Bleaching compositions

PH11998002378B1Inactive Publication Date: 2018-09-11PROCTER & GAMBLE CO
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Patent Information

Application Number
PH11998002378
Authority / Receiving Office
PH · PH
Patent Type
Patents
Current Assignee / Owner
Filing Date
1998-09-11
Publication Date
2018-09-11
Estimated Expiration
Not applicable · inactive patent

AI Technical Summary

Technical Problem

Existing bleach-containing compositions for laundry washing methods are not effective under stressed conditions such as low temperature washing, limited agitation, low detergent quantities, high metal ion presence, and storage under humid or high temperature, especially in low-density detergents with high phosphate levels, failing to provide adequate bleaching performance and bacterial reduction.

Method used

A bleaching composition with a low level of bleach activators and peroxide source, characterized by specific ratios of available oxygen from hydrophobic and hydrophilic bleach activators, and a peroxide source, optimized for use in low-density detergents and phosphate-containing compositions, achieving effective bleaching and bacterial reduction.

Benefits of technology

The composition provides enhanced bleaching performance and bacterial reduction even at low concentrations, effectively sanitizing fabrics and surfaces under stressed conditions, while minimizing fabric damage.

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Description

BLEACHING COMPOSITIONSTECHNICAL FIELDThe present invention relates to bleach-containing compositions, suitable for use in laundry washing methods.BACKGROUND OF THE INVENTIONIn the past decades research efforts have been directed towards the development of bleaching systems, based on organic peroxyacids, which can provide effective stain and / or soil removal from fabrics at lower wash temperatures. The organic peroxyacids are often obtained by the in situ perhydrolysis of organic peroxyacid bleach precursor compounds (bleach activators).A commonly employed precursor compound is tetraacetyl ethylene diamine (TAED) which provides effective hydrophilic cleaning especially on beverage stains. To achieve effective bleaching of a detergent, both hydrophobic and hydrophilic stains need to be bleached by the bleach system. Further, organic peroxyacid precursors have thus been developed to deal with hydrophobic stains and soils. Various documents disclose the use of mixtures of hydrophobic and hydrophilic bleaches in detergents, for example, JP 7 238 298, DE 19 616 782, WO 94 / 28103.However, the inventors have found that most prior art bleaching compositions do not always perform satisfactory when used under stressed conditions, such as low temperature washing, washing with limited agitation, use of low quantities of detergent actives, highly soiled fabrics, presence of high levels of metal ions, or after storage under humid or high temperature. These problems occur in particular in low density detergents, in particular when the overall level of the bleach system in the detergent composition is low, and also in detergents which contain high levels of phosphate-builder, which may introduce metal ions to the wash.Furthermore, to achieve an efficient bleach system, the system should provide excellent bleaching at low levels, thereby minimizing the chance of damage to the fabrics.Thus, there is a need to provide detergent compositions which comprise low levels of a bleaching system, which has a very effective bleaching performance under stressed conditions, on both hydrophobic soils and hydrophilic soils.The inventors have now surprisingly found that improved bleaching under stressed conditions can be achieved by use of a bleaching-composition containing a low level of bleach activators and peroxide source, namely having an available oxygen (AvO) derived from hydrophobic and hydrophilic bleach activators of less than 5,000 ppm, and having a specific ratio of AvO of the hydrophobic activator to the AvO of the hydrophilic activator, namely from 3:1 to 1:50, and a specific ratio of the total AvO to the AvO of the activators, namely more than 2:1. The bleach system has been found to be particularly useful in low density detergents, in hand washing detergents, in phosphate-containing positions, and also in washing processes where a low concentration of detergent is used.In general, bleach and in particular hypochlorite bleach is known to kill bacteria. High levels of bleach are normally required to provide a sufficient reduction of the bacteria or to eliminate the bacteria. Therefore, most detergents which comprise bleach systems known in the art, which only comprise low levels of bleach, are not effective as biocide agents for sanitization.The inventors have found that mixed bleach systems, comprising specific levels and ratios of hydrophobic, hydrophilic bleach additives and peroxide sources are very useful as biocide agents.They have found that even the use of low levels of specific bleach compositions in wash solution or in detergents or cleaning agents, provides effective sanitization of the washed fabrics or surfaces, or effective reduction of the bacteria when the bleaching components are used in the specific ratios, mentioned herein.All documents cited in the present description are, in relevant part, incorporated herein by reference.SUMMARY OF THE INVENTIONThe present invention relates to a detergent composition, having a density from 330 g / liter to 700 g / liter, comprising a bleaching system containing a hydrophilic and a hydrophobic peracid bleach or peracid bleach precursor and a peroxide source, characterized in that the total level of Available Oxygen from the hydrophilic and hydrophobic peracid bleach or bleach precursors (AvO-a) is less than 5,000 ppm, the ratio of Available Oxygen of the hydrophobic peracid or precursor (AvO-hb) to the Available Oxygen of the hydrophilic peracid or precursor (AvO-hp) is from 3:1 to 1:50 and the ratio of the Available Oxygen of the peroxide source (AvO-o) to the AvO-a is at least 2:1.DETAILED DESCRIPTION OF THE INVENTIONIn the detergent compositions of the invention, the total level of Available Oxygen from the hydrophilic and hydrophobic peracid bleach or bleach precursors (AvO-a) is less than 5,000 ppm, or even less than 4,000 ppm or even less than 3,000 ppm or even less than 2,500 ppm.The ratio of Available Oxygen of the hydrophobic peracid or precursor (AvO-hb) to the Available Oxygen of the hydrophilic peracid or precursor (AvO-hp) is from 3:1 to 1:50, more preferably from 2.5:1 to 1:30, or even 2:1 to 1:20.The ratio of the Available Oxygen of the peroxide source (AvO-o) to the AvO-a is at least 2:1, preferably at least 3:1 or even 4:1.The compositions preferably have a density from 370 g / liter to 700 g / liter, or even to 650 g / liter or even to 600 g / liter.It may be preferred that the composition is a low density granular composition, in particular phosphate-containing compositions and in particular high sudsing compositions, soaking or pre-treatment compositions, hand washing compositions.Thus, the invention also relates to a method of washing laundry by hand or pre-treating or soaking of laundry, whereby a detergent composition according to the invention.The invention also relates to the use of bleaching compositions, comprising hydrophobic and hydrophilic peracid bleach or precursors thereto, and a peroxide source for reduction of the activity of bacteria, whereby the ratio of AvO-hb to AvO-hp is from 3:1 to 1:50, preferably 2.5:1 to 1:10 as even 2:1 to 1:20 and whereby the ratio of AvO-o to AvO-a is at least 2:1, preferably at least 3:1 or even 4:1.When used herein, "reduction of the activity of bacteria" includes killing of the bacteria or part thereof and inhibition of further growth or development of bacteria.Preferably, the bleaching compositions are used for sanitization of the fabrics or surfaces, cleaning with the bleaching compositions. Then, it is preferred that the sanitization method involves contacting the fabrics or surfaces containing bacteria, in particularly present in stain on the fabrics or surfaces, with the compositions. Thus, the invention also encompasses a method for sanitization of fabrics whereby the fabrics are contacted with a composition or a solution of a composition, comprising a hydrophilic and hydrophobic peracid bleach or precursors thereto and a peroxide source, characterized in that the ratio of Available Oxygen of the hydrophobic peracid or precursor (AvO-hb) to the Available Oxygen of the hydrophilic peracid or precursor (AvO-hp) is from 3:1 to 1:50 and the ratio of the Available Oxygen of the peroxide source (AvO-o) to the total level of Available Oxygen from the hydrophilic and hydrophobic peracid bleach (AvO-a) is at least 2:1.The bleaching compositions are preferably present in cleaning compositions for cleaning fabrics or surfaces, preferably laundry or dishwashing detergents or hard-surface cleaners. Preferred are laundry detergent compositions for comprising the ingredients described herein.Preferably, the level of AvO-a in the cleaning compositions or detergent composition, or solutions thereof, which contain the bleaching composition and which are for use of reducing the activity of bacteria, is up to 10,000 ppm, more preferably, up to 5,000 ppm or even 4,000 ppm or even 3,000 ppm or 2,500 ppm.Preferred hydrophilic and hydrophobic peracid bleaches or precursors thereto and preferred peroxide sources are described hereinafter.Hydrophobic and Hydrophilic Peracids or Peracid PrecursorsAn essential feature of detergent compositions of the invention is a hydrophobic peracid or precursor thereto.The bleaching system preferably comprising a hydrophobic percarboxylic acid and / or precursor thereto, of the formula:R1 - CO3Mwherein R1 has at least 6 carbon atoms, and M is a counterion; or of formula:R1 - CO - L wherein L is a leaving group which is linked to the R1 -CO- group with an oxygen atom, and R1 has at least 6 carbon atoms. Preferred leaving groups are benzoic acid and derivatives thereof and especially benzene sulfonate.Percarboxylic acid bleach precursor are compounds which react with hydrogen peroxide in a perhydrolysis reaction to produce a percarboxylic acid.The counterion M of the percarboxylic acid is preferably sodium, potassium or hydrogen.Preferably, such hydrophobic peracids or precursors thereto are those whose parent carboxylic acid has a critical micelle concentration less than 0.5 moles / liter and wherein said critical micelle concentration is measured in aqueous solution at 20° - 50°C.The percarboxylic acid, preferably formed from the precursor, preferably contains at least 7 carbon atoms, or at least 8 or even 9 carbon atoms, and it may be preferred that it contains from 7 to 12 carbon atoms, more preferably from 8 to 11 carbon atoms, most preferably 9 or 10 carbon atoms. In a preferred aspect the percarboxylic acid formed from the precursor or the peroxy acid has an alkyl chain comprising at least 7 carbon atoms, more preferably at least 8 carbon atoms, most preferably 9 carbon atoms.The percarboxylic acid precursor can be any ester which had been described as a bleach activator for use in laundry detergents, for instance alkyl percarboxylic acid precursors described herein, sugar esters, such as pentaacetylglucose, esters of imidic acids such as ethyl benzimidate triacylcyanurates, such as triacetylcyanurate and tribenzoylcyanurate an esters giving relatively surface active oxidizing products for instance of Cs-Cis -alkanoic or -aralkanoic acids such as described in GB A 864 798, GB A 1 147 871 and the esters described in EP A 98 129 and EP A 106 634.Preferred can be phenyl esters of C14-C22 -alkanoic or alkenoic acids, esters of hydroxylamine, geminal diesters of lower alkanoic acids and gem-idols, such as those described in EP A 0 125 781 especially 1,1,5-triacetoxypent-4-ene and 1,1,5,5-tetraacetoxypentane and the corresponding butene and butane compounds, ethylidene benzoate acetate and bis(ethylidene acetate) adipate and enol esters, for instance as described in EP A 0 140 648 and EP A 0 092 932.Other highly preferred hydrophobic alkyl percarboxylic acid precursors include decanoly oxy benzoic acid or salt thereof, dodecanoyloxy-benzenesulfonate sodium or potassium salt, decanoyloxy - benzenesulfonate sodium or potassium salt (DOBS), benzoyloxy - benzenesulfonate 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 bleach activator compounds may also be useful herein, such as those described in EP A 0 170 386. Suitable examples of this class of agents include the precursors or the acids such as (6-hexylamino)-6-oxo-caproic acid, (6-octylamino)-6-oxo-caproic acid, (6-nonylamino)-6-oxo-caproic acid, (6-decylamino)-6-oxo-caproic acid, magnesium monoperoxyphthalate hexahydrate, the salt of metachloro perbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid and diperoxydodecanedioic acid, or precursors thereof, in particularly having a benzene sulfonate leaving group. Such bleaching agents are disclosed in U.S. 4,483,781; U.S. 4,634,551; EP 0 133 354; U.S. 4,412,934; and EP 0 170 386.Other suitable organic peroxyacids include diperoxyalkanedioc acids having more than 7 carbon atoms, such as diperoxydodecanedioc acid (DPDA), diperoxytetradecanedioc            acid            anddiperoxyhexadecanedioc 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.The compositions also comprise hydrophilic peracids or precursors thereto, preferably of the formula:wherein R1 has at less than 6 carbon atoms, and M is a counterion; or of formula:wherein L is a leaving group which is linked to the R1 -CO- group with an oxygen atom, and R1 has less than 6 carbon atoms.A preferred hydrophilic precursor is TAED.Peroxide SourceInorganic perhydrate salts are a preferred source of peroxide. Preferably these salts are present at a level of from 0.01% to 30% by weight, more preferably of from 0.5% to 10%.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 NaBO2H2O2 or the tetrahydrate NaBO2H2O2.3H2O.Alkali metal percarbonates, particularly sodium percarbonate are preferred perhydrates herein. Sodium percarbonate is an addition compound having a formula corresponding to 2Na2CO3.3H2O2, and is available commercially as a crystalline solid.Potassium peroxymonopersulfate is another inorganic perhydrate salt of use in the detergent compositions herein.Additional Detergent ComponentsThe detergent compositions in accord with the invention may also contain additional detergent components. The precise nature of these additional components, and levels of incorporation thereof will depend on the physical form of the composition or component, and the precise nature of the washing operation for which it is to be used.The compositions of the invention preferably contain one or more additional detergent components selected from additional surfactants, additional bleaches, bleach catalysts, alkalinity systems, builders, phosphate-containing builders, organic polymeric compounds, enzymes, suds suppressors, lime soap, dispersants, soil suspension and anti-redeposition agents soil releasing agents, perfumes, brighteners, photobleaching agents and additional corrosion inhibitors.Bleach CatalystThe bleach system can contain a transition metal containing bleach catalyst.One suitable type of bleach catalyst is a catalyst system comprising a transition metal cation of defined bleach catalytic activity, such as copper, iron or manganese cations, an auxiliary metal cation having little or no bleach catalytic activity, such as zinc or aluminum cations, and a sequestrant having defined stability constants for the catalytic and auxiliary metal cations, particularly ethylenediaminetetraacetic acid, ethylenediaminetetra (methylenephosphonic acid) and water-soluble salts thereof. Such catalysts are disclosed in U.S. Pat. 4,430,243.Other types of bleach catalysts include the manganese-based complexes disclosed in U.S. Pat. 5,246,621 and U.S. Pat. 5,244,594. Preferred examples of these catalysts include MnIV2(u-O)3(l,4,7-trimethyl-l,4,7-triazacyclononane)2-(PF6)2, Mnin2(u-O)i(u-OAc)2(l,4,7-trimethyl-l,4,7-triazacyclononane)2-(CIO4)2, MnIV4(u-O)6(l,4,7-triazacyclononane)4-(CIO4)2,MnniMnIV4(u-O)i(u-OAc)2-(l,4,7-trimethyl-l,4,7-triazacyclononane)2-(CIO4)3, and mixtures thereof. Others are described in European Patent ApplicationPublication No. 549 272. Other ligands suitable for use herein include l,5,9-trimethyl-l,5,9-triazacyclododecane, 2-methyl-l,4,7-triazacyclononane, 2-methyl-l,4,7-triazacyclononane,            l,2,4,7-tetramethyl-l,4,7-triazacyclononane, and mixtures thereof.For examples of suitable bleach catalysts see U.S. Pat. 4,246,612 and U.S. Pat. 5,227,084. See also U.S. Pat. 5,194,416 which teaches mononuclear manganese (IV) complexes such as Mn(l,4,7-trimethyl-l,4,7-triazacyclononane)(OCH3)3-(PF6).Still another type of bleach catalyst, as disclosed in U.S. Pat. 5,114,606, is a water-soluble complex of manganese (III), and / or (IV) with a ligand which is a non-carboxylate polyhydroxy compound having at least three consecutive C-OH groups. Preferred ligands include sorbitol, iditol, dulsitol, mannitol, xylithol, arabitol, adonitol, meso-erythritol, meso-inositol, lactose, and mixtures thereof.U.S. Pat. 5,114,611 teaches a bleach catalyst comprising a complex of transition metals, including Mn,Co, Fe, or Cu, with a non-(macro)-cyclic ligand. Said ligands are of the formula:R2 R3I I Ri-N=C-B-C=N-R4wherein R1, R2, R3, and R4 can each be selected from H, substituted alkyl and aryl groups such that each R1-N=C-R2 and R3-C=N-R4 form a five or six-membered ring. Said ring can further be substituted. B is a bridging group selected from O,S. CR5R6, NR7 and C=O, wherein R5, R6, and R7 can each be H, alkyl, or aryl groups, including substituted or unsubstituted groups. Preferred ligands include pyridine, pyridazine, pyrimidiine, pyrazine, imidazole, pyrazole, and triazole rings. Optionally, said rings may be substituted with substituents such as alkyl, aryl, alkoxy, halide, and nitro. Particularly preferred is the ligand 2,2'-bispyridylamine. Preferred bleach catalysts include Co, Cu, Mn, Fe, -bispyridylmethane and -bispyridylamine complexes. Highly preferred catalysts include Co(2,2'-bispyridylamine)Cl2, Di(isothiocyanato) bispyridylamine-cobalt (II), risdipyridylamine-cobalt(II) perchlorate, Co(2,2-bispyridylamine)2O2CIO4, Bis-(2,2'-bispyridylamine) copper(II) perchlorate, tris(di-2-pyridylamine) iron(II) perchlorate, and mixtures thereof. Highly preferred maybe manganese bridged cyclams, such as Mn dichloro cyclam or Mn 1,4,8,11 tetra azacyclotetradecane.Other examples include binuclear Mn complexed with tetra-N-dentate and bi-N-dentate ligands, including N4Mnin(u-O)2MnIVN4)+and [Bipy2Mnin(u-O)2MnIvbipy2]-(CIO4)3.Other bleach catalysts are described, for example, in European Patent Application, Publication No. 403 131 (cobalt complex catalysts), European Patent Applications, Publication Nos. 384 503, and 306, 089 (metallo-porphyrin catalysts), U.S. 4,728,455 (manganese /  multidentate ligand catalyst), U.S. 4,711,748 and European Patent Application, Publication No. 224 952, (absorbed manganese on aluminosilicate catalyst), U.S. 4,601,845 (aluminosilicate support with manganese and zinc or magnesium salt), U.S. 4,626,373 (manganese /  ligand catalyst), U.S. 4,119,557 (ferric complex catalyst), German Pat. Specification 2 054 019 (cobalt chelant catalyst) Canadian 866 191 (transition metal-containing salts), U.S. 4,430,243 (chelants with manganese cations and non-catalytic metal cations), and U.S. 4,728,455 (manganese gluconate catalysts). Highly preferred maybe pentaamine cobalt (III) acetate dichloride salt.The bleach catalyst is typically used in a catalytically effective amount in the compositions and processes herein. By "catalytically effective amount" is meant an amount which is sufficient, under whatever comparative test conditions are employed, to enhance bleaching and removal of the stain or stains of interest from the target substrate. The test conditions will vary, depending on the type of washing appliance used and the habits of the user. Some users elect to use very hot water; others use warm or even cold water in laundering operations. Of course, the catalytic performance of the bleach catalyst will be affected by such considerations, and the levels of bleach catalyst used in fully-formulated detergent and bleach compositions can be appropriately adjusted. 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 0.2 ppm to about 200 ppm, preferably 0.4 ppm to 100 ppm of the catalyst species in the wash liquor. To illustrate this point further, on the order of 3 micromolar manganese catalyst is effective at 40°C, pH 10 under European conditions using perborate and a bleach precursor. An increase in concentration of 3-5 fold may be required under U.S. conditions to achieve the same results.SurfactantThe detergent compositions in accord with the invention 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. Pat. 3,929,678 issued to Laughlin and Heuring on December 30, 1975. Further examples are given in "Surface Active Agents and Detergents" (Vol. I and II by Schwartz, Perry and Berch). A list of suitable cationic surfactants is given in U.S. Pat. 4,259,217 issued to Murphy on March 31, 1981.Where present, ampholytic, amphoteric and zwitterionic surfactants are generally used in combination with one or more anionic and / or nonionic surfactants.Anionic SurfactantThe detergent compositions in accord with the present invention preferably comprise an additional anionic surfactant. Essentially any anionic surfactants useful for detersive purposes can be comprised in the detergent composition. These can include salts (including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts) of the anionic sulfate, sulfonate, carboxylate and sarcosinate surfactants. Anionic sulfate and sulfonate surfactants are preferred.Highly preferred are surfactant systems comprising a sulfonate and a sulfate surfactant, preferably a linear or branched alkyl benzene sulfonate and alkyl ethoxy Isulfates, 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 C12-C18 monoesters) diesters of sulfosuccinate (especially saturated and unsaturated C6-C14 diesters), N-acyl sarcosinates. Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tallow oil.Anionic Sulfate SurfactantAnionic 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-C17 acyl-N-(Ci-C4 alkyl) and -N-(Ci-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 Cio-Ci8 alkyl sulfates, more preferably the C11-C15 branched chain alkyl sulfates and the C12-C14 linear chain alkyl sulfates.Alkyl ethoxysulfate surfactants are preferably selected from the group consisting of the Cio-Ci8 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 Cn-Ci8, most preferably C11-C15 alkyl sulfate which has been ethoxylated with from 0.5 to 7, preferably from 1 to 5, moles of ethylene oxide per molecule.A particularly preferred aspect of the invention employs mixtures of the preferred alkyl sulfate and / or sulfonate and alkyl ethoxysulfate surfactants. Such mixtures have been disclosed in PCT Patent Application No. WO 93 / 18124.Anionic Sulfonate SurfactantAnionic sulfonate surfactants suitable for use herein include the salts of C5-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 SurfactantSuitable 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 formula:RO(CH2CH2O)xCH2COOM+wherein R is a Ce-Cis alkyl group, x ranges from 0 to 10,and the ethoxylate distribution is such that, oh 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)-R3wherein R is a C6-Ci8 alkyl group, x is from 1 to 25, Ri 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-l-undecanoic acid, 2-ethyl-l-decanoic acid, 2-propyl-l-nonanionic acid, 2-butyl-l-octanoic acid and 2-pentyl-l-heptanoic acid.Certain soaps may also be included as suds suppressors.Alkali Metal Sarcosinate SurfactantOther suitable anionic surfactants are the alkali metal sarcosinates of formula:R-CON (R1) CH2 COOMwherein R is a C5-C17 linear or branched alkyl or alkenyl group, R1 is a C1-C4 alkyl group and M is an alkali metal ion. Preferred examples are the myristyl and oleoyl methyl sarcosinates in the form of their sodium salts.Alkoxvlated Nonionic SurfactantEssentially any alkoxylated nonionic surfactants are suitable herein. The ethoxylated and propoxylated nonionic surfactants are preferred.Preferred alkoxylated surfactants can be selected from the classes of the nonionic condensates of alkyl phenols, nonionic ethoxylated alcohols, nonionic ethoxylated / propoxylated fatty alcohols, nonionic ethoxylate / propoxylate condensates with propylene glycol, and the nonionic ethoxylate condensation products with propylene oxide / ethylene diamine adducts.Nonionic Alkoxylated Alcohol SurfactantThe condensation products of aliphatic alcohols with from 1 to 25 moles of alkylene oxide, particularly ethylene oxide and / or propylene oxide, are suitable for use herein. The alkyl chain of the aliphatic alcohol can either be straight or branched, primary or secondary, and generally contains from 6 to 22 carbon atoms. Particularly preferred are the condensation products of alcohols having an alkyl group containing from 8 to 20 carbon atoms with from 2 to 10 moles of ethylene oxide per mole of alcohol.Nonionic Polvhvdroxv Fattv Acid Amide SurfactantPolyhydroxy fatty acid amides suitable for use herein are those having the structural formula:wherein R1 is H, C1-C4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl, ethoxy, propoxy, or a mixture thereof, preferably C1-C4 alkyl, more preferably Ci or C2 alkyl, most preferably Ci alkyl (i.e., methyl); and R2 is a C5-C31 hydrocarbyl, preferably straight-chain C5-C19 alkyl or alkenyl, more preferably straight-chain C9-C17 alkyl or alkenyl, most preferably straight-chain C11-C17 alkyl or alkenyl, or mixture thereof, and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof. Z preferably will be derived from a reducing sugar in a reductive amination reaction; more preferably Z is a glycityl.Nonionic Fatty Acid Amide SurfactantSuitable fatty acid amide surfactants include those having the formula:R6CON(R7)2wherein 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, Ci-C4 alkyl, Ci-C4 hydroxyalkyl, and -(C2H4OXH, where x is in the range of from 1 to 3.Nonionic Alkvlpolvsaccharide SurfactantSuitable 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:R2O(CnH2nO)t(glycosyl)xwherein 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 SurfactantSuitable 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)xN°(R5)2wherein 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 Cw-Cis alkyl dimethylamine oxide, and Cio-Cis acylamido alkyl dimethylamine oxide.A suitable example of an alkyl aphodicarboxylic acid is Miranol(TM) C2M Cone, manufactured by Miranol, Inc., Dayton, NJ.Zwitterionic SurfactantZwitterionic 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 Ce-Cis hydrocarbyl group, each R1 is typically C1-C3 alkyl, and R2 is a C1-C5 hydrocarbyl group. Preferred betaines are Ci2-Ci8 dimethyl-ammonio hexanoate and the C10-C18 acylamidopropane (or ethane) dimethyl (or diethyl) betaines. Complex betaine surfactants are also suitable for use herein.Cationic SurfactantsSuitable cationic surfactants to be used in the detergent herein include the quaternary ammonium surfactants. Preferably the quaternary ammonium surfactants is a mono C6-Ci6, preferably C6-Cio 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 U.S. Patents Nos. 4,228,042, 4,239,660 and 4,260,529.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-0- linkages are excluded, while 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-alkoxvlated Amine SurfactantsHighly preferred herein are cationic mono-alkoxylated amine surfactant preferably of the general formula I:(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 an alkoxy group, especially an 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 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 —CH2-CH2OH, —CH2CH2CH2OH, -CH2CH(CH3)OH and -CH(CH3)CH2OH, with -CH2CH2OH being particularly preferred. Preferred R1 groups are linear alkyl groups. Linear R1 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:CH2CH2O)2-5Hch3ch3wherein R1 is Cio-Ci8 hydrocarbyl and mixtures thereof, especially C10-C14 alkyl, preferably C10 and Ci2 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)CH2O] 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 used in detergent compositions of the invention is preferably from 0.1% to 20%, more preferably from 0.2% to 7%, most preferably from 0.3% to 3.0% by weight of the composition.Cationic bis-Alkoxylated Amine SurfactantThe cationic bis-alkoxylated amine surfactantpreferably has the general formula II:R1               ApR3N+              X”R2                A'qR4(H)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 Ci-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: CH3CH2CH2OHCH2CH2OHwherein R1 is C10-C18 hydrocarbyl and mixtures thereof, preferably C10, C12, C14 alkyl and mixtures thereof. X is any convenient anion to provide charge balance, preferably chloride. With reference to the general cationic bis-alkoxylated amine structure noted above, since in a preferred compound R1 is derived from (coconut) C12-C14 alkyl fraction fatty acids, R2 is methyl and ApR3 and A'qR4 are each monoethoxy.Other cationic bis-alkoxylated amine surfactantuseful herein include compounds of the formula:R1(CH2CH2O)PHR2N+(CH2CH2O)qHwherein R1 is Cio-Ci8 hydrocarbyl, preferably Ci0-C14 alkyl, independently p is 1 to about 3 and q is 1 to about 3, R2 is C1-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)CH2O] and [CH2CH(CH3O] units (i-Pr) or n-propoxy units (Pr), or mixtures of EO and / or Pr and / or i-Pr units.Water-Soluble Builder CompoundThe detergent compositions in accord with the present invention 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 of the composition.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 than two carbon atoms, borates, and mixtures of any of the foregoing.The carboxylate or polycarboxylate builder can be monomeric or oligomeric in type although monomeric polycarboxylates are generally preferred for reasons of cost and performance.Suitable carboxylates containing one carboxy group include the water soluble salts of lactic acid, glycolic acidand 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 carboxymerthyloxysuccinates described in British Patent No. 1   379 241,lactoxysuccinates described in British Patent No. 1 389 732, and aminosuccinates described in Netherlands Application 7 205 873, and the oxypolycarboxylate materials such as 2-oxa-l,l,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 of the composition.Polycarboxylates containing four carboxy groups include oxydisuccinates disclosed in British Patent No. 1 261 829, 1,1,2,2-ethane tetracarboxylates, 1,1,3,3-propane tetracarboxylates and 1,1,2,3-propane tetracarboxylates. Polycarboxylates containing sulfo substituents include the sulfosuccinate derivatives disclosed in British Patent Nos. 1 398 421 and 1 398 422 and in U.S. Patent No. 3,936,448, and the sulfonated pyrolysed citrates described in British Patent No. 1 439 000. Preferred polycarboxylates are hydroxycarboxylates containing up to three carboxy groups per molecule, more particularly citrates.The parent acids of the monomeric or oligomeric polycarboxylate chelating agents or mixtures thereof with their salts, e.g., citric acid or citrate / citric acid mixtures are also contemplated as useful builder components.Borate builders, as well as builders containing borate-forming materials that can produce borate under detergent storage or wash conditions are useful watersoluble 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 CompoundThe detergent compositions in accord with the present invention may contain a partially soluble or insoluble builder compound, typically present in detergent compositions at a level of from 0.5% to 60% by weight, preferably from 5% to 50% by weight, most preferably from 8% to 40% weight of the composition.Examples of largely water insoluble builders include the sodium aluminosilicates.Suitable aluminosilicate zeolites have the unit cell formula:Naz[(AIO2)z(SiO2)y]. xH2Owherein 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% and 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:Na12[(AIO2)12(SiO2)i2]. xH2Owherein x is from 20 to 30, especially 27. Zeolite X has the formula Nase [AI02)86(Si02)io6]. 276 H2O.Another preferred aluminosilicate zeolite is zeolite MAP builder. The zeolite MAP can be present at a level of from 1% to 80%, more preferably from 15% to 40% by weight of the compositions.Zeolite MAP is described in EP 384 070 A (Unilever). It is defined as an alkali metal alumino-silicate of the zeolite P type having a silicon to aluminum 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 aluminum 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 dso value of from 1.0 to 10.0 micrometers, more preferably from 2.0 to 7.0 micrometers, most preferably from 2.5 to 5.0 micrometers.The d5o value indicates that 50% by weight of the particles have a diameter smaller than that figure. The particle size may, in particular be determined by conventional analytical techniques such as microscopic determination using a scanning electron microscope or by means of a laser granulometer. Other methods of establishing dso values are disclosed in EP 384 070 A.Heavy Metal Ion SeauestrantThe compositions of the invention preferably contain as an optional component a heavy metal ion sequestrant. By heavy metal ion sequestrant it is meant herein components which act to sequester (chelate) heavy metal ions. These 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 hydroxyethylene 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 p-alanine-N,N'-diacetic acid, aspartic acid-N,N'-diacetic acid, aspartic acid-N-monoacetic acid and iminodisuccinic acid sequestrants described in EP A 509 382 are also suitable.EP A 476 257 describes suitable amino based sequestrants. EP A 510 331 describes suitable sequestrants derived from collagen, keratin or casein. EP A 528 859 describes a suitable alkyl iminodiacetic acid sequestrant. Dipicolinic acid and 2-phosphonobutane-1,2,4-tricarboxylic acid are also suitable. Glycinamide-N,N'-disuccinic acid (GADS), ethylenediamine-N-N'-diglutaric acid (EDDG) and 2-hydroxypropylenediamine-N-N'-disuccinic acid (HPDDS) are also suitable.Especially preferred are diethylenetriamine pentacetic acid, ethylenediamine-N-N'-disuccinic acid (EDDS), 1,1 hydroxyethane diphosphonic acid and 1,1 hydroxyethane dimethylene phosphonic acid or the alkali metal, alkaline earth metal, ammonium, or substituted ammonium salts thereof, or mixtures thereof.EnzymeAnother preferred ingredient useful in the detergent compositions is one or more additional enzymes.Preferred additional enzymatic materials include the commercially available lipases, cutinases, amylases, neutral and alkaline proteases, cellulases, endolases, esterases, pectinases, lactases and peroxidases conventionally incorporated into detergent compositions. Suitable enzymes are discussed in U.S. 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, Maxacai and Maxapem by Gist-Brocades, those sold by Genencor International, and those sold under the tradename Opticlean and Optimase by Solvay Enzymes. Protease enzyme maybe 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-a myiases 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 9,703,635, and in WO 95 / 26397 and WO 96 / 23873.Amylase enzyme maybe incorporated into the composition in accordance with the invention at a level of from 0.0001% to 2% active enzyme by weight of the composition.Lipolytic enzyme maybe present at levels of active lipolytic enzyme of from 0.0001% to 2% by weight, preferably 0.001% to 1% by weight, most preferably from 0.001% to 0.5% by weight of the compositions.The lipase maybe fungal or bacterial in origin being obtained, for example, from a lipase producing strain of Humicola sp., Thermomvces sp. or Pseudomonas sp. including Pseudomonas oseudoalcaligenes or Pseudomas fluorescens. Lipase from chemically or genetically modified mutants of these strains are also useful herein. A preferred lipase is derived from Pseudomonas pseudoalcaliqenes, which is described in Granted European Patent, EP B 0 218 272.Another preferred lipase herein is obtained by cloning the gene from Humicola lanuginosa and expressing the gene in Aspergillus orvza, as host, as described in European Patent Application, EP A 0 258 068, which is commercially available from Novo Industri A / S, Bagsvaerd, Denmark, under the tradename Lipolase. This lipase is also described in U.S. Patent 4,810,414, Huge-Jensen et al, issued March 7, 1989.Organic Polymeric CompoundOrganic polymeric compounds are preferred additional components of the detergent compositions 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 quaternized 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.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 1,000-5,000 and their copolymers with maleic anhydride, such copolymers having a molecular weight of from 2,000 to 100,000, especially 40,000 to 80,000.The polyamino compounds are useful herein including those derived from aspartic acid such as those disclosed in EP A 305 282, EP A 305 283 and EP A 351 629.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 1,000-10,000, more particularly 2,000 to 8,000 and most preferably about 4,000.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. Patent5,415,807, Gosselink et al., and in particular accordingtoM -7U.S. Application No. 60 / 051517.Another organic compound, which is a preferred    ' n /  clay dispersant / anti-redeposition agent, for use herein,can be the ethoxylated cationic monoamines anddiamines of the formula:ch3CH-,I 3X-eOCH2CH2)n-lN+—CH2—CH2-eCH2)a -N+—CH2CH2O^-XLI                                         Jb |(CH2CH2O-)^X          (CH^^O-^Xwherein X is a nonionic group selected from the group consisting of H, C1-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 011 965 and U.S. 4,659,802 and U.S. 4,664,848.Suds Suppressing SystemThe detergent compositions of the invention, 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.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 compoundsBy 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 U.S. 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 Ci8-C4o ketones (e.g., stearone) N-alkylated amino triazines such as tri- to hexaalkylmelamines or di- to tetra alkyldiamine chlortriazines formed as products of cyanuric chloride with two or three moles of a primary or secondary amine containing 1 to 24 carbon atoms, propylene oxide, bis stearic acid amide and monostearyl di- alkali metal (e.g., sodium, potassium, lithium) phosphates and phosphate esters.A preferred suds suppressing system comprises:(a) antifoam compound, preferably silicone antifoam compound, most preferably a silicone antifoam compound comprising in combination(i)   polydimethyl siloxane, at a level of from 50% to 99%, preferably 75% to 95% by weight of the silicone antifoam compound; and(ii)   silica, at a level of from 1% to 50%, preferably 5% to 25% by weight of the silicone / silica antifoam compound;wherein said silica / silicone antifoam compound is incorporated at a level of from 5% to 50%, preferably 10% to 40% by weight;(b) a dispersant compound, most preferably comprising a silicone glycol rake copolymer with a polyoxyalkylene content of 72-78% and an ethylene oxide to propylene oxide ratio of from 1:0.9 to 1:1.1, at a level of from 0.5% to 10%, preferably 1% to 10% by weight; a particularly preferred silicone glycol rake copolymer of this type is DCO544, commercially available from DOW Corning under the trade name DCO544;(c) an inert carrier fluid compound, most preferably comprising a Ci6-Ci8 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 0 210 731 and comprises a silicone antifoam compound and an organic carriermaterial 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 0 210 721 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 AgentsThe detergent compositions herein may also comprise from 0.01% to 10%, preferably from 0.05% to 0.5% by weight of polymeric dye transfer inhibiting agents.The polymeric dye transfer inhibiting agents are preferably selected from polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinylpyrrolidonepolymers or combinations thereof, whereby these polymers can be cross-linked polymers.Optical BrightenerThe detergent compositions herein also optionally contain from about 0.005% to 5% by weight of certain types of hydrophilic optical brighteners.Hydrophilic optical brighteners useful herein include those having the structural formula:wherein 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%rfftn§7 cation such as sodium or potassium.                     Y7When in the above formula, Ri is anilino, IVis N^-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 5BM-GX by Ciba-Geigy Corporation.When in the above formula, Ri 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.Polymeric Soil Release AgentKnown polymeric soil release agents, hereinafter "SRA", can optionally be employed in the present detergent compositions. If utilized, SRA's will generally comprise from 0.01% to 10.0%, typically from 0.1% to 5%, preferably from 0.2% to 3.0% by weight, of the compositions.Preferred SRA's typically have hydrophilic segments to hydrophilize the surface of hydrophobic fibers such as polyester and nylon, and hydrophobic segments to deposit upon hydrophobic fibers and remain adhered thereto through completion of washing and rinsing cycles, thereby serving as an anchor for the hydrophilic segments. This can enable stains occurring subsequent to treatment with the SRA to be more easily cleaned in later washing procedures.Preferred SRA's include oligomeric terephthalate esters, typically prepared by processes involving at least one transesterification / oligomerization, often with a metal catalyst such as a titanium(IV) alkoxide. Such esters maybe 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 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 JJ. 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 3,400.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 Ci-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 s a 2% aqueous solution. Such materials are available as METOLOSE SM100 and METOLOSE SM200, which are the tradenames 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 maybe used as starting materials as long as they have hydroxyl terminal groups which maybe esterified. See U.S. 4,525,524 Tung et al. Other classes include: (III) anionic terephthalate-based SRA's of the urethane-linked variety, see U.S. 4,201,824, Violland et al.Other Optional IngredientsOther optional ingredients suitable for inclusion in the compositions of the invention include perfumes, colours and filler salts, with sodium sulfate being a preferred filler salt.Highly preferred maybe the inclusion of speckle particles. The following speckle particle is a preferred speckle particle: Sodium carbonate particles, having 75% of particles having a particle size of from 600 microns to 850 microns and 25% of particles having a particle size of from 425 microns to 600 microns are obtained by agglomerating and sieving sodium carbonate powder. Thus, the obtained particles are sprayed with a Monastral blue BV paste solution and subsequently dried, obtaining speckle particles comprising about 1,000 ppm of dye.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 U.S.Patent 4,285,841 to Barrat et al., issued August 25, 1981 (herein incorporated by reference), can be present.Form of the CompositionsThe detergent composition of the invention can be made via a variety of methods, including dry-mixing and agglomerating and / or spray-drying of the various compounds comprises in the detergent component.The compositions in accordance with the invention can take a variety of physical forms including liquid and solid forms such as tablet, flake, pastille and bar, and preferably granular forms.The compositions in accord with the present invention can also be used in or in combination with bleach additive compositions, for example, comprising chlorine bleach.Chlorine-Based BleachThe detergent compositions can include as an additional component a chlorine-based bleach. However, since preferred 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 bleachcompatible, 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 bleach is such that a hypochlorite species is formed in aqueous solution. The hypochlorite ion is chemically represented by the formula OCT.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 dodeca hydrate, potassium dichloroisocyanurate, sodium dichloroisocyanurate sodium dichloroisocyanurate dihydrate, trichlorocyanuric acid, l,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 chlorinebased bleach can be Triclosan (tradename).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.The mean particle size of the components of the granular compositions in accordance with the invention, should preferably be such that no more that 25% of the particles are greater than 1.8 mm in diameter and not more than 25% of the particles are less than 0.25 mm in diameter. Preferably the mean particle size is such that from 10% to 50% of the particles has a particle size of from 0.2 mm to 0.7 mm in diameter.The term mean particle size as defined herein is calculated by sieving a sample of the composition into a number of fractions (typically 5 fractions) on a series of sieves, preferably Tyler sieves. The weight fractions thereby obtained are plotted against the aperture size of the sieves. The mean particle size is taken to be the aperture size through which 50% by weight of the sample would pass.Laundry Washing MethodMachine 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 10 g to 300 g of product dissolved or dispersed in a wash solution of volume from 5 to 65 liters, as are typical product dosages and wash solution volumes commonly employed in conventional machine laundry methods.In a preferred use aspect, the detergent composition is formulated such that it is suitable for 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. Abbreviation Used in ExamplesIn the detergent compositions, the abbreviated component identifications have the following meanings:LAS Sodium linear Cn-n alkyl benzene sulfonate TAS Sodium tallow alkyl sulfate CxyAS Sodium Cix-Ciy alkyl sulfate C46SAS Sodium C14-C16 secondary (2,3) alkyl sulfate CxyEzS Sodium Cix-Ciy alkyl sulfate condensed with z moles of ethylene oxide CxyEz Cix-Ciy predominantly linear primary alcohol QASQAS 1SADSSADE2SMESAPASoapSTSCFAATFAA TPKFA STPP TSPPcondensed with an average of z^gjol^ -7 p^ .jy of ethylene oxide                            / R2.N+(CH3)2(C2H4OH) with R2 = C12-C14___ :R2.N+(CH3)2(C2H4OH) with R2 = C8-CnSodium Ci4-C22 alkyl disulfate of formula 2-(R).C4H7.-l,4-(SO4-)2 where R=Cio~Ci8Sodium Ci4-C22 alkyl disulfate of formula2-( R).C4H7.-l,4-(SO4-)2 where R=Cio-Ci8, condensed with z moles of ethylene oxide x-sulpho methylester of Ci8 fatty acidC8-Ci0 amido propyl dimethyl amineSodium linear alkyl carboxylate derived fromAn 80 / 20 mixture of tallow and coconut fattyAcidsSodium toluene sulfonateCi2-Ci4 (coco) alkyl N-methyl glucamideCig-Cis alkyl N-methyl glucamideC16-C18 topped whole cut fatty acidsAnhydrous sodium tripolyphosphateTetrasodium pyrpphpsph-?b?Zeolite A Hydrated sodium aluminosilicate of formula Nai2(AIO2SiO2)i2-27H2O 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 8- Na2Si20s Citric acid Anhydrous citric acid Borate Sodium borate Carbonate Anhydrous sodium carbonate with a particle size between 200 pm and 900 pm Bicarbonate : Anhydrous sodium bicarbonate with a particle size distribution between 400 pm and 1200 pm Silicate Amorphous sodium silicate (SiO2:Na2O=2.0:l) Sulfate Anhydrous sodium sulfate Mg sulfate Anhydrous magnesium sulfate Citrate Tri-sodium cirate dihydrate of activity 86.4% with a particle size distribution between 425 pm and 850 pm 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 ofProtease polymerization of 650 available from Shin Etsu Chemicals : 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 Amylase II : Amylolytic enzyme, as disclosed in PCT / US 9,703,635 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 : Sodium perborate tetrahydrate of nominal formula NaBO2.3H2O.H2O2 PB1 : Anhydrous sodium perborate bleach of nominal formula NaBO2.H2O2 Percarbonate : Sodium percarbonate of nominal formulaDOBS 2Na2CO3.3H2O2 : 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 : Dodecanoyloxybenzene sulfonate in the form of the sodium salt DOBA : Decanoyl oxybenzoic acid TAED : Tetraacetylethylenediamine DTPA : Diethylene triamine pentaacetic acid DTPMP : Diethylene triamine penta (methylene phosphonate), marketed by Monsanto under the tradename Dequest 2060EDDS : Ethylenediamine-N,N'-disuccinic acid, (S,S) isomer in the form of its sodium salt Photoactivated : Sulfonated zinc phthlocyanine encapsulated In bleach (1) dextrin soluble polymer Photoactivated : Sulfonated alumino phthlocyanine encapsul ated 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 HEDP : 1,1-hydroxyethane diphosphonic acid HEDMP : 1,1-hydroxyethane dimethylene phosphonic 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 5 an average molecular weight of 50,000 PVPVI : Copolymer of polyvinylpyrolidone and vinyllimidazole, with an average molecular weight of 20,000 QEA : bis((C2H5O)(C2H4O)n)(CH3)-N+-C6Hi2-N+- 10 (CH3)bis((C2H5O)-(C2H4O))n, wherein n = from 20 to 30 SRP 1 : Anionically end capped poly esters SRP 2 : Diethoxylated poly (1,2 propylene terephthalate) short block polymer 15       PEI : Polyethyleneimine with an average olecular weight of 1,800 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: Water based monostyrene latex mixturesold by BASF Aktiengesellchaft under the tradename Lytron 621Wax           : Paraffin waxSpeckle particle : Speckle particle as described herein on p.70In the following examples all levels are quoted as% by weight of the composition:EXAMPLE 1The following detergent formulations are in accordwith the invention.A B C D Blown Powder MES 2.0 0.5 1.0 — SADS - - - 2.0 LAS 6.0 5.0 11.0 6.0 A B C D TAS 2.0 - - 2.0 Zeolite A 24.0 - - 20.0 STPP — 27.0 24.0 — Sulfate 4.0 6.0 13.0 - MA / AA 1.0 4.0 6.0 2.0 Silicate 1.0 7.0 3.0 3.0 CMC 1.0 1.0 0.5 0.6 Brightener 1 0.2 0.2 0.2 0.2 Silicone antifoam 1.0 1.0 1.0 0.3 DTPMP 0.4 0.4 0.2 0.4 Spray on Brightener 0.02 — - 0.02 C45E7 — - — 5.0 C45E2 2.5 2.5 2.0 — C45E3 2.6 2.5 2.0 Perfume 0.5 0.3 0.5 0.2 Silicone antifoam 0.3 0.3 0.3 - Dry additives QEA - - - 1.0 EDDS 0.3 — - - Sulfate 2.0 3.0 5.0 10,0 Carbonate 6.0 13.0 15.0 14.0 Citric acid 2.5 - - 2.0 QAS II 0.5 - 0.5 SKS-6 10.0 - — - Percarbonate 4.0 3.0 - 1.9 PB4 - 5.0 NOBS 0.5 — 0.3 TAED 0.75 0.5 0.2 0.5 DOBS - 0.5 0.6 — Protease 1.0 1.0 1.0 1.0 Lipase 0.4 — 0.2 Lipase (1) 0.4 — 0.4 Amylase 0.2 0.2 0.2 0.4 Brightener 1 0.05 - - 0.05 Misc / minor to 100% EXAMPLE 2The following granular detergent formulations are in accord with the invention.E F G H I J Blown powder LAS 23.0 8.0 7.0 9.0 7.0 7.0 QAS - - — - 1.0 C45AS 6.0 6.0 5.0 8.0 - C45AE11S - 1.0 1.0 1.0 - - MES 2.0 - 2.0 4.0 Zeolite A 10.0 18.0 14.0 12.0 10.0 10.0 MA / AA — 0.5 - - - 2.0 MA / AA (1) 7.0 - - - - — AA — 3.0 3.0 2.0 3.0 3.0 Sulfate 5.0 6.3 11.1 11.0 11.0 18.1 Silicate 10.0 1.0 1.0 1.0 1.0 1.0 Carbonate 15.0 20.0 10.0 20.7 8.0 6.0 PEG 4000 0.4 1.5 1.5 1.0 1.0 1.0 DTPA — 0.9 0.5 - 0.5 Brightener 2 0.3 0.2 0.3 - 0.1 0.3 Spray on C45E7 2.0 — 2.0 2.0 C25E9 3.0 — — - C23E9 - 1.5 2.0 2.0 Perfume 0.3 0.3 0.3 2.0 0.3 0.3 Agglomerates C45AS - 5.0 5.0 2.0 5.0 LAS - 2.0 2.0 - - 2.0 Zeolite A - 7.5 7.5 8.0 — 7.5 Carbonate - 4.0 4.0 5.0 4.0 PEG 4000 - 0.5 0.5 - — 0.5 Misc (water etc.) - 2.0 2.0 2.0 - 2.0 Dry additives QAS (I) — — 1.0 — Citric acid - — — 2.0 — PB4 - 3.0 - - 5.0 - PB1 - - 4.0 1.0 - - Percarbonate 2.0 — - 1.0 - 2.0 Carbonate — 5.3 1.8 - 4.0 4.0 NOBS 0.5 — 0.4 0.3 — 0.6 DOBS — 0.9 — — 0.3 - TAED 0.6 0.4 0.6 0.3 0.9 0.5 Methyl cellulose 0.2 - - - - 0.5 DTPA 0.7 0.5 1.0 0.5 0.5 1.2 SKS-6 8.0 — - — STS - — 2.0 1.0 - Cumene sulfonic Acid - 1.0 - - - 2.0 Lipase 0.2 - 0.2 — 0.2 0.4 Cellulase 0.2 0.2 0.2 0.3 0.2 0.2 Amylase II 0.2 - 0.1 - 0.2 Protease 0.5 0.5 0.5 0.3 0.5 0.5 PVPVI — - - — 0.5 0.1 PVP - - - - 0.5 — PVNO — — 0.5 0.3 - — QEA — — — 1.0 — SRP1 0.2 0.5 0.3 0.2 - Silicone antifoam 0.2 0.4 0.2 0.4 0.1 - Mg sulfate — - 0.2 - 0.2 — Speckle — 2.0 1.0 0.5 2.0 6.0 Misc / minors to 100% EXAMPLE 3The following granular detergent formulations are in accord with the invention.K L M N Base granule STPP — 22.0 — 15.0 Zeolite A 30.0 - 24.0 5.0 Sulfate 5.5 5.0 7.0 7.0 MA / AA 3.0 — - — AA — 1.6 2.0 - MA / AA (1) - 12.0 - 6.0 LAS 14.0 10.0 9.0 20.0 C45AS 8.0 7.0 9.0 7.0 C45AE11S - 1.0 — 1.0 MES 0.5 4.0 6.0 - SADS 2.5 — - 1.0 Silicate - 1.0 0.5 10.0 Soap — 2.0 - - Brightener 1 0.2 0.2 0.2 0.2 Carbonate 6.0 9.0 8.0 10.0 PEG 4000 1.0 1.5 — DTPA — 0.4 - Spray on C25E9 — - — 5.0 C45E7 1.0 1.0 — — C23E9 — 1.0 2.5 - Perfume 0.2 0.3 0.3 — Dry additives Carbonate 5.0 10.0 13.0 8.0 PVPVI / PVNO 0.5 - 0.3 - Protease 1.0 1.0 1.0 0.5 Lipase 0.4 - - 0.4 Amylase 0.1 - 0.1 Cellulase 0.1 0.2 0.2 0.1 DTPA / HEDP 0.5 0.3 0.5 1.0 LOBS - 0.8 - 0.3 PB1 5.0 3.0 10.0 4.0 DOBA 1.0 - 0.4 — TAED 0.5 0.3 0.5 0.6 Sulfate 4.0 5.0 — 5.0 SRPI - 0.4 - - Sud suppressor - 0.5 — — Speckle 1.0 0.5 - 5.0 Misc / minor to 100% EXAMPLE 4The following compositions are pre-treatmentcompositions in accordance with the invention.0 P Q R s T u MES 1 2 0.8 4 - - - C45E7 6.5 7.5 - - - - - C23E3 — 2.0 5.0 5.0 7.0 9.0 3.0 C25E2.5S 10.0 14.0 17.0 8.0 5.0 15.0 20.0 SADS — — 3.0 - 1.0 1.0 2.0 Acetyltriethyl citrate 3.5 4 2.5 - - 3.0 3.5 Percarbonate - 3.0 2.0 3 - — Perborate 2.0 3.0 - — 1.0 5.0 NACA-OBS - 0.3 - — 0.6 0.4 NOBS / LOBS / DOBS 1 - 1 0.2 0.4 - - TAED 0.5 0.6 0.3 0.8 0.9 0.4 0.7 Chelant 0.3 0.5 - - 0.2 - 0.8 Water and minors H2SO4 up to pH4 V W X Y Z AA BB Sodium C11-C13 akylbenzene-sulfonate 12.0 16.0 23.0 19.0 18.0 20.0 16.0 Sodium C14-C15 alcohol sulfate 4.5 - - - 4.0 C14-C15 alcohol ethoxylate (0.5) sulfate - - - - - C14-C15 alcohol ethoxylate (3) sulfate - - 2.0 - 1.0 1.0 1.0 Sodium C14-C15 alcohol ethoxylate (3.0) 2.0 2.0 - 1.3 - - 0.6 C9-C14 alkyl dimethyl hydroxy ethyl quaternary ammonium salt - - 1.0 0.5 2.0 Tallow fatty acid — — — 1.0 Tallow alcohol Ethoxylate (50) - - - - - - - Sodium tripolyphosphate 23.0 25.0 24.0 22.0 20.0 15.0 20.0 Sodium carbonate 15.0 12.0 15.0 10.0 13.0 11.0 10.0 Sodium polyacrylate (45%) 0.5 0.5 0.5 0.5 Sodium polyacrylate /  maleate polymer - - 1.0 1.0 1.0 2.0 0.5 Sodium silicate (1:6 ratio NaO / SiO2)(46%) 3.0 6.0 9.0 8.0 9.0 6.0 8.0 Sodium sulfate 25.0 18.0 20.0 18.0 20.0 22.0 13.0 Sodium perborate 5.0 5.0 10.0 8.0 3.0 1.0 2.0 Polyethyleneglycol), MW -4000 (50%) 1.5 1.5 1.0 1.0 - - 0.5 Sodium carboxy methyl cellulose 1.0 1.0 1.0 - 0.5 0.5 0.5 Citric acid - — — — NOBS / DOBS 0.5 1.0 0.5 0.5 1.0 0.7 0.3 TAED 1.5 1.0 2.5 3.0 0.3 0.2 0.5 Soil release polymer1 1.5 1.5 1.0 1.0 - 1.0 - Soil release polymer2 - - - - 1.0 - 1.0 Moisture 7.5 7.5 6.0 7.0 5.0 3.0 5.0 Magnesium sulfate - - - - 1.0 0.5 1.5 Speckle 0.5 3.0 - 5.0 2.0 - 0.2 Chelants — — - — 0.8 0.6 1.0 Enzymes, including amylase, amylase II, cellulase, protease and lipase - - - - 2.0 1.5 2.0 Minors, e.g., perfume, brightener, photobleach, Dye 1.0 1.0 1.0 1.0 0.5 1.5 1.0 1. Non-cotton soil release polymer according to U.S.Patent 5,415,807, Gosselink, Pan, Kellett and Hall, issued May 16, 1995.2. Non-cotton soil release polymer according to U.S.Application No. 60 / 051517.CC DD EE FF Sodium C11-C13 Alkylbenzenesulfonate 13.3 13.7 10.4 8.0 Sodium C14-C15 alcohol sulfate 3.9 4.0 4.5 - C14-C15 alcohol ethoxylate (0.5) sulfate 2.0 2.0 - - C14-C15 alcohol ethoxylate (3) sulfate - - - - Sodium C14-C15 Alcohol ethoxylate (6.5) 0.5 0.5 0.5 5.0 C9-C14 alkyl dimethyl hydroxy ethyl quaternary ammonium salt 1.0 - 0.5 Tallow fatty acid 0.5 — — Tallow alcohol ethoxylate (50) - - 1.0 0.3 Sodium tripolyphosphate 41.0 20.0 Zeolite A, hydrate (0.1-10 micron size) 26.3 - 21.3 1.0 Sodium carbonate 23.9 12.4 25.2 17.0 Sodium polyacrylate (45%) 3.4 0.0 2.7 - Sodium polyacrylate / maleate polymer - - 1.0 1.5 Sodium silicate (1:6 ratio NaO / SiO2)(46%) 2.4 6.4 2.1 6.0 Sodium sulfate 10.5 10.9 8.2 15.0 Sodium perborate 1.0 1.0 1.0 2.0 Poly(ethyleneglycol), MW ~4000 (50%) 1.7 0.4 1.0 - Sodium carboxy Methyl cellulose 1.0 - - 0.3 Citric acid — 3.0 — NOBS / DOBS 0.2 0.5 0.5 0.1 TAED 0.6 0.5 0.4 0.3 Soil release polymer1 1.5 - - - Soil release polymer2 — 1.5 1.0 1.0 Moisture 7.5 3.1 6.1 7.3 Magnesium sulfate — - — 1.0 Chelants — — 0.5 Enzymes, including amylase, amylase II, cellulase, protease and lipase - 1.0 - 1.5

Claims

Minors, e.g., perfume, brightener, photobleach, dye 1.0 1.0 1.0 1.0 Minors, e.g., perfume, brightener, photobleach, dye 1.0 1.0 1.0 1.0 1.  Non-cotton soil release polymer according to U.S. Patent 4,968,451, Scheibel, et al., issued November 6, 1990.

2. Non-cotton soil release polymer according to U.S. Application No. 60 / 051517.What is claimed is:

1. A detergent composition, having a density of from 330 g / liter to 700 g / liter, comprising a bleaching system containing a hydrophilic and a hydrophobic peracid bleach or precursors thereto and a peroxide source, characterized in that the total level of Available Oxygen from the hydrophilic and hydrophobic peracid bleach (AvO-a) is less than 5,000 ppm by weight of the composition, the ratio of Available Oxygen of the hydrophobic peracid or precursor (AvO-hb)to the Available Oxygen of the hydrophilic peracid or precursor (AvO-hp) is from 3:1 to 1:50 and the ratio of the Available Oxygen of the peroxide source (AvO-o) to the AvO-a is at least 2:1.

2. A detergent composition according to claim 1 wherein the hydrophilic bleach precursor comprises TAED.

3. A detergent composition according to claim 2 wherein the hydrophobic peracid or precursor comprises a hydrophobic group which is derived from fatty acid comprising at least 8 carbon atoms.

4. A detergent composition according to claim 1 wherein the ratio of AvO-o to the AvO-a is at least 3:1.

5. A detergent composition according to claim 1, comprising a phosphate-builder.

6. A detergent composition according to claim 1 whereby the peroxide source bleaching comprises one or more inorganic perhydrate salts.

7. A detergent composition according to claim 1 comprising one or more enzyme.

8. Method for sanitization of fabrics comprising the step of contacting the fabrics with a composition or a solution of a composition, comprising a hydrophilic and hydrophobic peracid bleach or precursors and a peroxide source, characterized in that the ratio of Available Oxygen of the hydrophobic peracid or precursor (AvO-hb) to the Available Oxygen of the hydrophilic peracid or precursor (AvO-hp) is from 3:1 to 1:50 and the ratio of the Available Oxygen of the peroxide source (AvO-o) to the total level of Available Oxygen from the hydrophilic and hydrophobic peracid bleach (AvO-a) is at least 2:1.

9. A detergent composition according to claim 4 wherein the ratio of AvO-o to the AvO-a is at least 4:1.

10. A detergent composition according to claim 2 wherein the hydrophobic peracid or precursor comprises a peracid precursor having a oxybenzene sulfonate leaving group.Susan Judith MasonLudivine Pascale Marie Grippay Nour-Eddine GuediraDonald Ray BrownMichelle Frances MelleaINVENTORS