1 is especially from about 8 to about 12), R2 is alkylene, arylene or alkarylene containing from about 1 to about 14 carbon atoms, R5 is H, or an alkyl, aryl, or alkaryl containing from about 1 to about 10 carbon atoms, and L is a leaving group.

A leaving group as defined herein is any group that is displaced from the bleach activator as a consequence of attack by perhydroxide or equivalent reagent capable of liberating a more potent bleach from the reaction.

Perhydrolysis is a term used to describe such reaction. Thus bleach activators perhydrolyze to liberate peracid. Leaving groups of bleach activators for relatively low-pH washing are suitably electron-withdrawing. Preferred leaving groups have slow rates of reassociation with the moiety from which they have been displaced.

Leaving groups of bleach activators are preferably selected such that their removal and peracid formation are at rates consistent with the desired application, e. g., a wash cycle. In practice, a balance is struck such that leaving- groups are not appreciably liberated, and the corresponding activators do not appreciably hydrolyze or perhydrolyze, while stored in a bleaching composition.

The pK of the conjugate acid of the leaving group is a measure of suitability, and is typically from about 4 to about 16, or higher, preferably from about 6 to about 12, more preferably from about 8 to about 11.

Preferred bleach activators include those of the formulae, for example the amide-substituted formulae, hereinabove, wherein R, R2 and R5 are as defined for the corresponding peroxyacid and L is selected from the group consisting of : and mixtures thereof, wherein Ri is a linear or branched alkyl, aryl, or alkaryl group containing from about 1 to about 14 carbon atoms, R3 is an alkyl chain containing from 1 to about 8 carbon atoms, R4 is H or R3, and Y is H or a solubilizing group. These and other known leaving groups are, more generally, general suitable alternatives for introduction into any bleach activator herein.

Preferred solubilizing groups include-SO3-M+, -CO2-M+, -SO4-+,-N+ (R) 4X-and oeN (R3) 2, more preferably-S03 M and-C02 M wherein R3 is an alkyl chain containing from about 1 to about 4 carbon atoms, M is a bleach-stable cation and X is a bleach-stable anion, each of which is selected consistent with

maintaining solubility of the activator. Under some circumstances, for example solid-form European heavy-duty granular detergents, any of the above bleach activators are preferably solids having crystalline character and melting-point above about 50 deg. C ; in these cases, branched alkyl groups are preferably not included in the oxygen bleach or bleach activator. Melting-point reduction can be favored by incorporating branched, rather than linear alkyl moieties into the oxygen bleach or precursor.

When solubilizing groups are added to the leaving group, the activator can have good water-solubility or dispersability while still being capable of delivering a relatively hydrophobic peracid. Preferably, M is alkali metal, ammonium or substituted ammonium, more preferably Na or K, and X is halide, hydroxide, methylsulfate or acetate. Solubilizing groups can, more generally, be used in any bleach activator herein. Bleach activators of lower solubility, for example those with leaving group not having a solubilizing group, may need to be finely divided or dispersed in bleaching solutions for acceptable results.

Preferred bleach activators also include those of the above general formula wherein L is selected from the group consisting of : wherein R3 is as defined above and Y is-S03-M+ or-C02-M+ wherein M is as defined above.

Preferred examples of bleach activators of the above formulae include : (6-octanamidocaproyl) oxybenzenesulfonate, (6-nonanamidocaproyl) oxybenzenesulfonate, (6-decanamidocaproyl) oxybenzenesulfonate, and mixtures thereof.

Other useful activators, disclosed in U. S. 4, 966, 723, are benzoxazin-type, such as a C6H4 ring to which is fused in the 1, 2-positions a moiety --C (O) OC (Rl) =N-.

Depending on the activator and precise application, good bleaching results can be obtained from bleaching systems having with in-use pH of from about 6 to

about 13, preferably from about 9. 0 to about 10. 5. Typically, for example, activators with electron-withdrawing moieties are used for near-neutral or sub- neutral pH ranges. Alkalis and buffering agents can be used to secure such pH.

Acyl lactam activators are very useful herein, especially the acyl caprolactams (see for example WO 94-28102 A) and acyl valerolactams (see U. S. 5, 503, 639) of the formulae : wherein R6 is H, alkyl, aryl, alkoxyaryl, an alkaryl group containing from 1 to about 12 carbon atoms, or substituted phenyl containing from about 6 to about 18 carbons. See also U. S. 4, 545, 784 which discloses acyl caprolactams, including benzoyl caprolactam adsorbed into sodium perborate. In certain preferred embodiments of the detergent composition, NOBS, lactam activators, imide activators or amide-functional activators, especially the more hydrophobic derivatives, are desirably combined with hydrophilic activators such as TAED, typically at weight ratios of hydrophobic activator : TAED in the range of 1 : 5 to 5 : 1, preferably about 1 : 1. Other suitable lactam activators are alpha-modified, see WO 96-22350 A1, July 25, 1996. Lactam activators, especially the more hydrophobic types, are desirably used in combination with TAED, typically at weight ratios of amido-derived or caprolactam activators : TAED in the range of 1 : 5 to 5 : 1, preferably about 1 : 1. See also the bleach activators having cyclic amidine leaving-group disclosed in U. S. 5, 552, 556.

Nonlimiting examples of additional activators useful herein are to be found in U. S. 4, 915, 854, U. S. 4, 412, 934 and 4, 634, 551. The hydrophobic activator nonanoyloxybenzene sulfonate (NOBS) and the hydrophilic tetraacetyl ethylene diamine (TAED) activator are typical, and mixtures thereof can also be used.

The superior bleaching/cleaning action of the detergent compositions is also preferably achieved with safety to natural rubber machine parts, for example of certain European washing appliances (see WO 94-28104) and other natural

rubber articles, including fabrics containing natural rubber and natural rubber elastic materials. Complexities of bleaching mechanisms are legion and are not completely understood.

(5) Bleach Catalysts If desired, the bleaching compounds can be catalyzed by means of a manganese compound. Such compounds are well known in the art and include, for example, the manganese-based catalysts disclosed in U. S. Pat. 5, 246, 621, U. S. Pat. 5, 244, 594 ; U. S. Pat. 5, 194, 416 ; U. S. Pat. 5, 114, 606 ; and European Pat. App. Pub. Nos. 549, 271A1, 549, 272A1, 544, 440A2, and 544, 490A1 ; Preferred examples of these catalysts include Mniv2 (u-0) 3 (1, 4, 7-trimethyl-1, 4, 7- triazacyclononane) 2 (pF6) 2, Mn 1 l l2 (u-0) 1 (u-OAc) 2 (1, 4, 7-trimethyl-1, 4, 7- triazacyclononane) 2- (CI04) 2, Mnlv4 (u-0) 6 (1, 4, 7-triazacyclononane) 4 (CI04) 4, Mnl l iMnlV4 (u-O) 1 (u-OAc) 2- (1, 4, 7-trimethyl-1, 4, 7-triazacyclononane) 2 (CI04) 3, MnIV (1, 4, 7-trimethyl-1, 4, 7-triazacyclononane)- (OCH3) 3 (PF6), and mixtures thereof. Other metal-based bleach catalysts include those disclosed in U. S. Pat.

4, 430, 243 and U. S. Pat. 5, 114, 611. The use of manganese with various complex ligands to enhance bleaching is also reported in the following United States Patents : 4, 728, 455 ; 5, 284, 944 ; 5, 246, 612 ; 5, 256, 779 ; 5, 280, 117 ; 5, 274, 147 ; 5, 153, 161 ; and 5, 227, 084.

As a practical matter, and not by way of limitation, the compositions and processes herein can be adjusted to provide on the order of at least one part per ten million of the active bleach catalyst species in the aqueous washing liquor, and will preferably provide from about 0. 1 ppm to about 700 ppm, more preferably from about 1 ppm to about 500 ppm, of the catalyst species in the laundry liquor.

5. Brightener Any optical brighteners or other brightening or whitening agents known in the art can be incorporated at levels typically from about 0. 05% to about 1. 2%, by weight, into the detergent compositions herein. Commercial optical brighteners which may be useful in the detergent composition can be classified into subgroups, which include, but are not necessarily limited to, derivatives of

stilbene, pyrazoline, coumarin, carboxylic acid, methinecyanines, dibenzothiphene-5, 5-dioxide, azoles, 5-and 6-membered-ring heterocycles, and other miscellaneous agents. Examples of such brighteners are disclosed in"The Production and Application of Fluorescent Brightening Agents", M. Zahradnik, Published by John Wiley & Sons, New York (1982).

6. Chelating Agents The detergent compositions herein may also optionally contain one or more iron and/or manganese cheating agents. Such cheating agents can be selected from the group consisting of amino carboxylates, amino phosphonates, polyfunctionally-substituted aromatic cheating agents and mixtures therein, all as hereinafter defined.

A preferred biodegradable chelator for use herein is ethylenediamine disuccinate ("EDDS"), especially the [S, S] isomer as described in U. S. Patent 4, 704, 233, November 3, 1987, to Hartman and Perkins.

If utilized, these cheating agents will generally comprise from about 0. 1% to about 15% by weight of the detergent compositions herein.

7. Enzymes Enzymes can be included in the detergent compositions for a variety of purposes, including removal of protein-based, carbohydrate-based, or triglyceride-based stains from substrates, for the prevention of refugee dye transfer in fabric laundering, and for fabric restoration. Suitable enzymes include proteases, amylases, lipases, cellulases, peroxidases, and mixtures thereof of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin.

Preferred selections are influenced by factors such as pH-activity and/or stability optima, thermostability, and stability to active detergents, builders and the like. In this respect bacterial or fungal enzymes are preferred, such as bacterial amylases and proteases, and fungal cellulases.

"Detersive enzyme", as used herein, means any enzyme having a cleaning, stain removing or otherwise beneficial effect in a laundry, hard surface cleaning or personal care detergent composition. Preferred detersive enzymes are hydrolases such as proteases, amylases and lipases. Preferred enzymes for

laundry purposes include, but are not limited to, proteases, ceilulases, lipases and peroxidases. Highly preferred for automatic dishwashing are amylases and/or proteases, including both current commercially available types and improved types which, though more and more bleach compatible though successive improvements, have a remaining degree of bleach deactivation susceptibility.

Enzymes are normally incorporated into detergent or detergent additive compositions at levels sufficient to provide a"cleaning-effective amount". The term"cleaning effective amount"refers to any amount capable of producing a cleaning, stain removal, soil removal, whitening, deodorizing, or freshness improving effect on substrates such as fabrics, dishware and the like. In practical terms for current commercial preparations, typical amounts are up to about 5 mg by weight, more typically 0. 01 mg to 3 mg, of active enzyme per gram of the detergent composition. Stated otherwise, the compositions herein will typically comprise from 0. 001% to 5%, preferably 0. 01%-1% by weight of a commercial enzyme preparation. Protease enzymes are usually present in such commercial preparations at levels sufficient to provide from 0. 005 to 0. 1 Anson units (AU) of activity per gram of composition. For certain detergents, such as in automatic dishwashing, it may be desirable to increase the active enzyme content of the commercial preparation in order to minimize the total amount of non-catalytically active materials and thereby improve spotting/filming or other end-results.

Higher active levels may also be desirable in highly concentrated detergent formulations.

8. Suds Suppressors Compounds for reducing or suppressing the formation of suds can be incorporated into the detergent compositions. Suds suppression can be of particular importance in the so-called"high concentration cleaning process"as described in U. S. 4, 489, 455 and 4, 489, 574 and in front-loading European-style washing machines.

The compositions herein will generally comprise from 0% to about 5% of suds suppressor.

9. Additional Other Detersive ingredients A wide variety of other ingredients useful in detergent compositions can be included in the compositions herein, including other active ingredients, carriers, hydrotropes, processing aids, dyes or pigments, fillers for solid compositions, etc.

If high sudsing is desired, suds boosters such as the C10-C16 alkanolamides can be incorporated into the compositions, typically at 1 %-10% levels. The Ciao- C14 monoethanol and diethanol amides illustrate a typical class of such suds boosters. Use of such suds boosters with high sudsing adjunct surfactants such as the amine oxides, betaines and sultanes noted above is also advantageous. If desired, soluble magnesium salts such as MgCI2, MgSO4, and the like, can be added at levels of, typically, 0. 1%-2%, to provide additional suds and to enhance grease removal performance.

The detergent compositions herein will preferably be formulated such that, during use in aqueous cleaning operations, the wash water will have a pH of between about 6. 5 and about 11, preferably between about 7. 5 and 10. 5. Laundry product formulations preferably have a pH between about 9 and about 11. Techniques for controlling pH at recommended usage levels include the use of buffers, alkalis, acids, etc., and are well known to those skilled in the art.

Form of the detergent composition The granular detergent compositions of the present invention preferably have a bulk density of at least about 250 g/liter, more preferably from about 400 g/liter to 1200 g/liter.

In one embodiment of the present invention, the detergent composition is made into a solid form, such as a bar, a tablet, or other solid form.

In the following Examples, the abbreviations for the various ingredients used for the compositions have the following meanings.

NaLAS : Sodium linear C12 alkyl benzene sulfonate KLAS : Potassium linear C12 alkyl benzene sulfonate KAS : Potassium C14-15 linear alkyl sulfate KMBAS : Potassium Mid-chain branched primary alkyl sulfate

KMBAES Potassium Mid-chain branched primary alkyl ethoxylate (Avg. EO = 1) sulfate SRP 1 Sulfobenzoyl end capped esters with oxyethylene oxy and terephtaloyl backbone Borax Na tetraborate decahydrate PAA Polyacrylic Acid (mw = 4500) PEG Polyethylene glycol (mw=4600) NaMES Alkyl methyl ester sulfonate, sodium salt NaSAS Secondary alkyl sulfate, sodium salt NaPS Sodium paraffin sulfonate STPP Sodium Tri-polyphosphate QAS R2. N+ (CH3) 2 (C2H40H) with R2 = C12-C14 TFAA C16-C1g alkyl N-methyl glucamide STPP Anhydrous sodium tripolyphosphate NaZeolite A Hydrated Sodium Aluminosilicate of formula Na12 (A102SiO2) 12. 27H20 having a primary particle size in the range from 0. 1 to 10 micrometers size in the range from 0. 1 to 10 micrometers NaSKS-6 Crystalline layered silicate of formula 8-Na2Si2O5 NaCarbonate Anhydrous sodium carbonate (mean size of the particle size distribution is between 200µm and 900m)

KCarbonate Anhydrous potassium carbonate (mean size of the particle size distribution is between 200µm and 900pm) NaBicarbonate : Anhydrous sodium bicarbonate (mean size of the particle size distribution is between 400m and 1200m) KBicarbonate : Anhydrous potassium bicarbonate (mean size of the particle size distribution is between 400m and 1200m) NaSilicate Amorphous Sodium Silicate (Si02 : Na2O ; 2. 0 ratio) Silicate Amorphous Potassium Silicate (Si02 : K20 ; 2. 0 ratio) MA/AA Copolymer of 1 : 4 maleic/acrylic acid, average molecular weight about 70, 000.

CMC Sodium carboxymethyl cellulose Protease Proteolytic enzyme of activity 4KNPU/g sold by NOVO Industries A/S under the tradename Savinase Amylase Amylolytic enzyme of activity 60KNU/g sold by NOVO Industries A/S under the tradename Termamyl 60T Lipase Lipolytic enzyme of activity 100kLU/g sold by NOVO Industries A/S under the tradename Lipolase Cellulase Cellulytic enzyme of activity 1000 CEVU/g sold by NOVO Industries A/S under the tradename Carezyme.

NaPercarbonate : Sodium Percarbonate Kpercarbonate : Potassium Percarbonate NOBS : Nonanoyloxybenzene sulfonate in the form of the sodium salt.

DOBA Decyl oxybenzoic acid LOBS Sodium lauroyl oxybenzene sulfonate NACA-OBS Phenol sulfonate ester of N-nonanoyl-6-aminocaproic acid TAED Tetraacetylethylenediamine HEDP. 1, 1-hydroxyethane diphosphonic acid 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.

In the following Example all levels are quoted as % by weight of the composition. The following examples are illustrative of the present invention, but are not meant to limit or otherwise define its scope. All parts, percentages and ratios used herein are expressed as percent weight unless otherwise specified.

Example 1 The following laundry detergent compositions A to F are prepared in accordance with the invention : A B C D E F KLAS 22 15 0 11 0 0 KAS 0 7 0 0 0 0 KMBS (avg. total 0 0 0 0 11 0 carbon=16. 5) KMBAES 0 0 0 0 0 11 Any Combination of : 0 0 22 11 11 11 NaC45 AS NaC45E1S ALAS C16 NaSAS C14-17 NaPS C14-18 NaMES C23E6. 5 1. 5 1. 5 1. 5 1. 5 1. 5 1. 5 NaZeolite A 27. 8 PAA 2. 3 2. 3 2. 3 2. 3 2. 3 2. 3 NaCarbonate 0 5 0 20 20 20 KCarbonate 20 30 20 0 0 0 NaSilicate 0. 6 0. 6 0. 6 0. 6 0. 6 0. 6 Sodium 20 30 30 20 20 polyphosphate MxMg ((n-1 2 4 6 8 10 x+2)/2) PnO3n+1 Perborate 1. 0 1. 0 1. 0 1. 0 1. 0 1. 0 Protease 0. 3 0. 3 0. 3 0. 3 0. 3 0. 3 Cellulase 0. 3 0. 3 0. 3 0. 3 0. 3 0. 3 SRP 0. 4 0. 4 0. 4 0. 4 0. 4 0. 4 Brightener 0. 2 0. 2 0. 2 0. 2 0. 2 0. 2 PEG 1.6 1.6 1.6 1.6 1.6 1.6 Sulfate 5. 5 5. 5 5. 5 5. 5 5. 5 5. 5 Silicone Antifoam 0. 42 0. 42 0. 42 0. 42 0. 42 0. 42 Citric Acid 3 5 0 0 0 0 Oxalic Acid 0 0 3 0 0 0 Succinic Acid 0 0 0 10 10 10 K+ in total 13 18 10 1. 2 1. 2 1. 1 composition Moisture & Minors---up to 100%---