CA2264916A1 - Detergent composition - Google Patents

Abstract

There is provided an automatic dishwashing detergent composition comprising a high cloud point nonionic surfactant and an amount of water-soluble salt to provide conductivity in deionised water at 25~ of greater than 3 milli Siemens/cm.

Description

I01520253035wo 98/11 185 1CA 02264916 1999-03-05PCT/US97/15977Detergent CompositionTechnical Field The present invention relates to a detergent composition comprising at least one highcloud point nonionic surfactant and an amount of water-soluble salt to provideconductivity in deionised water measured at 25°C of greater than 3 milliSiemens/cm.BackgroundAlthough in general detergent compositions employed in automatic dishwashing andfabric laundering may be similar there is at least one distinct difference that is afunction of the different washing mechanisms of the dishwashing and fabriclaundering machines commonly available in the market. Fabric laundering isnormally done in purpose—built machines having a tumbling action, whereasautomatic dishwashing appliances use a spray action mechanism. Fabric launderingmachines are able to tolerate detergent compositions which produce suds, fabriclaundering detergent compositions are thus generally suds producing. By contrastthe spray action of dishwashing machines tends to cause sudsing. Suds can easilyoverflow the low sills of dishwashers and slow down the spray action, which in tumreduces the cleaning action. Fabric laundering detergent compositions are generallyunderstood to be incompatible with use in automatic dishwashing machines.Detergent compositions generally comprise at least one detergent surfactant.Surfactants can be selected from anionic, nonionic, cationic, zwitterionic oramphoteric. Surfactants are known to provide two distinct functions defined by thecloud point of the particular surfactant. Above the cloud point of the surfactant, thel01520253035W0 98/1 1 185CA 02264916 1999-03-05PCTIUS97/105977surfactant tends to become increasingly insoluble and provides a suds suppressionfunction, whereas below the cloud point, the surfactant tends to be soluble, providinga cleaning function. The majority of commonly available surfactants are generallyused below their cloud points providing cleaning benefits but also produce suds.Since suds reduce the cleaning action of the automatic dishwasher use of thesesurfactants is undesirable in automatic dishwashers. Generally, surfactants selectedfor use in automatic dishwashing are low-sudsing nonionic surfactants.Low-sudsing nonionic surfactants generally have low cloud points and are thereforegenerally above their cloud points, providing a suds suppression function, in use inthe dishwasher. As described above, surfactants above their cloud point generallyprovide only limited cleaning benefits, for example spot reduction benefits.Attempts at making use of higher cloud point nonionic surfactants that provide acleaning function have typically failed due to the unacceptable sudsing of suchsurfactants. ‘Despite the prejudice in the art, the Applicant has found that a nonionic surfactanthaving a high cloud point can be incorporated into an automatic dishwashingdetergent composition. In addition, the cleaning performance of the high cloud pointsurfactant is further improved, especially on cleaning greasy soils (e.g., lipstick)when the conductivity of the wash water of the dishwasher is greater than 3 milliSiemens/cm (measured at 25°C). In a preferred aspect of the present invention theautomatic dishwashing detergent composition additionally comprises a sudssuppresser and/or more particularly a low cloud point nonionic surfactant.Summg of the InventionAccording to the present invention there is provided an automatic dishwashingdetergent composition comprising:a) one or more high cloud point nonionic surfactants having a cloud point of greaterthan 40°C; andb) an amount of water-soluble salt to provide conductivity in deionised watermeasured at 25°C of greater than 3 milli Siemens/cm.Detailed Description of the InventionW0 98/1 1 185l01520253035CA 02264916 1999-03-05PCT/US97/15977High Cloud Point Nonionic Surfactant SystemHigh cloud point nonionic surfactants useful in the present invention are present atlevels of from 0.1% to 15% of the composition. In general, bleach-stable surfactantsare preferred.The nonionic surfactant of the present invention has a high cloud point. "Cloudpoint", as used herein, is a well known property of nonionic surfactants which is theresult of the surfactant becoming less soluble with increasing temperature, thetemperature at which the appearance of a second phase is observable is referred to asthe "cloud point" (See) Kirk Othmer’s Encyclopedia of Chemical Technology, 3"‘ Ed.Vol.22 pp. 360-379,”Surfactants and Detersive Systems”).The term "high cloud point" nonionic has a cloud point of greater than 40°C,preferably greater than 50°C, and more preferably greater than 60°C. Preferably thenonionic surfactant comprises an ethoxylated surfactant derived from the reaction ofa monohydroxy alcohol or alkylphenol containing from 8 to 20 carbon atoms, withfrom 6 to 15 moles of ethylene oxide per mole of alcohol or alkyl phenol on anaverage basis. Suitable high cloud point nonionic surfactants include, for example,Tergitol l5S9 (supplied by Union Carbide), Rhodasurf TMD 8.5 (supplied by Rhone Poulenc), and Neodol 91-8 (supplied by Shell).It is also preferred for the purposes of the present invention that the high cloud pointnonionic surfactant additionally has a hydrophile-lipophile balance ("I-ILB"; see KirkOthmer hereinbefore) value within the range of from 9 to 15, preferably 1 1 to 15.Such materials include, for example, Tergitol l5S9 (supplied by Union Carbide),Rhodasurf TMD 8.5 (supplied by Rhone Poulenc), and Neodol 91-8 (supplied byShell).Another preferred high cloud point nonionic surfactant is derived from a straight orpreferably branched chain or secondary fatty alcohol containing from 6 to 20 carbonatoms (C6-C20 alcohol), including secondary alcohols and branched chain primaryalcohols. Preferably, high cloud point nonionic surfactants are branched orsecondary alcohol ethoxylates, more preferably mixed C9/C11 or C11/C15 branchedalcohol ethoxylates, condensed with an average of from 6 to 15 moles, preferablyfrom 6 to 12 moles, and most preferably from 6 to 9 moles of ethylene oxide perCA 02264916 1999-03-05wo 93/11135 PCT/US97/15977mole of alcohol. Preferably such ethoxylated nonionic surfactants have a narrowethoxylate distribution relative to the average.Nonionic surfactants can optionally contain propylene oxide in an amount up to 15%by weight. Other preferred nonionic surfactants can be prepared by the processesdescribed in U.S. Patent 4,223,163, issued September 16, 1980, Builloty,incorporated herein by reference.W0 98/ 1 1 18510152025CA 02264916 1999-03-05PCT/US97/15977Water-Soluble SaltSuitable water-soluble salts include any known water-soluble salt commonlyavailable and suitable for incorporation into an automatic dishwashing detergentcomposition. Preferred water-soluble salts dissolve in water, preferably attemperature less than40°C, more preferably less than 35°C and even more preferably less than 30°C.Most preferably the water-soluble salt dissolves at ambient temperature.The water-soluble salt is present in an amount such that when dissolved in deionisedwater it provides conductivity in deionised water measured at 25°C of greater than 3milli Siemens/cm, preferably greater than 4 milli Siemens/cm, most preferablygreater than 4.5 milli Siemens/cm.Preferred water-soluble salts incorporated into the detergent composition of thepresent invention include those that readily dissociate in water. Preferred saltsinclude those which provide multi valent dissociated ions, for example the salts ofsulphate, nitrate or perborate, however salts that provide dissociated ions with singlevalency (eg. chloride) may also be used. Preferred salts are those which remaindissociated in water providing sustained conductivity, for example water solublesulphate salts. However, salts that dissociate but then re-associate with the sameand/or other ions to form the same and/or other salts, thus providing only transientconductivity, may also be used. In this embodiment however, it is preferred thatseveral water-soluble salts are used such that a combination of a number of water-soluble salts provide conductivity greater than 3 milli Siemens/cm, preferably greaterthan 4 milli Siemens/cm, most preferably greater than 4.5 milli Siemens/cm.51020253035W0 98/11185CA 02264916 1999-03-05PCT/US97/ 15977Conductivitv Measurement methodFor the purposes of the present invention, conductivity was measured using a Jenway4020 conductivity meter calibrated against a standard sample of known conductivity;for example a 0.01M solution of potassium chloride provides conductivity of1.413 milli Siemens/cm.A solution comprising 4g of detergent composition in 1 litre of deionised water wasprepared. The solution was continuously. stirred at a constant rate to aid dissolutionof the detergent composition. 60ml samples of the solution are removed at intervalsand the conductivity measured using the Jenway 4020 conductivity meter.Sulphate SaltA highly preferred water-soluble salt is a water-soluble sulphate salt. Where present,the water-soluble sulphate salt is present at a level of from 0.1% to 40%, morepreferably from 1% to 30%, most preferably from 5% to 25% by weight of thecompositions.The water-soluble sulphate salt may be essentially any sulphate salt with any suitable“counter cation. Preferred salts are selected from the sulphates of the alkali andalkaline earth metals, particularly sodium sulphate.Silicate SaltAnother preferred water-soluble salt is a water-soluble silicate salt. Preferably thewater-soluble silicate salt is an alkali or alkaline earth metal silicate. A preferredalkali metal silicate is sodium silicate having an SiO2:Na2O ratio of from 1.8 to 3.0,preferably from 1.8 to 2.4, most preferably 2Ø Sodium silicate is preferably presentat a level of less than 20%, preferably from 1% to 15%, most preferably from 3% to12% by weight of SiO2. The alkali metal silicate may be in the form of either theanhydrous salt or a hydrated salt.Alkali metal silicate whilst providing conductivity in the wash water will alsoprovide alkalinity. Alkalinity is also preferably provided by the presence of sodiummetasilicate. Where present the sodium metasilicate is present at a level of at leastCA 02264916 1999-03-05PCT/US97/15977wo 98/11185 7l015202530350.4%, preferably at least 1%, most preferably at least 1.5%. Sodium metasilicate hasa nominal SiO2 : Na2O ratio of 1Ø The weight ratio of said sodium silicate to saidsodium metasilicate, measured as SiO2, is preferably from 50:1 to 5:4, morepreferably from 15:1 to 2:1, most preferably from 10:1 to 5:2.Water-soluble salts of Bleaching AgentsOther preferred water-soluble salts include salts of bleaching agents, for example thesalts of oxygen-releasing or chloride bleaching agents. Preferred water-solubleinclude those of perborate and chloride bleaching agents. These and other suitablebleaching agents are described in more detail hereafter.Suds SuppressersParticularly preferred components of .the detergent composition are compounds for .reducing or suppressing the formation of suds. Suds suppression can be of particularimportance in the so-called "high concentration cleaning process" as described inU.S. 4,489,455 and 4,489,574 and in front-loading European-style washingmachines.A wide variety of materials may be used as suds suppressers, and suds suppressersare well known to those skilled in the art. See, for example, Kirk OthmerEncyclopedia of Chemical Technology, Third Edition, Volume 7, pages 430-447(John Wiley & Sons, Inc., 1979). One category of suds suppresser of particularinterest encompasses monocarboxylic fatty acid and soluble salts therein. See U.S.Patent 2,954,347, issued September 27, 1960 to Wayne St. John. Themonocarboxylic fatty acids and salts thereof used as suds suppresser typically havehydrocarbyl 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 lithiumsalts, and ammonium and alkanolammonium salts.The detergent compositions herein may also contain non-surfactant suds suppressers.These include, for example: high molecular weight hydrocarbons such as paraffin,fatty acid esters (e.g., fatty acid triglycerides), fatty acid esters of monovalentalcohols, aliphatic C13-C40 ketones (e.g., stearone), etc. Other suds inhibitorsinclude N-alkylated amino triazines such as tri— to hexa-alkylmelamines or di- toCA 02264916 1999-03-05PCTIUS97/15977wo 98l11185 b 8l01520253035tetra—alkyldiamine chlortriazines formed as products of cyanuric chloride with two orthree moles of a primary or secondary amine containing 1 to 24 carbon atoms,propylene oxide, and monostearyl phosphates such as monostearyl alcohol phosphateester and monostearyl di-alkali metal (e.g., K, Na, and Li) phosphates and phosphateesters. The hydrocarbons such as paraffin and haloparaffin can be utilized in liquidform. The liquid hydrocarbons will be liquid at room temperature and atmosphericpressure, and will have a pour point in the range of -40°C and 50°C, and a minimumboiling point not less than 110 C (atmospheric pressure). It is also known to utilizewaxy hydrocarbons, preferably having a melting point below 100°C. Thehydrocarbons constitute a preferred category of suds suppressor for detergentcompositions. Hydrocarbon suds suppressors are described, for example, in U.S.Patent 4,265,779, issued May 5, 1981 to Gandolfo et al. The hydrocarbons, thus,include aliphatic, alicyclic. aromatic, and heterocyclic saturated or unsaturatedhydrocarbons having from 12 to 70 carbon atoms. The term "paraffin," as used inthis suds suppressor discussion, is intended to include mixtures of true paraffins andcyclic hydrocarbons.Another preferred category of non-surfactant suds suppressors comprises siliconesuds suppressors. This category includes the use of polyorganosiloxane oils, such aspolydimethylsiloxane, dispersions or emulsions of polyorganosiloxane oils or resins,and combinations of polyorganosiloxane with silica particles wherein thepolyorganosiloxane is chemisorbed or fused onto the silica. Silicone sudssuppressors are well known in the art and are, for example, disclosed in U.S. Patent4,265,779, issued May 5, 1981 to Gandolfo et al and European Patent ApplicationNo. 8930785l.9, published February 7, 1990, by Starch, M. S.Other silicone suds suppressors are disclosed in U.S. Patent 3,455,839 which relatesto compositions and processes for defoaming aqueous solutions by incorporatingtherein small amounts of polydimethylsiloxane fluids.Mixtures of silicone and silanated silica are described, for instance. in German PatentApplication DOS 2,124,526. Silicone defoamers and suds controlling agents ingranular detergent compositions are disclosed in U.S. Patent 3,933,672, Bartolotta etal, and in U.S. Patent 4,652,392, Baginski et al, issued March 24, 1987.CA 02264916 1999-03-05PCT/US97/15977wo 98ll1l85 9l0I520253035An exemplary silicone based suds suppressor for use herein is a suds suppressingamount of a suds controlling agent consisting essentially of:(i) polydimethylsiloxane fluid having a viscosity of from about 20 cs. toabout 1,500 cs. at 25°C;(ii) from about 5 to about 50 parts per 100 parts by weight of (i) of siloxaneresin composed of (CH3)3SiO1/2 units of SiO2 units in a ratio of from(CH3)3 SiO1/2 units and to SiO2 units of from about 0.621 to about1.221; and(iii) from about 1 to about 20 parts per 100 parts by weight of (i) of a solidsilica gel.In the preferred silicone suds suppressor used herein, the solvent for a continuousphase is made up of certain polyethylene glycols or polyethylene-polypropyleneglycol copolymers or mixtures thereof (preferred), or polypropylene glycol. Theprimary silicone suds suppressor is branched/crosslinked and preferably not linear.The silicone suds suppressor herein preferably comprises polyethylene glycol and acopolymer of polyethylene glycol/polypropylene glycol, all having an averagemolecular weight of less than about 1,000, preferably between about 100 and 800.The polyethylene glycol and polyethylene/polypropylene copolymers herein have asolubility in water at room temperature of more than about 2 weight %, preferablymore than about 5 weight %.The preferred solvent herein is polyethylene glycol having an average molecularweight of less than about 1,000, more preferably between about 100 and 800, mostpreferably between 200 and 400, and aglycol/polypropylene glycol, preferably PPG 200/PEG 300. Preferred is a weightratio of between about 1:1 and 1:10, most preferably between 1:3 and 1:6, ofcopolymer of polyethylenepolyethylene glycolzcopolymer of polyethylene-polypropylene glycol.In a preferred embodiment of the present invention, the detergent compositionadditionally comprises a low cloud point nonionic surfactant sud suppressor. Asused herein, a "low cloud point" nonionic surfactant is defined as a nonionicsurfactant system ingredient having a cloud point of less than 30°C, preferably lessthan 20°C, and most preferably less than 10°C. Typical low cloud point nonionicsurfactants include nonionic alkoxylated surfactants, especially ethoxylates derivedfrom primary alcohol, and polyoxypropylene/polyoxyethylene/polyoxypropylenel01520253035W0 98/11185CA 02264916 1999-03-0510 PCT/US97/ 15977(PO/E0/PO) reverse block polymers. Also, such low cloud point nonionicsurfactants include, for example, ethoxylated-propoxylated alcohol (e.g., OlinCorporation's Poly—Tergent® SLF 18), epoxy—capped poly(oxyalkylated) alcohols(e. g., Olin Corporation's Poly-Tergent® SLF18B series of nonionics, described inWO 94/22800, published October 13, 1994 by Olin Corporation) and ether-cappedpoly(oxyalkylated) alcohol surfactants described in more detail later.Low cloud point nonionic surfactants may comprise a polyoxyethylene,polyoxypropylene block polymeric compound. Block polyoxyethylene-polyoxypropylene polymeric compounds include those based on ethylene glycol,propylene glycol, glycerol, trimethylolpropane and ethylenediamine as initiatorreactive hydrogen compound. Certain of the block polymer surfactant compoundsdesignated PLURONIC®, REVERSED PLURONIC®, and TETRONIC® by the _BASF-Wyandotte Corp., Wyandotte, Michigan, are suitable in ADD compositions ofthe invention. Preferred examples include REVERSED PLURONIC® 25R2 andTETRONIC® 702, Such surfactants are typically useful herein as low cloud pointnonionic surfactants.Where the detergent composition of the present invention comprises a low cloudpoint as well as a high cloud point surfactant the surfactants are combined in a weightratio preferably within the range of from 10:1 to 1:10.Other suds suppressors useful herein comprise the secondary alcohols (e.g., 2-alkylalkanols) and mixtures of such alcohols with silicone oils, such as the siliconesdisclosed in U.S. 4,798,679, 4,075,118 and EP 150,872. The secondary alcoholsinclude the C6-C16 alkyl alcohols having a C1-C16 chain. A preferred alcohol is 2-butyl octanol, which is available from Condea under the trademark ISOFOL 12.Mixtures of secondary alcohols are available under the trademark I SALCHEM 123from Enichem. Mixed suds suppressors typically comprise-mixtures of alcohol +silicone at a weight ratio of 1:5 to 5:1.For any detergent compositions to be used in automatic laundry or dishwashingmachines, suds should not form to the extent that they either overflow the washingmachine or negatively affect the washing mechanism of the dishwasher. Sudssuppressors, when utilized, are preferably present in a "suds suppressing amount. By"suds suppressing amount" is meant that the formulator of the composition can select1020253035W0 98/1 1 185CA 02264916 1999-03-051 1 PCT/US97/15977an amount of this suds controlling agent that will sufficiently control the suds toresult in a low-sudsing laundry or dishwashing detergents for use in automaticlaundry or dishwashing machines.The compositions herein will generally comprise from 0% to 10% of sudssuppressor. When utilized as suds suppressors, monocarboxylic fatty acids, and saltstherein, will be present typically in amounts up to 5%, by weight, of the detergentcomposition. Preferably, from 0.5% to 3% of fatty monocarboxylate suds suppressoris utilized. Silicone suds suppressors are typically utilized in amounts up to 2.0%, byweight, of the detergent composition, although higher amounts may be used. Thisupper limit is practical in nature, due primarily to concern with keeping costsminimized and effectiveness of lower amounts for effectively controlling sudsing.Preferably from 0.01% to 1% of silicone suds suppressor is used, more preferablyfrom 0.25% to 0.5%. As used herein, these weight percentage values include any 1silica that may be utilized in combination with polyorganosiloxane, as well as anyoptional materials that may be utilized. Monostearyl phosphate suds suppressors aregenerally utilized in amounts ranging from 0.1% to 2%, by weight, of thecomposition. Hydrocarbon suds suppressors are typically utilized in amountsranging from 0.01% to 5.0%, although higher levels can be used. The low cloudpoint nonionic surfactant suds suppressors are typically used at 0.1%-15% by weightof the finished compositionsProcessThe detergent composition described herein is prepared by conventional methods, inthat particulate components are premixed in a suitable mixer and liquid componentsare applied to, preferably sprayed onto the premix to form the detergent composition.Particulate components may be prepared by any known method for example spraydrying granulation or agglomeration. Suitable mixers may be batch or continuousmixers and include, but are not limited to‘ pan, rotary drum and vertical blender types.A particularly preferred process for preparing the detergent composition describedherein is described in co-pending GB Patent Application (Attorney docket numberCM l572F).Detergent Compositionl01520W0 98/11185CA 02264916 1999-03-05PCT/US97/15977The detergent composition described herein may include a variety of differentingredients including builder compounds. additional surfactants, enzymes, bleachingagents, alkalinity sources, lime soap dispersants, organic polymericcompounds including polymeric dye transfer inhibiting agents, crystal growthinhibitors, heavy metal ion sequestrants, metal ion salts, enzyme stabilisers, corrosioninhibitors, suds suppressors, solvents, fabric softening agents, optical brighteners andhydrotropes.Highly preferred components of the detergent composition as described earlierinclude a builder compound, a surfactant, an enzyme and a bleaching agent.Builder CompoundThe detergent compositions of the present invention preferably contain a buildercompound, typically present at a level of from 1% to 80% by weight, preferably fiom10% to 70% by weight, most preferably from 20% to 60% by weight of thecomposition.Where water-soluble builders compounds are present in salt form, the salt may alsoprovide conductivity in the wash water. Such builder compounds include salts ofpolycarboxylates, carbonates, bicarbonates, borates, phosphates.1020253035WO 98/11185CA 02264916 1999-03-051 3 PCT/US97/15977Water-Soluble Builder CompoundSuitable water-soluble builder compounds include the water soluble monomericpolycarboxylates, or their acid forms, homo or copolymeric polycarboxylic acids" ortheir salts in which the polycarboxylic acid comprises at least two carboxylic radicalsseparated from each other by not more that two carbon atoms, carbonates,bicarbonates, borates, phosphates, and mixtures of any of the foregoing.The carboxylate or polycarboxylate builder can be monomeric or oligomeric in typealthough monomeric polycarboxylates are generally preferred for reasons of cost andperformance.Suitable carboxylates containing one carboxy group include the water soluble salts oflactic acid, glycolic acid and ether derivatives thereof. Polycarboxylates containingtwo carboxy groups include the water-soluble salts ‘of succinic acid, malonic acid,(ethylenedioxy) diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acidand fitmaric acid, as well as the ether carboxylates and the sulfinyl carboxylates.Polycarboxylates containing three carboxy groups include, in particular, water-soluble citrates, aconitrates and citraconates as well as succinate derivatives such asthe carboxymethyloxysuccinates described in British Patent No. 1,379,241,lactoxysuccinates described in British Patent No. 1,389,732, and aminosuccinatesdescribed in Netherlands Application 7205873, and the oxypolycarboxylate materialssuch as 2-oxa-1,1,3-propane tricarboxylates described in British Patent No.1,387,447.Polycarboxylates containing four carboxy groups include oxydisuccinates disclosedin British Patent No. 1,261,829, 1,l,2,2-ethane tetracarboxylates, 1,1,3,3-propanetetracarboxylates and l,l,2,3-propane tetracarboxylates. Polycarboxylatescontaining sulfo substituents include the sulfosuccinate derivatives disclosed inBritish Patent Nos. 1,398,421 and 1,398,422 and in U.S. Patent No. 3,936,448, andthe sulfonated pyrolysed citrates described in British Patent No. 1,439,000.Alicyclic and heterocyclic polycarboxylates include cyclopentane-cis,cis,cis-tetracarboxylates, cyclopentadienide pentacarboxylates, 2,3,4,5-tetrahydrofuran - cis,cis, cis-tetracarboxylates, 2,5—tetrahydrofuran - cis - dicarboxylates, 2,2,5,5-tetrahydrofuran - tetracarboxylates, 1,2,3,4,5,6-hexane - hexacarboxylates andl01520253035W0 98/1 1 185CA 02264916 1999-03-0514 PCT/US97/15977carboxymethyl derivatives of polyhydric alcohols such as sorbitol, mannitol andxylitol. Aromatic polycarboxylates include mellitic acid, pyromellitic acid and thephthalic acid derivatives disclosed in British Patent No. 1,425,343.Of the above, the preferred polycarboxylates are hydroxycarboxylates containing upto three carboxy groups per molecule, more particularly citrates.The parent acids of the monomeric or oligomeric polycarboxylate chelating agents ormixtures thereof with their salts, e.g. citric acid or citrate/citric acid mixtures are alsocontemplated as useful builder components.Borate builders, as well as builders containing borate-forming materials that can ‘produce borate under detergent storage or wash conditions can also be used but arenot preferred at wash conditions less that about 50°C, especially less than about40°C.Examples of carbonate builders are the alkaline earth and alkali metal carbonates,including sodium carbonate and sesqui-carbonate and mixtures thereof with ultra-finecalcium carbonate as disclosed in German Patent Application No. 2,321,001published on November 15, 1973.Highly preferred builder compounds for use in the present invention are water-soluble phosphate builders. Specific examples of water-soluble phosphate buildersare the alkali metal tripolyphosphates, sodium, potassium and ammoniumpyrophosphate, sodium and potassium and ammonium pyrophosphate, sodium andpotassium orthophosphate, sodium polymeta/phosphate in which the degree ofpolymerisation ranges from about 6 to 21, and salts of phytic acid.Specific examples of water-soluble phosphate builders are the alkali metaltripolyphosphates, sodium, potassium and ammonium pyrophosphate, sodium andpotassium and ammonium pyrophosphate, sodium and potassium orthophosphate,sodium polymeta/phosphate in which the degree of polymerization ranges from about6 to 21, and salts of phytic acid.Partiallv Soluble or Insoluble Builder Compound1020253035WO 98/11185CA 02264916 1999-03-051 5 PCT/US97/15977The compositions of the present invention may Contain a partially soluble orinsoluble builder compound. Partially soluble and insoluble builder compounds areparticularly suitable for use in detegent compositions prepared for use in laundrycleaning methods. Examples of partially water soluble builders include thecrystalline layered silicates as disclosed for example, in EP-A—0l645l4, DE-A-3417649 and DE-A-3 742043. Preferred are the crystalline layered sodium silicatesof general formulaNaMSixO2+1 .yH2Owherein M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a numberfrom 0 to 20. Crystalline layered sodium silicates of this type preferably have a twodimensional ‘sheet’ structure, such as the so called 8-layered structure, as described inEP 0 164514 and EP 0 293640.Methods for preparation of crystalline layered silicates of this type are disclosed inDE-A-3417649 and DE-A-3 742043. For the purpose of the present invention, x inthe general formula above has a value of 2,3 or 4 and is preferably 2.The most preferred crystalline layered sodium silicate compound has the formula 5-Na2Si2O5 , known as NaSKS—6 (trade name), available from Hoechst AG.The crystalline layered sodium silicate material is preferably present in granulardetergent compositions as a particulate in intimate admixture with a solid, water-soluble ionisable material as described in PCT Patent Application No. W092/18594.The solid, water-soluble ionisable material is selected from organic acids, organicand inorganic acid salts and mixtures thereof, with citric acid being preferred.Examples of largely water insoluble builders include the sodium aluminosilicates.Suitable aluminosilicates include the aluminosilicate zeolites having the unit cellformula NaZ[(AlO2)Z(SiO2)y]. xH3O wherein z and y are at least 6; the molar ratioof z to y is from 1.0 to 0.5 and x is at least 5, preferably from 7.5 to 276, morepreferably from 10 to 264. The aluminosilicate material are in hydrated form andare preferably crystalline, containing from 10% to 28%, more preferably from 18% to22% water in bound form.wo 98/11185 16I520253035CA 02264916 1999-03-05PCT/U S97/ 15977The aluminosilicate zeolites can be naturally occurring materials, but are preferablysynthetically derived. Synthetic crystalline aluminosilicate ion exchange materialsare available under the designations Zeolite A, Zeolite B, Zeolite P, Zeolite X,Zeolite HS and mixtures thereof.A preferred method of synthesizing aluminosilicate zeolites is that described bySchoeman et al (published in Zeolite (1994) 14(2), 110-116), in which the authordescribes a method of preparing colloidal aluminosilicate zeolites. The colloidalaluminosilicate zeolite particles should preferably be such that no more than 5% ofthe particles are of size greater than lum in diameter and not more than 5% ofparticles are of size less then 0.05 um in diameter. Preferably the aluminosilicatezeolite particles have an average particle size diameter of between0.01 um and lum, more preferably between 0.05 pm and 0.9 um, most preferablybetween 0.1 pm and 0.6 pm.Zeolite A has the formulaNa 12 [A102) 12 (Si02)12]- xH20wherein x is from 20 to 30, especially 27. Zeolite X has the formula Na36[(AlO2)36(SiO2)106]. 276 H2O. Zeolite MAP, as disclosed in EP-B-384,070 is apreferred zeolite builder herein.Preferred aluminosilicate zeolites are the colloidal aluminosilicate zeolites. Whenemployed as a component of a detergent composition colloidal aluminosilicatezeolites, especially colloidal zeolite A, provide enhanced builder performance interms of providing improved stain removal. Enhanced builder performance is alsoseen in terms of reduced fabric encrustation and improved fabric whitenessmaintenance; problems believed to be associated with poorly built detergentcompositions.A surprising finding is that mixed aluminosilicate zeolite detergent compositionscomprising colloidal zeolite A and colloidal zeolite Y provide equal calcium ionsequestration performance versus an equal weight of commercially available zeoliteA. Another surprising finding is that mixed aluminosilicate zeolite detergent. -..,...__..__......__._..._.....___...CA 02264916 1999-03-05PCT/US97/ 15977wo 98/11185 1720253035compositions, described above, provide improved magnesium ion sequestrationperformance versus an equal weight of commercially available zeolite A.Additional SurfactantThe detergent composition of the present invention may comprise an additionalsurfactant. Suitable surfactants are selected from anionic, cationic, nonionicampholytic and zwitterionic surfactants and mixtures thereof. Automaticdishwashing machine products should be low foaming in character, thus the foamingof the surfactant system for use in dishwashing methods is preferably suppressed.The total surfactant is typically present at a level of from 0.2% to 30% by weight, Amore preferably from 0.5% to 10% by weight, most preferably from 1% to 5% byweight of the compositions.A typical listing of anionic, nonionic, ampholytic and zwitterionic classes, andspecies of these surfactants, is given in U.S.P. 3,929,678 issued to Laughlin andHeuring on December, 30, 1975. A list of suitable cationic surfactants is given inU.S.P. 4,259,217 issued to Murphy on March 31,1981. A listing of surfactantstypically included in automatic dishwashing detergent compositions is given forexample, in EP-A-0414 549 and PCT Applications No.5 WO 93/08876 and WO93/08874.Nonionic SurfactantEssentially any nonionic surfactants useful for detersive purposes can be included inthe compositions. Preferred, non-limiting classes of useful nonionic surfactants arelisted below.Nonionic Ethoxylated Alcohol SurfactantThe alkyl ethoxylate condensation products of aliphatic alcohols with from about 1 toabout 25 moles of ethylene oxide are suitable for use herein. The alkyl chain of thealiphatic alcohol can either be straight or branched, primary or secondary, andgenerally contains from 6 to 22 carbon atoms. Particularly preferred are thecondensation products of alcohols having an alkyl group containing from 8 to 20l015203035W0 98/1 1185CA 02264916 1999-03-051 8 PCT/US97/15977carbon atoms with from about 2 to about 10 moles of ethylene oxide per mole ofalcohol.End-Capped Alkvl Alkoxvlate SurfactantA suitable endcapped alkyl alkoxylate surfactant is the epoxy-cappedpoly(oxyalkylated) alcohols represented by the formula:R1O[CH2CH(CH3)O]x[CH2CH2O]y[CH2CH(OH)R2] (I)wherein R1 is a linear or branched, aliphatic hydrocarbon radical having from about4 to about 18 carbon atoms; R2 is a linear or branched aliphatic hydrocarbon radicalhaving from about 2 to about 26 carbon atoms; x is an integer having an averagevalue of from 0.5 to about 1.5, more preferably about 1; and y is an integer having avalue of at least about 15, more preferably at least about 20.Preferably, the surfactant of formula I, at least about 10 carbon atoms in the terminalepoxide unit [CH2CH(OH)R2]. Suitable surfactants of formula 1, according to thepresent invention, are Olin Corporation's POLY-TERGENT® SLF-18B nonionicsurfactants, as described, for example, in WO 94/22800, published October 13, 1994/ by Olin Corporation.Ether-capped poly; oxyalkylated) alcoholsPreferred surfactants for use herein include ether-capped poly(oxyalkylated) alcoholshaving the formula: 'R1O[CH2CH(R3)O]x[CH2]kCH(OH)[CH2]jOR2wherein R1 and R2 are linear or branched, saturated or unsaturated, aliphatic oraromatic hydrocarbon radicals having from 1 to 30 carbon atoms; R3 is H, or a linearaliphatic hydrocarbon radical having from 1 to 4 carbon atoms; x is an integer havingan average value from 1 to 30, wherein when x is 2 or greater R3 may be the same ordifferent and k and j are integers having an average value of from 1 to 12, and morepreferably 1 to 5.W0 98/111851020253035CA 02264916 1999-03-05PCT/US97/1597719R1 and R2 are preferably linear or branched, saturated or unsaturated, aliphatic oraromatic hydrocarbon radicals having from 6 to 22 carbon atoms with 8 to 18 carbonatoms being most preferred. H or a linear aliphatic hydrocarbon radical having from1 to 2 carbon atoms is most preferred for R3. Preferably, x is an integer having anaverage value of from 1 to 20, more preferably from 6 to 15.As described above, when, in the preferred embodiments, and x is greater than 2, R3may be the same or different. That is, R3 may vary between any of the alklyeneoxyunits as described above. For instance, if x is 3, R3may be be selected to fonnethlyeneoxy(EO) or propy1eneoxy(PO) and may vary in order of (EO)(PO)(EO),(EO)(EO)(PO); (EO)(EO)(EO); (PO)(EO)(PO); (PO)(PO)(EO) and (PO)(PO)(PO).Of course, the integer three is chosen for example only and the variation may bemuch larger with a higher integer value for x and include, for example, mulitple (E0)units and a much small number of (PO) units.Particularly preferred surfactants as described above include those that have a lowcloud point of less than 20°C. These low cloud point surfactants may then beemployed in conjunction with a high cloud point surfactant as described in detailbelow for superior grease cleaning benefits.Most preferred ether-capped poly(oxyalkylated) alcohol surfactants are those whereink is 1 and j is 1 so that the surfactants have the formula:R1O[CH2CH(R3)O]xCH2CH(OH)CH2OR3where R1, R2 and R3 are defined as above and x is an integer with an average valueof from 1 to 30, preferably from 1 to 20, and even more preferably from 6 to 18.Most preferred are surfactants wherein R1 and R2 range from 9 to 14, R3 is Hforming ethyleneoxy and x ranges from 6 to 15.The ether-capped poly(oxyalkylated) alcohol surfactants comprise three generalcomponents, namely a linear or branched alcohol, an alkylene oxide and an alkylether end cap. The alkyl ether end cap and the alcohol serve as a hydrophobic, oil-soluble portion of the molecule while the alkylene oxide group forms thehydrophilic, water-soluble portion of the molecule.l015203035W0 98/11185CA 02264916 1999-03-05PCT/US97/15977. 20These surfactants exhibit significant improvements in spotting and filmingcharacteristics and removal of greasy soils, when used in conjunction with high cloudpoint surfactants, relative to conventional surfactants.Generally speaking, the ether-capped po1y(oxya1kylene) alcohol surfactants of thepresent invention may be produced by reacting an aliphatic alcohol with an epoxideto form an ether which is then reacted with a base to form a second epoxide. Thesecond epoxide is then reacted with an alkoxylated alcohol to form the novelcompounds of the present invention. Examples of methods of preparing the ether-capped po1y(oxyalkylated) alcohol surfactants are described below:Preparation of C 1;/_1£;_ alkyl glycidyl etherA C12/14 fatty alcohol (100.00 g, 0.515 mol.) and tin (IV) chloride (0.58 g, 2.23mmol, available from Aldrich) are combined in a 500 mL three-necked round-bottomed flask fitted with a condenser, argon inlet, addition funnel, magnetic stirrerand internal temperature probe. The mixture is heated to 60 °C. Epichlorhydrin(47.70 g, 0.515 mol, available from Aldrich) is added dropwise so as to keep thetemperature between 60-65 °C. After stirring an additional hour at 60 °C, themixture is cooled to room temperature. The mixture is treated with a 50% solution ofsodium hydroxide (61.80 g, 0.773 mol, 50%) while being stirred mechanically. Afteraddition is completed, the mixture is heated to 90 °C for 1.5 h, cooled, and filteredwith the aid of ethanol. The filtrate is separated and the organic phase is washed withwater (100 mL), dried over MgSO4, filtered, and concentrated. Distillation of the oilat 100-120 °C (0.1 mm Hg) providing the glycidyl ether as an oil.Preparation of C _1_;_;__/_1_4 alkyl-Cfil ether capped alcohol surfactantNeodol® 91-8 (20.60 g, 0.0393 mol ethoxylated alcohol available from the Shellchemical Co.) and tin (IV) chloride (0.58 g, 2.23 mmol) are combined in a 250 mLthree-necked round-bottomed flask fitted with a condensergargon inlet, additionfunnel, magnetic stirrer and internal temperature probe. The mixture is heated to 60 °C at which point C12/14 alkyl glycidyl ether (1 1.00 g, 0.0393 mol) is addeddropwise over 15 min. After stirring for 18 h at 60 °C, the mixture is cooled to roomtemperature and dissolved in an equal portion of dichloromethane. The solution ispassed through a 1 inch pad of silica gel while eluting with dichloromethane. Thefiltrate is concentrated by rotary evaporation and then stripped in a kugelrohr oven(100 °C, 0.5 mm Hg) to yield the surfactant as an oil.l0CA 02264916 1999-03-05wo 93/1 1 135 PCT/US97/ 1597721Nonioriic Ethoxvlated/Propoxylated Fatty Alcohol SurfactantThe ethoxylated C5-C13 fatty alcohols and C6-C13 mixed ethoxylated/propoxylatedfatty alcohols are suitable surfactants for use herein, particularly where water soluble.Preferably the ethoxylated fatty alcohols are the C10—C1g ethoxylated fatty alcoholswith a degree of ethoxylation of from 3 to 50, most preferably these are the C12-C18ethoxylated fatty alcohols with a degree of ethoxylation from 3 to 40. Preferably themixed ethoxylated/propoxylated fatty alcohols have an alkyl chain length of from 10to 18 carbon atoms, a degree of ethoxylation of from 3 to 30 and a degree ofpropoxylation of from 1 to 10.101520253035W0 98/1 1 185 22CA 02264916 1999-03-05PCT/U S97/ 15977Nonionic EO/PO Condensates with Propylene GlycolThe condensation products of ethylene oxide with a hydrophobic base formed by thecondensation of propylene oxide with propylene glycol are suitable for use herein.The hydrophobic portion of these compounds preferably has a molecular weight offrom about 1500 to about 1800 and exhibits water insolubility. Examples ofcompounds of this type include certain of the commercially—available PluronicTMsurfactants, marketed by BASF.Nonionic EO Condensation Products with Propylene Oxide/Ethylene DiamineAdductsThe condensation products of ethylene oxide with the product resulting from thereaction of propylene oxide and ethylenediarnine are suitable for use herein. Thehydrophobic moiety of these products consists of the reaction product ofethylenediamine and excess propylene oxide, and generally has a molecular weightof from about 2500 to about 3000. Examples of this type of nonionic surfactantinclude certain of the commercially availableTetronicm compounds, marketed by BASF.Anionic SurfactantEssentially any anionic surfactants useful for detersive purposes are suitable. Thesecan include salts (including, for example, sodium, potassium, armnonium, andsubstituted ammonium salts such as mono-, di- and triethanolamine salts) of theanionic sulfate, sulfonate, carboxylate and sarcosinate surfactants. Anionic sulfatesurfactants are preferred.Other anionic surfactants include the isethionates such as the acyl isethionates, N-acyl taurates, fatty acid amides of methyl tauride, alkyl succinates andsulfosuccinates, monoesters of sulfosuccinate (especially saturated and unsaturatedCC 6~C1 4 diesters), N-acyl sarcosinates. Resin acids and hydrogenated resin acids are12-C18 monoesters) diesters of sulfosuccinate (especially saturated and unsaturatedalso suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenatedresin acids present in or derived from tallow oil.W0 98/11185l01520CA 02264916 1999-03-05PCT/US97/ 1597723Anionic Sulfate SurfactantAnionic sulfate surfactants suitable for use herein include the linear and branchedprimary and secondary alkyl sulfates, alkyl ethoxysulfates, fatty oleoyl glycerolsulfates, alkyl phenol ethylene oxide ether sulfates, the C 5-C17 acyl-N-(C1-C4 alkyl)and -N-(C1-C2 hydroxyalkyl) glucamine sulfates, and sulfates ofalkylpolysaccharides such as the sulfates of alkylpolyglucoside (the nonionicnonsulfated compounds being described herein).Alkyl sulfate surfactants are preferably selected from the linear and branched primaryC10-C13 alkyl sulfates, more preferably the C11-C15 branched chain alkyl sulfatesand the C12-C 14 linear chain alkyl sulfates.Alkyl ethoxysulfate surfactants are preferably selected from the group consisting ofthe C10-C13 alkyl sulfates which have been ethoxylated with from 0.5 to 20 molesof ethylene oxide per molecule. More preferably, the alkyl ethoxysulfate surfactantis a C1 1-C13, most preferably C11~C15 alkyl sulfate which has been ethoxylatedwith 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 preferredalkyl sulfate and alkyl ethoxysulfate surfactants. Such mixtures have been disclosedin PCT Patent Application No. W0 93/ 18124.CA 02264916 1999-03-05PCT/US97/ 15977W0 98/ 11185 24l01520253035Anionic Sulfonate SurfactantAnionic sulfonate surfactants suitable for use herein include the salts of C5-C20linear alkylbenzene sulfonates, alkyl ester sulfonates, C6-C22 primary or secondaryalkane sulfonates, C5-C24 olefin sulfonates, sulfonated polycarboxylic acids, alkylglycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfonates, andany mixtures thereof.Anionic Carboxylate SurfactantSuitable anionic carboxylate surfactants include the alkyl ethoxy carboxylates, thealkyl polyethoxy polycarboxylate surfactants and the soaps ('alkyl carboxyls'),especially certain secondary soaps as described herein.Suitable alkyl ethoxy carboxylates include those with the formula RO(CH2CH20)xCH2C00'M+ wherein R is a C5 to C13 alkyl group, x ranges from O to 10, and theethoxylate distribution is such that, on a weight basis, the amount of material where xis 0 is less than 20 % and M is a cation. Suitable alkyl polyethoxy polycarboxylatesurfactants include those having the formula R0-(CHR1-CHR2—O)-R3 wherein R isa C6 to C13 alkyl group, x is from 1 to 25, R1 and R2 are selected from the groupconsisting of hydrogen, methyl acid radical, succinic acid radical, hydroxysuccinicacid radical, and mixtures thereof, and R3 is selected from the group consisting ofhydrogen, substituted or unsubstituted hydrocarbon having between 1 and 8 carbonatoms, and mixtures thereof.Suitable soap surfactants include the secondary soap surfactants which contain acarboxyl unit connected to a secondary carbon. Preferred secondary soap surfactantsfor use herein are water-soluble members selected from the group consisting of thewater-soluble salts of 2-methy1—l-undecanoic acid, 2-ethyl-l-decanoic acid, 2-propyl-l-nonanoic acid, 2-butyl-I-octanoic acid and 2-pentyl-l-heptanoic acid. Certainsoaps 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 COOM, wherein R is a C 5-C17 linear or branched alkyl or alkenyl group,., ..,._........_......_...—_—.—.._.._.—..—-~—~»~ > "CA 02264916 1999-03-05PCT/US97/15977wo 93/11135 A 25l01520R1 is a C1-C4 alkyl group and M is an alkali metal ion. Preferred examples are themyristyl and oleoyl methyl sarcosinates in the form of their sodium salts.Amphoteric SurfactantSuitable amphoteric surfactants for use herein include the amine oxide surfactantsand the alkyl amphocarboxylic acids.Suitable amine oxides include those compounds having the formulaR3(OR4)xN0(R5)2 wherein R3 is selected from an alkyl, hydroxyalkyl,acylamidopropoyl and alkyl phenyl group, or mixtures thereof, containing from 8 to26 carbon atoms; R4 is an alkylene or hydroxyalkylene group containing from 2 to 3carbon atoms, or mixtures thereof; x is from O to 5, preferably from 0 to 3; and eachR5 is an alkyl or hydroxyalkyl group containing from 1 to 3, or a polyethylene oxidegroup containing from 1 to 3 ethylene oxide groups. Preferred are C10-C13 alkyldimethylamine oxide, and C10_1g acylamido alkyl dimethylamine oxide.A suitable example of an alkyl aphodicarboxylic acid is Miranol(TM) C2M Conc.manufactured by Miranol, Inc., Dayton, NJ.10152025W0 98/11185CA 02264916 1999-03-05PCT/US97/15977Zwitterionic SurfactantZwitterionic surfactants can also be incorporated into the detergent compositionshereof. These surfactants can be broadly described as derivatives of secondary andtertiary amines, derivatives of heterocyclic secondary and tertiary amines, orderivatives of quaternary ammonium, quatemaiy phosphonium or tertiary sulfoniumcompounds. Betaine and sultaine surfactants are exemplary zwitterionic surfactantsfor use herein.Suitable betaines are those compounds having the formula R(R')2N+R2COO'wherein R is a C6-C18 hydrocarbyl group, each R1 is typically C 1-C3 alkyl, and R2is a C 1 -C 5 hydrocarbyl group. Preferred betaines are C12_1g dimethyl-arnmoniohexanoate and the C10-1 3 acylarnidopropane (or ethane) dimethyl (or diethyl)betaines. Complex betaine surfactants are also suitable for use herein.Cationic SurfactantsCationic ester surfactants used in this invention are preferably water dispersiblecompound having surfactant properties comprising at least one ester (i.e. -COO-)linkage and at least one cationically charged group. Other suitable cationic estersurfactants, including choline ester surfactants, have for example been disclosed inUS Patents No.5 4228042, 4239660 and 4260529.Suitable cationic surfactants include the quaternary ammonium surfactants selectedfrom mono C6-C15, preferably C6-C10 N-alkyl or alkenyl ammonium surfactantswherein the remaining N positions are substituted by methyl, hydroxyethyl orhydroxypropyl groups.20253035W0 98/ l 1 185CA 02264916 1999-03-05PCTfUS97/ 159772 7EnzymesThe detergent compositions described herein may comprise an enzyme. Saidenzymes include enzymes selected from cellulases, hemicellulases, peroxidases,proteases, gluco-amylases, amylases, xylanases, lipases, phospholipases, esterases,cutinases, pectinases, keratanases, reductases, oxidases, phenoloxidases,lipoxygenases, ligninases, pullulanases, tannases, pentosanases, malanases, I3-glucanases, arabinosidases, hyaluronidase, chondroitinase, Iaccase or mixturesthereof.A preferred combination is a cleaning composition having cocktail of conventional.applicable enzymes like protease, amylase, lipase, cutinase and/or cellulase inconjunction with one or more plant cell wall degrading enzymes.The cellulases usable in the present invention include both bacterial or fungalcellulase. Preferably, they will have a pH optimum of between 5 and 12 and anactivity above 50 CEVU (Cellulose Viscosity Unit). Suitable cellulases are disclosedin U.S. Patent 4,435,307, Barbesgoard et al, 161078384 and W096/02653 whichdisclose fimgal cellulases produced respectively from Humicola insolens,Trichoderma, Thielavia and Sporotrichum. EP 739 982 describes cellulases isolatedfi'om novel Bacillus species. Suitable cellulases are also disclosed in GB-A-2.075.028; GB-A-2.095.275; DE-OS-2.247.832 and W095/26398.Examples of such cellulases are cellulases produced by a strain of Humicola insolens(Humicola grisea var. therrnoidea), particularly the Humicola strain DSM 1800.Other suitable cellulases are cellulases originated from Humicola insolens having amolecular weight of about 5OKDa, an isoelectric point of 5.5 and containing 415amino acids; and a "43kD endoglucanase derived from Humicola insolens, DSM1800, exhibiting cellulase activity; a preferred endoglucanase component has theamino acid sequence disclosed in PCT Patent Application No. W0 91/ 1 7243. Alsosuitable cellulases are the EGIII cellulases from Trichoderma longibrachiatumdescribed in W094/21801, Genencor, published September 29, 1994. Especiallysuitable cellulases are the cellulases having color care benefits. Examples of suchcellulases are cellulases described in European patent application No. 912028792,filed November 6, 1991 (Novo). Carezyme and Celluzyme (Novo Nordisk A/S) areespecially useful. See also W091/17244 and W091/21801. Other suitable cellulasesl01520253035W0 98/11185 28CA 02264916 1999-03-05PCTIUS97/15977for fabric care and/or cleaning properties are described in WO96/ 34092,W096/17994 and W095/24471.Said cellulases are normally incorporated in the detergent composition at levels from0.0001% to 2% of active enzyme by weight of the detergent composition.Peroxidase enzymes are used in combination with oxygen sources, e.g. percarbonate,perborate, persulfate, hydrogen peroxide, etc. They are used for "solution bleaching",i.e. to prevent transfer of dyes or pigments removed from substrates during washoperations to other substrates in the wash solution. Peroxidase enzymes are known inthe art, and include, for example, horseradish peroxidase, ligninase andhaloperoxidase such as chloro- and bromo-peroxidase. Peroxidase-containingdetergent compositions are disclosed, for example, in PCT International ApplicationWO 89/099813, W089/09813 and in European Patent application EP No. 4912028826, filed on November 6, 1991 and EP No. 968700138, filed February 20,1996. Also suitable is the laccase enzyme.Preferred enhancers are substitued phenthiazine and phenoxasine 10-Phenothiazinepropionicacid (PPT), 10-ethylphenothiazine-4-carboxylic acid (EPC),10-phenoxazinepropionic acid (POP) and 10-methylphenoxazine (described in W094/ 12621) and substitued syringates (C3-C5 substitued alkyl syringates) and phenols.Sodium percarbonate or perborate are preferred sources of hydrogen peroxide.Said cellulases and/or peroxidases are normally incorporated in the detergentcomposition at levels from 0.0001% to 2% of active enzyme by weight of thedetergent composition.Other preferred enzymes that can be included in the detergent compositions of thepresent invention include lipases. Suitable lipase enzymes for detergent usage includethose produced by microorganisms of the Pseudomonas group, such as Pseudomonasstutzeri ATCC 19.154, as disclosed in British Patent 1,372,034. Suitable lipasesinclude those which show a positive immunological cross-reaction with the antibodyof the lipase, produced by the microorganism Pseudomonas fluorescent IAM 1057.This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, underthe trade name Lipase P "Amano," hereinafter referred to as "Amano-P". Othersuitable commercial lipases include Amano-CES, lipases ex Chromobacter viscosum,CA 02264916 1999-03-05PCT/US97/1 5977W0 98/1 1 185 29I020253035e.g. Chromobacter viscosum var. lipolyticum NRRLB 3673 from Toyo Jozo Co.,Tagata, Japan; Chromobacter viscosum lipases from U.S. Biochemical Corp., U.S.A.and Disoynth Co., The Netherlands, and lipases ex Pseudomonas gladioli. Especiallysuitable lipases are lipases such as M1 LipaseR and LipomaxR (Gist-Brocades) andLipolaseR and Lipolase UltraR(Novo) which have found to be very effective whenused in combination with the compositions of the present invention. Also suitablesare the lipolytic enzymes described in EP 258 068, WO 92/05249 and WO 95/22615by Novo Nordisk and in WO 94/03578, WO 95/35381 and WO 96/00292 byUnilever.Also suitable are cutinases [EC 3.1.1.50] which can be considered as a special kindof lipase, namely lipases which do not require interfacial activation. Addition ofcutinases to detergent compositions have been described in e. g. WO—A-88/09367(Genencor); WO 90/09446 (Plant Genetic System) and W0 94/ 14963 and W094/ 14964 (Unilever).The lipases and/or cutinases are normally incorporated in the detergent compositionat levels from 0.000l% to 2% of active enzyme by weight of the detergentcomposition./ Suitable proteases are the subtilisins which are obtained from particular strains of B.subtilis and B. licheniformis (subtilisin BPN and BPN'). One suitable protease isobtained from a strain of Bacillus, having maximum activity throughout the pH rangeof 8-12, developed and sold as ESPERASE® by Novo Industries N8 of Denmark,hereinafter "Novo". The preparation of this enzyme and analogous enzymes isdescribed in GB 1,243,784 to Novo. Other suitable proteases include ALCALASE®,DURAZYM® and SAVINASE® from Novo and MAxATAs13®, MAXACAL®,PROPERASE® and MAXAPEM® (protein engineered Maxacal) from Gist-Brocades. Proteolytic enzymes also encompass modified bacterial serine proteases,such as those described in European Patent Application Serial Number 87 303761 .8,filed April 28, 1987 (particularly pages 17, 24 and 98), and which is called herein"Protease B", and in European Patent Application 199,404, Venegas, publishedOctober 29, 1986, which refers to a modified bacterial serine protealytic enzymewhich is called "Protease A" herein. Suitable is what is called herein "Protease C",which is a variant of an alkaline serine protease from Bacillus in which lysinereplaced arginine at position 27, tyrosine replaced valine at position 104, serineCA 02264916 1999-03-05PCT/US97I15977W0 98/11185 30101520253035replaced asparagine at position 123, and alanine replaced threonine at position 274.Protease C is described in EP 909l5958:4. corresponding to W0 91/06637,Published May 16, 1991. Genetically modified variants, particularly of Protease C,are also included herein.A preferred protease referred to as "Protease D" is a carbonyl hydrolase varianthaving an amino acid sequence not found in nature, which is derived from aprecursor carbonyl hydrolase by substituting a different amino acid for a plurality ofamino acid residues at a position in said carbonyl hydrolase equivalent to position+76, preferably also in combination with one or more amino acid residue positionsequivalent to those selected from the group consisting of +99, +101, +103, +104,+107, +123, +27, +105, +109, +126, +128, +135, +156, +166, +195, +197, +204,+206, +210, +216, +217, +218, +222, +260, +265, and/or +274 according to thenumbering of Bacillus amyloliquefaciens subtilisin, as described in W095/ 10591 andin the patent application of C. Ghosh, et al, "Bleaching Compositions ComprisingProtease Enzymes" having US Serial No. 08/322,677, filed October 13, 1994.Also suitable for the present invention are proteases described in patent applicationsEP 251 446 and W0 91/0663 7, protease BLAP® described in W091/02792 and theirvariants described in W0 95/23221.See also a high pH protease from Bacillus sp. NCIMB 40338 described in W093/ 1 8140 A to Novo. Enzymatic detergents comprising protease, one or more otherenzymes, and a reversible protease inhibitor are described in W0 92/03 529 A toNovo. When desired, a protease having decreased adsorption and increasedhydrolysis is available as described in W0 95/07791 to Procter & Gamble. Arecombinant trypsin-like protease for detergents suitable herein is described in W094/25583 to Novo. Other suitable proteases are described in EP 516 200 by Unilever.The proteolytic enzymes are incorporated in the detergent compositions of thepresent invention a level of from 0.000l% to 2%, preferably from 0.001% to 0.2%,more preferably from 0.005% to 0.1% pure enzyme by weight of the composition.Amylases (on and/or 13) can be included for removal of carbohydrate-based stains.W094/02597, Novo Nordisk A/ S published February 03, 1994, describes cleaningcompositions which incorporate mutant amylases. See also W095/ 10603, Novo15203035WO 98/11185CA 02264916 1999-03-053 1 PCT/U S97/ 15977Nordisk A/S, published April 20, 1995. Other amylases known for use in cleaningcompositions include both a- and [3-amylases. on-Amylases are known in the art andinclude those disclosed in US Pat. no. 5,003,257; EP 252,666; W0/91/00353; FR2,676,456; EP 285,123; EP 525,610; EP 368,341; and BritishiPatent specification no.1,296,839 (Novo). Other suitable amylases are stability-enhanced amylases describedin W094/18314, published August 18, 1994 and W096/05295, Genencor, publishedFebruary 22, 1996 and amylase variants having additional modification in theimmediate parent available from Novo Nordisk A/S, disclosed in W0 95/ 10603,published April 95. Also suitable are amylases described in EP 277 216,W095/26397 and W096/23873 (all by Novo Nordisk).Examples of commercial ot—amylases products are Purafect Ox Am® from Genencorand Terrnamyl®, Ban® ,Fungamyl® and Duramyl®, all available from NovoNordisk A/S Denmark. WO95/26397 describes other suitable amylases : on-amylasescharacterised by having a specific activity at least 25% higher than the specificactivity of Termamyl® at a temperature range of 25°C to 55°C and at a pH value inthe range of 8 to 10, measured by the Phadebas® ot-amylase activity assay. Suitableare variants of the above enzymes, described in W096/23 873 (Novo Nordisk). Otheramylolytic enzymes with improved properties with respect to the activity level andthe combination of thermostability and a higher activity level are described inW095/35382.The amylolytic enzymes are incorporated in the detergent compositions of thepresent invention a level of from 0.0001% to 2%, preferably from 0.00018% to0.06%, more preferably from 0.00024% to 0.048% pure enzyme by weight of thecomposition.The above-mentioned enzymes may be of any suitable origin, such as vegetable,animal, bacterial, fungal and yeast origin. Origin can further be mesophilic orextremophilic (psychrophilic, psychrotrophic, thermophilic, barophilic, alkalophilic,acidophilic, halophilic, etc.). Purified or non-purified forms of these enzymes may beused. Also included by definition, are mutants of native enzymes. Mutants can beobtained e.g. by protein and/or genetic engineering, chemical and/or physicalmodifications of native enzymes. Common practice as well is the expression of theenzyme via host organisms in which the genetic material responsible for theproduction of the enzyme has been cloned.CA 02264916 1999-03-05PCT/U S97/ 15977W0 98/11185 32102025Said enzymes are normally incorporated in the detergent composition at levels from0,0001% to 2% of active enzyme by weight of the detergent composition. Theenzymes can be added as separate single ingredients (prills, granulates, stabilizedliquids, etc... containing one enzyme ) or as mixtures of two or more enzymes ( e.g.cogranulates ).Other suitable detergent ingredients that can be added are enzyme oxidationscavengers which are described in Copending European Patent application92870018.6 filed on January 31, 1992. Examples of such enzyme oxidationscavengers are ethoxylated tetraethylene polyamines.A range of enzyme materials and means for their incorporation into syntheticdetergent compositions is also disclosed in W0 9307263 A and WO 9307260 A to AGenencor International, WO 8908694. A to Novo, and U.S. 3,553,139, January 5,1971 to McCarty et al. Enzymes are further disclosed in U.S. 4,101,457, Place et al,July 18, 1978, and in U.S. 4,507,219, Hughes, March 26, 1985. Enzyme materialsuseful for liquid detergent formulations, and their incorporation into suchformulations, are disclosed in U.S. 4,261,868, Hora et al, April 14, 1981. Enzymesfor use in detergents can be stabilised by various techniques. Enzyme stabilisationtechniques are disclosed and exemplified in U.S. 3,600,319, August 17, 1971, Gedgeet al, EP 199,405 and EP 200,586, October 29, 1986, Venegas. Enzyme stabilisationsystems are also described, for example, in U.S. 3,519,570. A useful Bacillus, sp.AC13 giving proteases, xylanases and cellulases, is described in WO 9401532 A toNovo.W0 98/11185I015203035CA 02264916 1999-03-053 3 PCT/U S97/ 15977Bleaching AgentA highly preferred component of the detergent composition is a bleaching agent.Suitable bleaching agents include chlorine and oxygen-releasing bleaching agents.In one preferred aspect the oxygen-releasing bleaching agent contains a hydrogenperoxide source and an organic peroxyacid bleach precursor compound. Theproduction of the organic peroxyacid occurs by an in situ reaction of the precursorwith a source of hydrogen peroxide. Preferred sources of hydrogen peroxide includeinorganic perhydrate bleaches. In an alternative preferred aspect a preformed organicperoxyacid is incorporated directly into the composition. Compositions containingmixtures of a hydrogen peroxide source and organic peroxyacid precursor incombination with a preformed organic peroxyacid are also envisaged.Inorganic Perhydrate BleachesThe compositions in accord with the invention preferably include a hydrogenperoxide source, as an oxygen-releasing bleach. Suitable hydrogen peroxide sourcesinclude the inorganic perhydrate salts.The inorganic perhydrate salts are normally incorporated in the form of the sodiumsalt at a level of from 1% to 40% by weight, more preferably from 2% to 30% byweight and most preferably from 5% to 25% by weight of thecompositions.Examples of inorganic perhydrate salts include perborate, percarbonate,perphosphate, persulfate and persilicate salts. The inorganic perhydrate salts arenormally the alkali metal salts. The inorganic perhydrate salt may be included as thecrystalline solid without additional protection. For certain perhydrate salts however,the preferred executions of such granular compositions utilize a coated form of thematerial which provides better storage stability for the perhydrate salt in the granularproduct.Sodium perborate can be in the form of the monohydrate of nominal formulaNaBO2H2O2 or the tetrahydrate NaBO2H2O2.3H2O.W0 98/11 1851015203035CA 02264916 1999-03-05PCTIUS97/15977Alkali metal percarbonates, particularly sodium percarbonate are preferredperhydrates for inclusion in compositions in accordance with the invention. Sodiumpercarbonate is an addition compound having a formula corresponding to2Na2CO3.3I-I202, and is available commercially as a crystalline solid. Sodiumpercarbonate, being a hydrogen peroxide addition compound tends on dissolution torelease the hydrogen peroxide quite rapidly which can increase the tendency forlocalised high bleach concentrations to arise. The percarbonate is most preferablyincorporated into such compositions in a coated form which provides in-productstability.A suitable coating material providing in product stability comprises mixed salt of awater soluble alkali metal sulphate and carbonate. Such coatings together withcoating processes have previously been described in GB-1,466,799, granted toInterox on 9th March 1977. The weight ratio of the mixed salt coating material topercarbonate lies in the range from 1 : 200 to 1 : 4, more preferably from 1 : 99 to 1 :9, and most preferably from 1 : 49 to 1 : 19. Preferably, the mixed salt is of sodiumsulphate and sodium carbonate which has the general formula Na2SO4.n.Na2CO3wherein n is from 0.1 to 3, preferably n is from 0.3 to 1.0 and most preferably n isfrom 0.2 to 0.5.Another suitable coating material providing in product stability, comprises sodiumsilicate of SiO2 :Na2O ratio from 1.8 2 1 to 3.0 : 1, preferably 1.8:] to 2.4:1, and/orsodium metasilicate, preferably applied at a level of from 2% to 10%, (normally from3% to 5%) of SiO2 by weight of the inorganic perhydrate salt. Magnesium silicatecan also be included in the coating. Coatings that contain silicate and borate salts orboric acids or other inorganics are also suitable.Other coatings which contain waxes, oils, fatty soaps can also be usedadvantageously within the present invention.Potassium peroxymonopersulfate is another inorganic perhydrate salt of utility in thecompositions herein.Peroxvacid Bleach PrecursorW0 98/1 I 18510152530CA 02264916 1999-03-05PCT/US97/159773 5Peroxyacid bleach precursors are compounds which react with hydrogen peroxide ina perhydrolysis reaction to produce a peroxyacid. Generally peroxyacid bleachprecursors may be represented asOX-C—Lwhere L is a leaving group and X is essentially any functionality, such that onperhydrolysis the structure of the peroxyacid produced isOX- CeOOHPeroxyacid bleach precursor compounds are preferably incorporated at a level offrom 0.5% to 20% by weight, more preferably from 1% to 10% by weight, mostpreferably from 1.5% to 5% by weight of the compositions.Suitable peroxyacid bleach precursor compounds typically contain one or more N- orO-acyl groups, which precursors can be selected from a wide range of classes.Suitable classes include anhydrides, esters, imides, lactams and acylated derivativesof imidazoles and oximes. Examples of useful materials within these classes aredisclosed in GB-A-1586789. Suitable esters are disclosed in GB-A-836988, 864798,1147871, 2143231 and EP-A-0170386.Leaving GroupsThe leaving group, hereinafter L group, must be sufficiently reactive for theperhydrolysis reaction to occur within the optimum time frame (e.g., a wash cycle).However, if L is too reactive, this activator will be difficult to stabilise for use in ableaching composition.Preferred L groups are selected from the group consisting of:20W0 98/1 1 185CA 02264916 1999-03-05PCT/US97ll597736——ITl—C—R‘ , —N N —rT1——c.—cl;H__R4If —— ' R3 Y 'YR3 Yi.’ Y E?Q -H CH2 c\ 4 _N >—c\NR4"O—C-‘R1 N\CJNR $C/ v' n no o‘$3 T-0-C=CHR“ ,and -—l?l—%-—CH-R4R3 0and mixtures thereof, wherein R1 is an alkyl, aryl, or alkaryl group containing from 1to 14 carbon atoms, R3 is an alkyl chain containing from 1 to 8 carbon atoms, R4 isH or R3, R5 is an alkenyl chain containing from 1 to 8 carbon atoms and'Y is H or asolubilizing group. Any of R1, R3 and R4 may be substituted by essentially anyfunctional group including, for example alkyl, hydroxy, alkoxy, halogen, amine,nitrosyl, amide and ammonium or alkyl ammonium groups.The preferred solubilizing groups are -SO3_M+, -CO2'M+, -SO4'M+, -N+(R3)4X'and O<--N(R3)3 and most preferably -SO3'M+ and -CO2-M+ wherein R3 is an alkylchain containing from l to 4 carbon atoms, M is a cation which provides solubility tothe bleach activator and X is an anion which provides solubility to the bleachactivator. Preferably, M is an alkali metal, ammonium or substituted ammoniumcation, with sodium and potassium being most preferred, and X is a halide,hydroxide, methylsulfate or acetate anion.l01520W0 98/1 1 185CA 02264916 1999-03-05PCT/US97I1597737Perbenzoic Acid PrecursorPerbenzoic acid precursor compounds provide perbenzoic acid on perhydrolysis.Suitable O-acylated perbenzoic acid precursor compounds include the substituted andunsubstituted benzoyl oxybenzene sulfonates, including for example benzoyloxybenzene sulfonate:OO’@S°3'Also suitable are the benzoylation products of sorbitol, glucose, and all saccharides Vwith benzoylating agents, including for example:OAcACO 0OAcOAcOBzAc = COCH3; B2 = BenzoylPerbenzoic acid precursor compounds of the imide type include N-benzoylsuccinimide, tetrabenzoyl ethylene diamine and the N-benzoyl substituted ureas.Suitable imidazole type perbenzoic acid precursors include N-benzoyl imidazole andN-benzoyl benzimidazole and other useful N-acyl group-containing perbenzoic acidprecursors include N-benzoyl pyrrolidone, dibenzoyl taurine and benzoylpyroglutamic acid.CA 02264916 1999-03-05PCT/U S97/ 15977wo 98/11185 38l0152025Other perbenzoic acid precursors include the benzoyl diacyl peroxides, the benzoyltetraacyl peroxides, and the compound having the formula:0 33o0 0/\/\COOHPhthalic anhydride is another suitable perbenzoic acid precursor compound herein:0O0Suitable N-acylated lactam perbenzoic acid precursors have the formula:‘H’C”) l-CH2-CH2R6—c—N\C Hg-{-CH2 inwherein n is from 0 to 8, preferably from 0 to 2, and R6 is a benzoyl group.Perbenzoic Acid Derivative PrecursorsPerbenzoic acid derivative precursors provide substituted perbenzoic acids onperhydrolysis.Suitable substituted perbenzoic acid derivative precursors include any of the hereindisclosed perbenzoic precursors in which the benzoyl group is substituted byessentially any non—positively charged (i.e.; non-cationic) functional group including,for example alkyl, hydroxy, alkoxy, halogen, amine, nitrosyl and amide groups.___ __~__...._,..... ...........................-..._—--——~-- -"W0 98/11 18515202530CA 02264916 1999-03-05PCT/U S97! 159773 9A preferred class of substituted perbenzoic acid precursor compounds are the amidesubstituted compounds of the following general formulae:R1———cFN~~R2~-c~—L R1~-N~—C——R2—-C——Lo R5 0 or R5 o 0wherein R1 is an aryl or alkaryl group with from 1 to 14 carbon atoms, R2 is anarylene, or alkarylene group containing from 1 to 14 carbon atoms, and R5 is H or analkyl, aryl, or alkaryl group containing 1 to 10 carbon atoms and L can be essentiallyany leaving group. R1 preferably contains from 6 to 12 carbon atoms. R2preferably contains from 4 to 8 carbon atoms. R1 may be aryl, substituted aryl oralkylaryl containing branching, substitution, or both and may be sourced from eithersynthetic sources or natural sources including for example, tallow fat. Analogousstructural variations are permissible for R2. The substitution can include alkyl, aryl,halogen, nitrogen, sulphur and other typical substituent groups or organiccompounds. R5 is preferably H or methyl. R1 and R5 should not contain morethan 18 carbon atoms in total. Amide substituted bleach activator compounds of thistypeare described in EP-A-01 703 86.Cationic Peroxvacid PrecursorsCationic erox acid recursor com ounds produce cationic erox acids onP Y P P P Yperhydrolysis.Typically, cationic peroxyacid precursors are formed by substituting the peroxyacidpart of a suitable peroxyacid precursor compound with a positively chargedfunctional group, such as an ammonium or alkyl ammonium group, preferably anethyl or methyl ammonium group. Cationic peroxyacid precursors are typicallypresent in the compositions as a salt with a suitable anion, such as for example ahalide ion or a methylsulfate ion.The peroxyacid precursor compound to be so cationically substituted may be aperbenzoic acid, or substituted derivative thereof. precursor compound as describedhereinbefore. Alternatively, the peroxyacid precursor compound may be an alkyl W0 98/1118510152025CA 02264916 1999-03-05PCT/US97/ 1597740percarboxylic acid precursor compound or an amide substituted alkyl peroxyacidprecursor as described hereinafterCationic peroxyacid precursors are described in U.S. Patents 4,904,406; 4,751,015;4,988,451; 4,397,757; 5,269,962; 5,127,852; 5,093,022; 5,106,528; U.K. 1,382,594;EP 475,512, 458,396 and 284,292; and in JP 87—318,332.Suitable cationic peroxyacid precursors include any of the ammonium or alkylammonium substituted alkyl or benzoyl oxybenzene sulfonates, N-acylatedcaprolactams, and monobenzoyltetraacetyl glucose benzoyl peroxides.A preferred cationically substituted benzoyl oxybenzene sulfonate is the 4-(trimethylammonium) methyl derivative of benzoyl oxybenzene sulfonate:Oo@s0s‘+/\A preferred cationically substituted alkyl oxybenzene sulfonate has the formula:Preferred cationic peroxyacid precursors of the N-acylated caprolactam class includethe trialkyl ammonium methylene benzoyl caprolactams, particularly trimethylammonium methylene benzoyl caprolactam:\\ :Q§/N-\/\/CA 02264916 1999-03-05W0 98ll1185 PCT/US97l1597741Other preferred cationic peroxyacid precursors of the N—acylated caprolactam classinclude the trialkyl ammonium methylene alkyl caprolactams:where n is from 0 to 12, particularly from 1 to 5.Another preferred cationic peroxyacid precursor is 2-(N,N,N-trimethyl ammonium)ethyl sodium 4-sulphophenyl carbonate chloride.W0 98/11185l0l5202530CA 02264916 1999-03-05PCT/US97l1597742Alfll Percarboxylic Acid Bleach PrecursorsAlkyl percarboxylic acid bleach precursors form percarboxylic acids onperhydrolysis. Preferred precursors of this type provide peracetic acid onperhydrolysis.Preferred alkyl percarboxylic precursor compounds of the imide type include the N-,N,N1N1 tetra acetylated alkylene diamines wherein the alkylene group containsfrom 1 to 6 carbon atoms, particularly those compounds in which the alkylene groupcontains 1, 2 and 6 carbon atoms. Tetraacetyl ethylene diamine (TAED) isparticularly preferred.Other preferred alkyl percarboxylic acid precursors include sodium 3,5,5-tri-methylhexanoyloxybenzene sulfonate (iso-NOBS), sodium nonanoyloxybenzene sulfonate(N OBS), sodium acetoxybenzene sulfonate (ABS) and penta acetyl glucose.Amide Substituted Alkyl Peroxyacid PrecursorsAmi-de substituted alkyl peroxyacid precursor compounds are also suitable, includingthose of the following general formulae:Rl~I§i~—p-——R2——fi—-Li |i lR50 0R1—c—~N~—R2——c——L5ii R5 Q orwherein R1 is an alkyl group with from 1 to 14 carbon atoms, R2 is an alkylenegroup containing from 1 to 14 carbon atoms, and R5 is H or an alkyl groupcontaining 1 to 10 carbon atoms and L can be essentially any leaving group. R1preferably contains from 6 to 12 carbon atoms. R2 preferably contains from 4 to 8carbon atoms. R1 may be straight chain orbranched alkyl containing branching,substitution, or both and may be sourced from either synthetic sources or naturalsources including for example, tallow fat. Analogous structural variations arepermissible for R2. The substitution can include alkyl, halogen, nitrogen, sulphurand other typical substituent groups or organic compounds. R5 is preferably H ormethyl. R1 and R5 should not contain more than 18 carbon atoms in total. Amidesubstituted bleach activator compounds of this type are described in EP-A-01703 86.CA 02264916 1999-03-05WO 98/11185 PCT/US97/15977Benzoxazin Organic Peroxyacid PrecursorsAlso suitable are precursor compounds of the benzoxazin-type, as disclosed for5 example in EP-A—332,294 and EP-A-482,807, particularly those having the formula:0IIc\?,/C—R1Nincluding the substituted benzoxazins of the type10wherein R1 is H, alkyl, alkaryl, aryl, arylalkyl, and wherein R2, R3, R 4, and R5 maybe the same or different substituents selected from H, halogen, alkyl, alkenyl, aryl,hydroxyl, alkoxyl, amino, alkyl amino, COOR6 (wherein R6 is H or an-alkyl group)15 and carbonyl ftmctions.An especially preferred precursor of the benzoxazin-type is:ouC\©I,a5©Preformed Organic Peroxvacid20The organic peroxyacid bleaching system may contain, in addition to, or as analternative to, an organic peroxyacid bleach precursor compound, a preformed_ ., ,..M_......_.:.._...—.._-.—.___....i.._ . .,CA 02264916 1999-03-05PCT/U S97/ 1597 7W0 98/11185 44l5202530organic peroxyacid , typically at a level of from 0.5% to 25% by weight, morepreferably from 1% to 10% by weight of the composition.A preferred class of organic peroxyacid compounds are the amide substitutedcompounds of the following general formulae:R1—~c-N—~R2——c-ooHo R5 o MR1»-N-c«~R2—~c——ooHR5 o 0wherein R1 is an alkyl, aryl or alkaryl group with from 1 to 14 carbon atoms, R2 isan alkylene, arylene, and alkarylene group containing from 1 to 14 carbon atoms, andR5 is H or an alkyl, aryl, or alkaryl group containing 1 to 10 carbon atoms. R1preferably contains from 6 to 12 carbon atoms. R2 preferably contains from 4 to 8carbon atoms. R1 may be straight chain or branched alkyl, substituted aryl oralkylaiyl containing branching, substitution, or both and may be sourced from eithersynthetic sources or natural sources including for example, tallow fat. Analogousstructural variations are permissible for R2. The substitution can include alkyl, aryl,halogen, nitrogen, sulphur and other typical substituent groups or organiccompounds. R5 is preferably H or methyl. R1 and R5 should not contain morethan 18 carbon atoms in total. Amide substituted organic peroxyacid compounds ofthis type are described in EP-A-01 703 86.Other organic peroxyacids include diacyl and tetraacylperoxides, especiallydiperoxydodecanedioc acid, diperoxytetradecanedioc acid, anddiperoxyhexadecanedioc acid. Dibenzoyl peroxide is a preferred organic peroxyacidherein. Mono- and diperazelaic acid, mono- and diperbrassylic acid, and N-phthaloylaminoperoxicaproic acid are also suitable herein.Metal-Containing Bleach CatalystCompositions comprising a bleach described herein may additionally contain a metalcontaining bleach catalyst as a preferred component. Preferably the metal containingWO 98/11185101520253035CA 02264916 1999-03-05PCT/US97/1597745bleach catalyst is a transition metal containing bleach catalyst, more preferably amanganese or cobalt-containing bleach catalyst.A suitable type of bleach catalyst is a catalyst comprising a heavy metal cation ofdefined bleach catalytic activity, such as copper, iron cations, an auxiliary metalcation having little or no bleach catalytic activity, such as zinc or aluminium cations,and a sequestrant having defined stability constants for the catalytic and auxiliarymetal cations, particularly ethylenediaminetetraacetic acid,ethylenediaminetetra(methylenephosphonic acid) and water-soluble salts thereof.Such catalysts are disclosed in U.S. Pat. 4,430,243.Preferred types of bleach catalysts include the manganese-based complexes disclosedin U.S. Pat. 5,246,621 and U.S. Pat. 5,244,594. Preferred examples of thesecatalysts include MnIV2(u-O)3(1,4,7-trimethyl-1,4,7-triazacyclononane)2-(PF6)2,Mn1H2(u-O)1(u-OAc)2(l ,4,7-trimethyl-1 ,4,7-triazacyclononane)2-(ClO4)2,MnIV4(u-O)6(1.,4,7-triazacyclononane)4-(ClO4)2, MnmMnIV4(u~O)1(u-OAc)2_(1,4,7-trimethyl-l,4,7-triazacyclononane)2-(ClO4)3, and mixtures thereof. Othersare described in European patent application publication no. 549,272. Other ligandssuitable for use herein include 1,5,9—trimethy1-1,5,9-triazacyclododecane, 2—methy1-1,4,7-triazacyclononane, 2-methyl-1 ,4,7-triazacyclononane, l,2,4,7-tetramethyl-1,4,7-triazacyclononane, and mixtures thereof.The bleach catalysts useful in the compositions herein may also be selected asappropriate for the present invention. For examples of suitable bleach catalysts seeU.S. Pat. 4,246,612 and U.S. Pat. 5,227,084. See also U.S. Pat. 5,194,416 whichteaches mononuclear manganese (IV) complexes such as Mn(1,4,7-trimethyl-1,4,7-triazacyc1ononane)(OCI-13)3_(PF5).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.202530WO 98/11185 g 46CA 02264916 1999-03-05PCT/U S9 7/ 15977U.S. Pat. 5,114,611 teaches a bleach catalyst comprising a complex of transitionmetals, including Mn, Co, Fe, or Cu, with an non—(macro)—cyclic ligand. Saidligands are of the formula:R2 R3R1-N=C-B—C=N—R4wherein R1, R2, R3, and R4 can each be selected from H, substituted alkyl and arylgroups such that each R1-N=C-R2 and R3-C=N-R4 form a five or six-memberedring. Said ring can further be substituted. B is a bridging group selected from O, S.CRSR6, 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, pyrimidine, 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, F e,-bispyridylmethane and -bispyridylamine complexes. Highly preferred catalysts include Co(2,2'-bisp_yridylamine)C12, Di(isothiocyanato)bispyridylamine-cobalt (II),trisdipyridylamine-coba1t(II) perchlorate, Co(2,2-bispyridylamine)2O2ClO4, Bis-(2,2'-bispyridylamine) copper(lI) perchlorate, tris(di-2-pyridylamine) iron(Il)perchlorate, and mixtures thereof.Preferred examples include binuclear Mn complexes with tetra-N-dentate and bi-N-dentate ligands, including N4MnHI(u-O)2MnIVN4)+and [Bipy2Mnm(u-o>2Mn1Vbipy21-<c1o4>3.While the structures of the bleach-catalyzing manganese complexes of thepresent invention have not been elucidated, it may be speculated that theycomprise chelates or other hydrated coordination complexes which resultfrom the interaction of the carboxyl and nitrogen atoms of the ligand withthe manganese cation. Likewise, the oxidation state of the manganesecation during the catalytic process is not known with certainty, and may bethe (+11), (+III), (+IV) or (+V) valence state. Due to the ligands‘ possiblesix points of attachment to the manganese cation, it may be reasonablyspeculated that multi-nuclear species and/or "cage" structures may exist inCA 02264916 1999-03-05PCT/US97/15977wo 98/11185 471015203035the aqueous bleaching media. Whatever the form of the active Mn-ligandspecies which actually exists, it functions in an apparently catalytic mannerto provide improved bleaching perfonnances on stubborn stains such astea, ketchup, coffee, wine, juice, and the like.Other bleach catalysts are described, for example, in European patentapplication, publication no. 408,131 (cobalt complex catalysts), Europeanpatent applications, publication nos. 384,503, and 306,089 (meta1lo-porphyrin catalysts), US. 4,728,455 (manganese/multidentate ligandcatalyst), 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 ormagnesium 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 86_6,191 (transition metal-containingsalts), U.S. 4,430,243 (chelants with manganese cations and non-catalyticmetal cations), and U.S. 4,728,455 (manganese gluconate catalysts).Other preferred examples include cobalt (III) catalysts having the formula:C0l(NH3)nM'mB'bT'tQqPp] Yywherein cobalt is in the +3 oxidation state; n is an integer from 0 to 5(preferably 4 or 5; most preferably 5); M’ represents a monodentate ligand;m is an integer from 0 to 5 (preferably 1 or 2’; most preferably 1); B’represents a bidentate ligand; b is an integer from 0 to 2; T‘ represents atridentate ligand; t is 0 or 1; Q is a tetradentate ligand; q is 0 or 1; P is apentadentate ligand; p is 0 or 1; and n + m + 2b + 3t + 4q + 5p = 6; Y isone or more appropriately selected counteranions present in a number y,where y is an integer from 1 to 3 (preferably 2 to 3; most preferably 2when Y is a -1 charged anion), to obtain a charge-balanced salt, preferredY are selected from the group consisting of chloride, nitrate, nitrite,sulfate, citrate, acetate, carbonate, and combinations thereof; and whereinfurther at least one of the coordination sites attached to the cobalt is labileunder automatic dishwashing use conditions and the remaining co-ordination sites stabilise the cobalt under automatic dishwashingW0 98/11185I01520253035CA 02264916 1999-03-05PCT/US97/ 1597748conditions such that the reduction potential for cobalt (III) to cobalt (11)under alkaline conditions is less than about 0.4 volts (preferably less thanabout 0.2 volts) versus a nonnal hydrogen electrode.Preferred cobalt catalysts of this type have the formula:[co<NH3>n<M'>m1 Yywherein n is an integer from 3 to 5 (preferably 4 or 5; most preferably 5);M’ is a labile coordinating moiety, preferably selected from the groupconsisting of chlorine, bromine, hydroxide, water, and (when m is greaterthan 1) combinations thereof; In is an integer from 1 to 3 (preferably 1 or2; most preferably 1); m+n = 6; and Y is an appropriately selectedcounteranion present in a number y, which is an integer from 1 to 3(preferably 2 to 3; most preferably 2 when Y is a -1 charged anion), toobtain a charge-balanced salt.The preferred cobalt catalyst of this type useful herein are cobaltpentaarnine chloride salts having the formula [Co(NH3)5Cl] Yy, andespecially [Co(NH3)5Cl]Cl2.More preferred are the present invention compositions which utilize cobalt(III) bleach catalysts having the formula: 3[C0(NH3)n(M)m(B)bl Tywherein cobalt is in the +3 oxidation state; 11 is 4 or 5 (preferably 5); M isone or more ligands coordinated to the cobalt by one site; In is 0, I or 2(preferably 1); B is a ligand co-ordinated to the cobalt by two sites; b is 0or 1 (preferably 0), and when b=0, then m+n = 6, and when b=l , then m=0and n=4; and T is one or more appropriately selected counteranions presentin a number y, where y is an integer to obtain a charge~balanced salt(preferably y is 1 to 3; most preferably 2 when T is a -1 charged anion);and wherein further said catalyst has a base hydrolysis rate constant of lessthan 0.23 M-1 s-1 (25°c).WO 98/11185l020253035CA 02264916 1999-03-05PCT/U S97/ 1597749Preferred T are selected from the group consisting of chloride, iodide, 13‘,formate, nitrate, nitrite, sulfate, sulfite, citrate, acetate, carbonate, bromide,PF6', BF4‘, B(Ph)4', phosphate, phosphite, silicate, tosylate,methanesulfonate, and combinations thereof. Optionally, T can beprotonated if more than one anionic group exists in T, e.g., HPO42‘,HCO3', H2PO4', etc. Further, T may be selected from the groupconsisting of non-traditional inorganic anions such as anionic surfactants(e.g., linear alkylbenzene sulfonates (LAS), alkyl sulfates (AS),alkylethoxysulfonates (AES), etc.) and/or anionic polymers (e.g.,polyacrylates, polymethacrylates, etc.).The M moieties include, but are not limited to, for example, F‘, SO4'2,NCS', SCN‘, S2O3'2, NH3, P043‘, and carboxylates (which preferablyare mono-carboxylates, but more than one carboxylate may be present inthe moiety as long as the binding to the cobalt is by only one carboxylateper moiety, in which case the other carboxylate in the M moiety may beprotonated or in its salt form). Optionally, M can be protonated if morethan one anionic group exists in M (e.g., HPO42', HCO3', H2PO4',I-IO€(O)CH2C(O)O-, etc.) Preferred M moieties are substituted andunsubstituted C1-C30 carboxylic acids having the formulas:RC(O)O-wherein R is preferably selected from the group consisting of hydrogenand C1—C30 (preferably C1-C13) unsubstituted and substituted alkyl, C6-C30 (preferably C6-C13) unsubstituted and substituted aryl, and C3-C30(preferably C5-C18) unsubstituted and substituted heteroaryl, whereinsubstituents are selected from the group consisting of -NR'3, -NR'4"', -C(O)OR', -OR’, -C(O)NR'2, wherein R’ is selected from the groupconsisting of hydrogen and C1-C6 moieties. Such substituted R thereforeinclude the moieties -(CH2)nOH and -(CH2)nNR'4+, wherein n is aninteger from 1 to about 16, preferably from about 2 to about 10, and mostpreferably from about 2 to about 5.Most preferred M are carboxylic acids having the formula above whereinR is selected from the group consisting of hydrogen, methyl, ethyl, propyl,101520253035W0 98/11185CA 02264916 1999-03-050 PCT/U S97/ 159775straight or branched C4-C12 alkyl, and benzyl. Most preferred R ismethyl. Preferred carboxylic acid M moieties include formic, benzoic,octanoic, nonanoic, decanoic, dodecanoic, malonic, maleic, succinic,adipic, phthalic, 2-ethylhexanoic, naphthenoic, oleic, palmitic, triflate,tartrate, stearic, butyric, citric, acrylic, aspartic, fumaric, lauric, linoleic,lactic, malic, and especially acetic acid.The B moieties include carbonate, di- and higher carboxylates (e.g.,oxalate, malonate, malic, succinate, maleate), picolinic acid, and alpha andbeta amino acids (e.g., glycine, alanine, beta-alanine, phenylalanine).Cobalt bleach catalysts useful herein are known, being described forexample along with their base hydrolysis rates, in M. L. Tobe, "BaseHydrolysis of Transition-Metal Complexes", Adv. Inorg. Bioinorg.Mech., (1983), 2, pages 1-94. For example, Table 1 at page 17, providesthe base hydrolysis rates (designated therein as k0H) for cobalt pentaamine catalysts complexed with oxalate (kQH= 2.5 x 10"4 M4 s'1(25°c)), NCS‘ (koH= 5.0 x 10-4 M-1 s-1 (25°c)), fonnate (k0H= 5.8 x10-4 M-1 s-1 (25°c)), and acetate (k0H= 9.6 x 10-4 M-1 s-1 (25°c)).The most preferred cobalt catalyst useful herein are cobalt pentaamineacetate salts having the formula [Co(N H3) 5OAc] Ty, wherein OAcrepresents an acetate moiety, and especially cobalt pentaamine acetatechloride, [Co(NH3)5OAc]Cl2; as well as [Co(NH3)5OAc](OAc)2;[Co(NH3)50Ac](PF6)2; [Co(NH3)50Ac](S04); [Co(NH3)50A<=](BF4)2;and [Co(NH3)5OAc](NO3)2 (herein "PAC").These cobalt catalysts are readily prepared by known procedures, such astaught for example in the Tobe article hereinbefore and the references citedtherein, in U.S. Patent 4,810,410, to Diakun et al, issued March 7,1989, _J_.Chem. Ed. (1989), _6_§ (12), 1043-45; The Synthesis and Characterizationof Inorganic Compounds, W.L. Jolly (Prentice-Hall; 1970), pp. 461-3;Inorg. Chem., _1_8, 1497-1502 (1979); Inorg. Chem., 2_1_, 2881-2885(1982); Inor . Chem., _l_8_, 2023-2025 (1979); Inorg. Synthesis, 173-176(1960); and Journal of Physical Chemistry, §__6_, 22-25 (1952); as well as thesynthesis examples provided hereinafter.I01520253035W0 98/11185CA 02264916 1999-03-05PCTIUS97/159775 1These catalysts may be coprocessed with adjunct materials so as to reducethe color impact if desired for the aesthetics of the product, or to beincluded in enzyme-containing particles as exemplified hereinafter, or thecompositions may be manufactured to contain catalyst "speckles".Hydrocarbon OilsAnother preferred detergent component for use in the present invention is ahydrocarbon oil, typically a predominantly long chain, aliphatic hydrocarbons havinga number of carbon atoms in the range of from 20 to 50; preferred hydrocarbons aresaturated and/or branched; preferred hydrocarbon oil selected from predominantlybranched C25_45 species with a ratio of cyclic to noncyclic hydrocarbons of from1:10 to 2: 1, preferably from 1:5 to 121. A preferrred hydrocarbon oil is paraffin. A ,paraffin oil meeting the characteristics as outlined above, having a ratio of cyclic tononcyclic hydrocarbons of about 32:68, is sold by Wintershall, Salzbergen,Germany, under the trade name WINOG 70.Water-Soluble Bismuth CompoundThe compositions of the may contain a water-soluble bismuth compound, preferablypresent at a level of from 0.005% to 20%, more preferably from 0.01% to 5%, mostpreferably from 0.1% to 1% by weight of the compositions.The water-soluble bismuth compound may be essentially any salt or complex ofbismuth with essentially any inorganic or organic counter anion. Preferred inorganicbismuth salts are selected from the bismuth trihalides, bismuth nitrate and bismuthphosphate. Bismuth acetate and citrate are preferred salts with an organic counteranion.Bismuth salts are preferred components of the detergent compositions describedherein, in that they may additionally provide conductivity.Corrosion Inhibitor CompoundThe compositions of the present invention may contain corrosion inhibitorspreferably selected from organic silver coating agents, particularly paraffin, nitrogen-l01520253035W0 98/11185CA 02264916 1999-03-05PCTIUS97/1597752containing corrosion inhibitor compounds and Mn(II) compounds, particularlyMn(II) salts of organic ligands.Organic silver coating agents are described in PCT Publication No. WO94/ 16047and copending European application No. EP-A-690122. Nitrogen—containingcorrosion inhibitor compounds are disclosed in copending European Application no.EP—A-634,478. Mn(II) compounds for use in corrosion inhibition are described incopending European Application No. EP-A-672 749.Organic silver coating agent may be incorporated at a level of from 0.05% to 10%,preferably from 0.1% to 5% by weight of the total composition.The functional role of the silver coating agent is to form 'in use‘ a protective coatinglayer on any silverware components of the washload to which the compositions ofthe invention are being applied. The silver coating agent should hence have a high .affinity for attachment to solid silver surfaces, particularly when present in as acomponent of an aqueous washing and bleaching solution with which the solid silversurfaces are being treated.Suitable organic silver coating agents herein include fatty esters of mono- orpolyhydric alcohols having from 1 to about 40 carbon atoms in the hydrocarbonchain.The fatty acid portion of the fatty ester can be obtained from mono- or poly-carboxylic acids having from 1 to about 40 carbon atoms in the hydrocarbon chain.Suitable examples of monocarboxylic fatty acids include behenic acid, stearic acid,oleic acid, palmitic acid, myristic acid, lauric acid, acetic acid, propionic acid, butyricacid, isobutyric acid, Valerie acid, lactic acid, glycolic acid and B,B'-dihydroxyisobutyric acid. Examples of suitable polycarboxylic acids include: n-butyl-malonic acid, isocitric acid, citric acid, maleic acid, malic acid and succinicacid.The fatty alcohol radical in the fatty ester can be represented by mono- or polyhydricalcohols having from 1 to 40 carbon atoms in the hydrocarbon chain. Examples ofsuitable fatty alcohols include; behenyl, arachidyl, cocoyl, oleyl and lauryl alcohol,l01520253035W0 98ll1l85CA 02264916 1999-03-05PCT/US97/ 159775 3ethylene glycol, glycerol, ethanol, isopropanol, vinyl alcohol, diglycerol, xylitol,sucrose, erythritol, pentaerythritol, sorbitol or sorbitan.Preferably, the fatty acid and/or fatty alcohol group of the fatty ester adjunct materialhave from 1 to 24 carbon atoms in the alkyl chain.Preferred fatty esters herein are ethylene glycol, glycerol and sorbitan esters whereinthe fatty acid portion of the ester normally comprises a species selected from behenicacid, stearic acid, oleic acid, palmitic acid or myristic acid.The glycerol esters are also highly preferred. These are the mono-, di- or tri-estersof glycerol and the fatty acids as defined above.Specific examples of fatty alcohol esters for use herein include: stearyl acetate,palmityl di-lactate, cocoyl isobutyrate, oleyl maleate, oleyl dimaleate , and tallowylproprionate. Fatty acid esters useful herein include: xylitol monopalmitate,pentaerythritol monostearate, sucrose monostearate, glycerol monostearate, ethyleneglycol monostearate, sorbitan esters. Suitable sorbitan esters include sorbitanmonostearate, sorbitan palmitate, sorbitan monolaurate, sorbitan monomyristate,sorbitan monobehenate, sorbitan mono-oleate, sorbitan dilaurate, sorbitan distearate,sorbitan dibehenate, sorbitan dioleate, and also mixed tallowalkyl sorbitan mono- anddi-esters.Glycerol monostearate, glycerol mono-oleate, glycerol monopalmitate, glycerolmonobehenate, and glycerol distearate are preferred glycerol esters herein.Suitable organic silver coating agents include triglycerides, mono or diglycerides,and wholly or partially hydrogenated derivatives thereof, and any mixtures thereof.Suitable sources of fatty acid esters include vegetable and fish oils and animal fats.Suitable vegetable oils include soy bean oil, cotton seed oil, castor oil, olive oil,peanut oil, safflower oil, sunflower oil, rapeseed oil, grapeseed oil, palm oil and cornoil.Waxes, including microcrystalline waxes are suitable organic silver coating agentsherein. Preferred waxes have a melting point in the range from about 35°C to about110°C and comprise generally from 12 to 70 carbon atoms. Preferred are petroleum101520253035W0 98/11185CA 02264916 1999-03-05PCT/US97/1597754waxes of the paraffin and microcrystalline type which are composed of long-chainsaturated hydrocarbon compounds.Alginates and gelatin are suitable organic silver coating agents herein.Dialkyl amine oxides such as C12-C20 methylamine oxide, and dialkyl quaternaryammonium compounds and salts, such as the C12-C20 methylammonium halides arealso suitable.Other suitable organic silver coating agents include certain polymeric materials.Polyvinylpyrrolidones with an average molecular weight of from 12,000 to 700,000,polyethylene glycols (PEG) with an average molecular weight of from 600 to10,000, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, and cellulose derivatives such as methylcellulose,carboxymethylcellulose and hydroxyethylcellulose are examples of such polymericmaterials.Certain perfume materials, particularly those demonstrating a high substantivity formetallic surfaces, are also useful as the organic silver coating agents herein.Polymeric soil release agents can also be used as an organic silver coating agent.Suitable polymeric soil release agents include those soil release agents having: (a)one or more nonionic hydrophile components consisting essentially of (i)polyoxyethylene segments with a degree of polymerization of at least 2, or (ii)oxypropylene or polyoxypropylene segments with a degree of polymerization offrom 2 to 10, wherein said hydrophile segment does not encompass anyoxypropylene unit unless it is bonded to adjacent moieties at each end by etherlinkages, or (iii) a mixture of oxyalkylene units comprising oxyethylene and from 1to about 30 oxypropylene units, said hydrophile segments preferably comprising atleast about 25% oxyethylene units and more preferably, especially for suchcomponents having about 20 to 30 oxypropylene units, at least about 50%oxyethylene units; or (b) one or more hydrophobe components comprising (i) C3oxyalkylene terephthalate segments, wherein, if said hydrophobe components alsocomprise oxyethylene terephthalate, the ratio of oxyethylene terephthalate:C3oxyalkylene terephthalate units is about 2:1 or lower, (ii) C4-C6 alkylene or oxy C4-101520253035W0 98/11185CA 02264916 1999-03-05PCT/US97l159775 5C6 alkylene segments, or mixtures therein, (iii) poly (vinyl ester) segments,preferably polyvinyl acetate, having a degree of polymerization of at least 2, or (iv)C1-C4 alkyl ether or C4 hydroxyalkyl ether substituents, or mixtures therein,wherein said substituents are present in the form of C1-C4 alkyl ether or C4hydroxyalkyl ether cellulose derivatives, or mixtures therein, or a combination of (a)and (b).Typically, the polyoxyethylene segments of (a)(i) will have a degree ofpolymerization of from about 200, although higher levels can be used, preferablyfrom 3 to about 150, more preferably from 6 to about 100. Suitable oxy C4-C5alkylene hydrophobe segments include, but are not limited to, end-caps of polymericsoil release agents such as MO3S(CH2)nOCl-l2CH2O-, where M is sodium and n isan integer from 4-6, as disclosed in U.S. Patent 4,721,580, issued January 26, 1988.to Gosselink.Polymeric soil release agents useful herein also include cellulosic derivatives such ashydroxyether cellulosic polymers, copolymeric blocks of ethylene terephthalate orpropylene terephthalate with polyethylene oxide or polypropylene oxideterephthalate, and the like. Such agents are commercially available and includehydroxyethers of cellulose such as METHOCEL (Dow). Cellulosic soil releaseagents for use herein also include those selected from the group consisting of C 1 -C4alkyl and C4 hydroxyalkyl cellulose; see U.S. Patent 4,000,093, issued December28, 1976 to Nicol, et al.Soil release agents characterized by poly(vinyl ester) hydrophobe segments includegraft copolymers of poly(vinyl ester), e.g., C1-C5 vinyl esters, preferably poly(vinylacetate) grafted onto polyalkylene oxide backbones, such as polyethylene oxidebackbones. See European Patent Application 0 219 048, published April 22, 1987 byKud, et al.Another suitable soil release agent is a copolymer having random blocks of ethyleneterephthalate and polyethylene oxide (PEO) terephthalate. The molecular weight ofthis polymeric soil release agent is in the range of from about 25,000 to about 55,000.See U.S. Patent 3,959,230 to Hays, issued May 25, 1976 and U.S. Patent 3,893,929to Basadur issued July 8, 1975.1020253035W0 98/ I 1 185CA 02264916 1999-03-05PCT/US97/159775 6Another suitable polymeric soil release agent is a polyester with repeat units ofethylene terephthalate units contains 10-15% by weight of ethylene terephthalateunits together with 90-80% by weight of polyoxyethylene terephthalate units, derivedfrom a polyoxyethylene glycol of average molecular weight 300-5,000.Another suitable polymeric soil release agent is a sulfonated product of asubstantially linear ester oligomer comprised of an oligomeric ester backbone ofterephthaloyl and oxyalkyleneoxy repeat units and terminal moieties covalentlyattached to the backbone. These soil release agents are described fully in U.S.Patent 4,968,451, issued November 6, 1990 to J .J . Scheibel and E.P. Gosselink.Other suitable polymeric soil release agents include the terephthalate polyesters ofU.S. Patent 4,711,730, issued December 8, 1987 to Gosselink et al, the anionic end-capped oligomeric esters of U.S. Patent 4,721,580, issued January 26, 1988 to_Gosselink, and the block polyester oligomeric compounds of U.S. Patent 4,702,857,issued October 27, 1987 to Gosselink. Other polymeric soil release agents alsoinclude the soil release agents of U.S. Patent 4,877,896, issued October 31, 1989 toMaldonado et al, which discloses anionic, especially sulfoarolyl, end-cappedterephthalate esters.Another soil release agent is an oligomer with repeat units of terephthaloyl units,sulfoisoterephthaloyl units, oxyethyleneoxy and oxy-1,2-propylene units. Therepeat units form the backbone of the oligomer and are preferably terminated withmodified isethionate end-caps. A particularly preferred soil release agent of thistype comprises about one sulfoisophthaloyl unit, 5 terephthaloyl units,oxyethyleneoxy and oxy-1,2-propyleneoxy units in a ratio of from about 1.7 to about1.8, and two end-cap units of sodium 2-(2-hydroxyethoxy)-ethanesulfonate.A preferred organic silver coating agent is a paraffin oil, typically a predominantlybranched aliphatic hydrocarbon having a number of carbon atoms in the range offrom 20 to 50; preferred paraffin oil selected from predominantly branched C25_45species with a ratio of cyclic to noncyclic hydrocarbons of from 1:10 to 2:1,preferably from 1:5 to 1:1. A paraffin oil meeting these characteristics, having aratio of cyclic to noncyclic hydrocarbons of about 32:68, is sold by Wintershall,Salzbergen, Germany, under the trade name WINOG 70.Nitrogen-Containing Corrosion Inhibitor CompoundsI01520253035W0 98/11185CA 02264916 1999-03-05PCT/US97ll 59775 7Suitable nitrogen-containing corrosion inhibitor compounds include imidazole andderivatives thereof such as benzimidazole, 2-heptadecyl imidazole and thoseimidazole derivatives described in Czech Patent No. 139, 279 and British PatentGB-A-1,137,741, which also discloses a method for making imidazole compounds.Also suitable as nitrogen-containing corrosion inhibitor compounds are pyrazolecompounds and their derivatives, particularly those where the pyrazole is substitutedin any of the 1, 3, 4 or 5 positions by substituents R1, R3, R4 and R5 where R1 isany of H, CH2OH, CONH3, or COCH3, R3 and R5 are any of C1-C2() alkyl orhydroxyl, and R4 is any of H, NH2 or N02.Other suitable nitrogen-containing corrosion inhibitor compounds includebenzotriazole, 2-mercaptobenzothiazole, 1-phenyl-5-mercapto-1 ,2,3,4-tetrazole,thionalide, morpholine, melamine, distearylamine, stearoyl stearamide, cyanuric acid,aminotriazole, aminotetrazole and indazole.Nitrogen—containing compounds such as amines, especially distearylamine andammonium compounds such as ammonium chloride, ammonium bromide,ammonium sulphate or diammonium hydrogen citrate are also suitable.Mn(II) Corrosion Inhibitor CompoundsThe compositions may contain an Mn(II) corrosion inhibitor compound. The Mn(II)compound is preferably incorporated at a level of from 0.005% to 5% by weight,more preferably from 0.01% to 1%, most preferably from 0.02% to 0.4% by weightof the compositions. Preferably, the Mn(II) compound is incorporated at a level toprovide from 0.1 ppm to 250 ppm, more preferably from 0.5 ppm to 50 ppm, mostpreferably from 1 ppm to 20 ppm by weight of Mn(II) ions in any bleaching solution.The Mn (II) compound may be an inorganic salt in anhydrous, or any hydratedforms. Suitable salts include manganese sulphate, manganese carbonate, manganesephosphate, manganese nitrate, manganese acetate and manganese chloride. TheMn(II) compound may be a salt or complex of an organic fatty acid such asmanganese acetate or manganese stearate.I020253035W0 98/11185 A 58CA 02264916 1999-03-05PCT/US97/ 15977The Mn(II) compound may be a salt or complex of an organic ligand. In onepreferred aspect the organic ligand is a heavy metal ion sequestrant. In anotherpreferred aspect the organic ligand is a crystal growth inhibitor.Other Corrosion Inhibitor CompoundsOther suitable additional corrosion inhibitor compounds include, mercaptans anddiols, especially mercaptans with 4 to 20 carbon atoms including lauryl mercaptan,thiophenol, thionapthol, thionalide and thioanthranol. Also suitable are saturated orunsaturated C10-C20 fatty acids, or their salts, especially aluminium tristearate. TheC12-C20 hydroxy fatty acids, or their salts, are also suitable. Phosphonated octa-decane and other anti-oxidants such as betahydroxytoluene (BHT) are also suitable.Copolymers of butadiene and maleic acid, particularly those supplied under the tradereference no. 07787 by Polysciences Inc have been found to be of particular utilityas corrosion inhibitor compounds.Total Available Oxygen (AVO) LevelIt has been found that, for optimal anti-silver tarnishing performance, the level ofavailable oxygen in the present compositions, measured in units of % availableoxygen by weight of the composition, is preferably controlled; the level of availableoxygen should hence preferably be in the range from 0.3% to‘2.5%, preferably from0.5% to 1.7%, more preferably from 0.6% to 1.5%, most preferably from 0.7% to1.2%, measured according to the method described hereunder.Rate of Release of AVO The rate of release of available oxygen is preferably also controlled; the rate ofrelease of available oxygen from the compositions herein preferably should be suchthat, when using the method described hereinafter, the available oxygen is notcompletely released from the composition until after 3.5 minutes, preferably theavailable oxygen is released in a time interval of from 3.5 minutes to 10.0 minutes,more preferably from 4.0 minutes to 9.0 minutes, most preferably from 5.0 minutesto 8.5 minutes.101520253035W0 98/11185CA 02264916 1999-03-05PCT/US97/1597759Method for Measuring Level of Total Available Oxygen (Avo) and Rate of Releaseof AvO in a Detergent CompositionMethod1. A beaker of water (typically 2L) is placed on a stirrer Hotplate, and the stirrerspeed is selected to ensure that the product is evenly dispersed through the solution.2. The detergent composition (typically 8g of product which has been sampleddown from a bulk supply using a Pascal sampler), is added and simultaneously a stopclock is started.3. The temperature control should be adjusted so as to maintain a constanttemperature of 20°C throughout the experiment.4. Samples are taken from the detergent solution at 2 minute time intervals for20 minutes, starting after 1 minute, and are titrated by the "titration procedure"described below to determine the level of available oxygen at each point.Titration Procedure1. An aliquot from the detergent solution (above) and 2ml sulphuric acid areadded into a stirred beaker2. Approximately 0.2g ammonium molybdate catalyst (tetra hydrate form) areadded '3. 3mls of 10% sodium iodide solutionare added4. Titration with sodium thiosulphate is conducted until the end point. The endpoint can be seen using either of two procedures. First procedure consists simply inseeing the yellow iodine colour fading to clear. The second and preferred procedureconsists of adding soluble starch when the yellow colour is becoming faint, turningthe solution blue. More thiosulphate is added until the end point is reached (bluestarch complex is decolourised).15202530CA 02264916 1999-03-05wo 93/11135 PCT/US97/1597760The level of AvO, measured in units of % available oxygen by weight, for the sampleat each time interval corresponds to the amount of titre according to the followingequationVol S2O3(m|) xMo|arity (8203) x 8Sample mass (g)AvO level is plotted versus time to determine the maximum level of AvO, and therate of release of AvOControlled Rate of Release — MeansA means may be provided for controlling the rate of release of oxygen bleach to thewash solution.Means for controlling the rate of release of the bleach may provide for controlledrelease of peroxide species to the wash solution. Such means could, for example,include controlling the release of any inorganic perhydrate salt, acting -as a hydrogenperoxide source, to the wash solution.Suitable controlled release means can include coating any suitable component with acoating designed to provide the controlled release. The coating may therefore, forexample, comprise a poorly water soluble material, or be a coating of sufficientthickness that the kinetics of dissolution of the thick coating provide the controlledrate of release.The coating material may be applied using various methods. Any coating material istypically present at a weight ratio of coating material to bleach of from 1:99 to 1:2,preferably from 1:49 to 1:9.Suitable coating materials include triglycerides (e.g. partially) hydrogenatedvegetable oil, soy bean oil, cotton seed oil) mono or diglycerides, microcrystallinewaxes, gelatin, cellulose, fatty acids and any mixtures thereof.101520253035W0 98/11185CA 02264916 1999-03-05PCT/US97/ 159776 1Other suitable coating materials can comprise the alkali and alkaline earth metalsulphates, silicates and carbonates, including calcium carbonate and silicas.A preferred coating material, particularly for an inorganic perhydrate salt bleachsource, comprises sodium silicate of SiO2 : Na2O ratio from 1.8 : 1 to 3.0 : 1,preferably 1.8:] to 2.4: 1 , and/or sodium metasilicate, preferably applied at a level offrom 2% to 10%, (normally from 3% to 5%) of SiO2 by weight of the inorganicperhydrate salt. Magnesium silicate can also be included in the coating.Any inorganic salt coating materials may be combined with organic binder materialsto provide composite inorganic salt/organic binder coatings. Suitable bindersinclude the C10-C20 alcohol ethoxylates containing from 5 — 100 moles of ethyleneoxide per mole of alcohol and more preferably the C15-C20 primary alcoholethoxylates containing from 20 - 100 moles of ethylene oxide per mole of alcohol.Other preferred binders include certain polymeric materials. Polyvinylpyrrolidoneswith an average molecular weight of from 12,000 to 700,000 and polyethyleneglycols (PEG) with an average molecular weight of from 600 to 5 x 106 preferably1000 to 400,000 most preferably 1000 to 10,000 are examples of such polymericmaterials. Copolymers of maleic anhydride with ethylene, methylvinyl ether ormethacrylic acid, the maleic anhydride constituting at least 20 mole percent of thepolymer are further examples of polymeric materials useful as binder agents. Thesepolymeric materials may be used as such or in combination with solvents such aswater, propylene glycol and the above mentioned C10-C20 alcohol ethoxylatescontaining from 5 - 100 moles of ethylene oxide per mole. Further examples ofbinders include the C10-C20 mono- and diglycerol ethers and also the C10—C20 fattyacids.Cellulose derivatives such as methylcellulose, carboxymethylcellulose andhydroxyethylcellulose, and homo- or co-polymeric polycarboxylic acids or their saltsare other examples of binders suitable for use herein.One method for applying the coating material involves agglomeration. Preferredagglomeration processes include the use of any of the organic binder materialsdescribed hereinabove. Any conventional agglomerator/mixer may be usedincluding, but not limited to pan, rotary drum and vertical blender types. Moltenl0l520253035W0 98/1 I 185CA 02264916 1999-03-05PCT/US97/1597762coating compositions may also be applied either by being poured onto, or sprayatomized onto a moving bed of bleaching agent.Other means of providing the required controlled release include mechanical meansfor altering the physical characteristics of the bleach to control its solubility and rateof release. Suitable protocols could include compression, mechanical injection,manual injection, and adjustment of the solubility of the bleach compound byselection of particle size of any particulate component.Whilst the choice of particle size will depend both on the composition of theparticulate component, and the desire to meet the desired controlled release kinetics,it is desirable that the particle size should be more than 500 micrometers, preferablyhaving an average particle diameter of from 800 to 1200 micrometers.Additional protocols for providing the means of controlled release include thesuitable choice of any other components of the detergent composition matrix suchthat when the composition is introduced to the wash solution the ionic strengthenvironment therein provided enables the required controlled release kinetics to beachieved.T-Ieafl Metal Ion SeguestrantThe detergent compositions of the invention preferably contain as an optionalcomponent a heavy metal ion sequestrant. By heavy metal ion sequestrant it is meantherein components which act to sequester (chelate) heavy metal ions. Thesecomponents may also have calcium and magnesium chelation capacity, butpreferentially they show selectivity to binding heavy metal ions such as iron,manganese and copper.Heavy metal ion sequestrants are generally present at a level of from 0.005% to 20%,preferably from 0.1% to 10%, more preferably from 0.25% to 7.5% and mostpreferably from 0.5% to 5% by weight of the compositions.Heavy metal ion sequestrants, which are acidic in nature, having for examplephosphonic acid or carboxylic acid functionalities, may be present either in their acidform or as a complex/salt with a suitable counter cation such as an alkali or alkalinel01520253035W0 98/1 1 185CA 02264916 1999-03-05PCT/US97/1597763metal ion, ammonium, or substituted ammonium ion, or any mixtures thereof.Preferably any salts/complexes are water soluble. The molar ratio of said countercation to the heavy metal ion sequestrant is preferably at least 1:1.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 amongthe above species are diethylene triamine penta (methylene phosphonate), ethylenediamine tri (methylene phosphonate) hexamethylene diamine tetra (methylenephosphonate) and hydroxy-ethylene 1,1 diphosphonate.Other suitable heavy metal ion sequestrant for use herein include nitrilotriacetic acidand polyaminocarboxylic acids such as ethylenediaminotetracetic acid,ethylenetriamine pentacetic acid, ethylenediamine disuccinic acid, ethylenediaminediglutaric acid, 2-hydroxypropylenediamine disuccinic acid or any salts thereof.Especially preferred is ethylenediamine-N,N'~disuccinic acid (EDDS) or the alkalimetal, alkaline earth metal, ammonitun, or substituted ammonium salts thereof, ormixtures thereof. Preferred EDDS compounds are the flee acid form and the sodiumor magnesium salt or complex thereof.Cflstal Growth Inhibitor ComponentThe detergent compositions preferably contain a crystal growth inhibitor component,preferably an organodiphosphonic acid component, incorporated preferably at a levelof from 0.01% to 5%, more preferably from 0.1% to 2% by weight of thecompositions.By organo diphosphonic acid it is meant herein an organo diphosphonic acid whichdoes not contain nitrogen as part of its chemical structure. This definition thereforeexcludes the organo aminophosphonates, which however may be included incompositions of the invention as heavy metal ion sequestrant components.The organo diphosphonic acid is preferably a C1-C4 diphosphonic acid, morepreferably a C2 diphosphonic acid, such as ethylene diphosphonic acid, or most101520253035W0 98/ 11185CA 02264916 1999-03-05PCT/U S97/ 15977. 64preferably ethane 1-hydroxy-1,1-diphosphonic acid (HEDP) and may be present inpartially or fully ionized form, particularly as a salt or complex.Enyme Stabilizing SystemPreferred enzyme-containing compositions herein may comprise from about 0.001%to about 10%, preferably from about 0.005% to about 8%, most preferably fromabout 0.01% to about 6%, by weight of an enzyme stabilizing system. The enzymestabilizing system can be any stabilizing system which is compatible with thedetersive enzyme. Such stabilizing systems can comprise calcium ion, boric acid,propylene glycol, short chain carboxylic acid, boronic acid, chlorine bleachscavengers and mixtures thereof. Such stabilizing systems can also comprisereversible enzyme inhibitors, such as reversible protease inhibitors.Organic Polymeric CompoundOrganic polymeric compounds may be added as preferred components of thecompositions in accord with the invention. By organic polymeric compound it ismeant essentially any polymeric organic compound commonly used as dispersants,and anti-redeposition and soil suspension agents in detergent compositions.Organic polymeric compound is typically incorporated in the detergent compositionsof the invention at a level of from 0.1% to 30%, preferably from 0.5% to 15%, mostpreferably from 1% to 10% by weight of the compositions.Examples of organic polymeric compounds include the water soluble organic homo-or co-polymeric polycarboxylic acids or their salts in which the polycarboxylic acidcomprises at least two carboxyl radicals separated from each other by not more thantwo carbon atoms. Polymers of the latter type are disclosed in GB-A-1,596,756.Examples of such salts are polyacrylates of molecular weight 2000-10000 and theircopolymers with any suitable other monomer units including modified acrylic,fumaric, maleic, itaconic, aconitic, mesaconic, citraconic and methylenemalonic acidor their salts, maleic anhydride, acrylamide, alkylene, vinylmethyl ether, styrene andany mixtures thereof. Preferred are the copolymers of acrylic acid and maleicanhydride having a molecular weight of from 20,000 to 100,000.101520253035WO 98/11185CA 02264916 1999-03-05PCT/U S97/ 1597765Preferred commercially available acrylic acid containing polymers having amolecular weight below 15,000 include those sold under the tradename SokalanPA30, PA20, PAl5, PA10 and Sokalan CP10 by BASF GmbH, and those sold underthe tradename Acusol 45N by Rohm and Haas.Preferred acrylic acid containing copolymers include those which contain asmonomer units: a) from 90% to 10%, preferably from 80% to 20% by weight acrylicacid or its salts and b) from 10% to 90%, preferably from 20% to 80% by weight of asubstituted acrylic monomer or its salts having the general formula —[CR2-CR1(CO-O-R3)]- wherein at least one of the substituents R1, R2 or R3, preferably R1 or R2 isa 1 to 4 carbon alkyl or hydroxyalkyl group, R1 or R2 can be a hydrogen and R3 canbe a hydrogen or alkali metal salt. Most preferred is a substituted acrylic monomerwherein R1 is methyl, R2 is hydrogen (i.e. a methacrylic acid monomer). The mostpreferred copolymer of this type has a molecular weight of 3500 and contains 60% to80% by weight of acrylic acid and 40% to 20% by weight of methacrylic acid.The polyamino compounds are useful herein including those derived from asparticacid such as those disclosed in EP—A-305282, EP-A-305283 and EP-A-351629.Lime Soap Dispersant CompoundThe compositions of the invention may contain a lime soap dispersant compound,preferably present at a level of from 0.1% to 40% by weight, more preferably 1% to20% by weight, most preferably from 2% to 10% by weight of the compositions.A lime soap dispersant is a material that prevents the precipitation of alkali metal,ammonium or amine salts of fatty acids by calcium or magnesium ions. Preferredlime soap disperant compounds are disclosed in PCT Application No. W093/08877.Polymeric Dve Transfer Inhibiting AgentsThe compositions herein may also comprise from 0.01% to 10 %, preferably from0.05% to 0.5% by weight of polymeric dye transfer inhibiting agents.15202530W0 98/11 185CA 02264916 1999-03-05PCT/U S97] 1597766The polymeric dye transfer inhibiting agents are preferably selected from polyamineN-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole,polyvinylpyrrolidonepolymers or combinations thereof.Other Optional IngredientsOther optional ingredients suitable for inclusion in the compositions of the inventioninclude perfumes, colours and filler salts, with sodium sulfate being a preferred fillersalt.pH of the CompositionsThe detergent compositions used in the present invention are preferably notformulated to have an unduly high pH, in preference having a pH measured as a 1%solution in distilled water of from 8.0 to 12.5, more preferably from 9.0 to 11.8, mostpreferably from 9.5 to 11.5.Machine Dishwashing MehodAny suitable methods for machine washing or cleaning soiled tableware, particularlysoiled silverware are envisaged.A preferred machine dishwashing method comprises treating soiled articles selectedfrom crockery, glassware, hollowware, silverware and cutlery and mixtures thereof,with an aqueous liquid having dissolved or dispensed therein an effective amount ofa detergent composition in accord with the invention. By an effective amount of thedetergent composition it is meant from 8g to 60g of product dissolved or dispersed ina wash solution of volume from 3 to 10 litres, as are typical product dosages andwash solutionvolumes commonly employed in conventional machine dishwashingmethods.W0 98/11185Abbreviations used in Examples02264916 1999-03-05PCT/U S97/ 1597767ExamplesIn the detergent compositions, the abbreviated component identifications have thefollowing meanings:STPPCitrateBicarbonateCarbonateSilicateMetasilicatePB 1PB4PeroarbonatePlurafacTergitolSLF 1 8BTAEDHEDPDETPMPMnTACNSodium tripolyphosphateTri-sodium citrate dihydrateSodium hydrogen carbonateAnhydrous sodium carbonateAmorphous Sodium Silicate (SiO2:Na2O ratio = 1.6-3.2)Sodium metasilicate (SiO2:Na2O ratio = 1.0)Anhydrous sodium perborate monohydrateSodium perborate tetrahydrate of nominal formulaNaBO2.3H2O.H2O2Anhydrous sodium percarbonate of nominal formula2.Na2CO3_3H2O2C13-C15 mixed ethoxylated/propoxylated fatty alcoholwith an average degree of ethoxylation of 3.8 and anaverage degree of propoxylation of 4.5, sold under thetradename Plurafac byNonionic surfactant available under the tradenameTergitol 15S9 fi'om Union CarbideEpoxy-capped poly(oxyalkylated) alcohol of ExampleIII of WO 94/22800 wherein 1,2-epoxydodecane issubstituted for 1,2-epoxydecane available under thetradename Polytergent SLF18B from OLIN.Tetraacetyl ethylene diamineEthane 1-hydroxy-1 ,1 -diphosphonic acidDiethyltriamine penta (methylene) phosphonate,marketed by monsanto under the tradename Dequest2060Manganese 1 ,4,7-trirnethyl-1 ,4,7—triazacyclononane.CA 02264916 1999-03-05W0 98/11185 68 PCT/US97/ 15977PAAC : Pentaamine acetate cobalt (III) saltBzP : Benzoyl PeroxideParaffin : Paraffin oil sold under the tradename Winog 70 byWintershall.Protease 2 Proteolytic enzymeAmylase : Amylolytic enzyme.BTA : BenzotriazolePA30 2 Polyacrylic acid of average molecular weightapproximately 4,500MA/AA 2 Random copolymer of 4:1 acrylate/maleate, averagemolecular weight about 70,000480N : Random copolymer of 7:3 acrylate/methacrylate,average molecular weight about 3,500Sulphate : Anhydrous sodium sulphate.pH : Measured as a 1% solution in distilled water at 20°CIn the following examples all levels are quoted as % by weight of the composition:CA 02264916 1999-03-05wo 93/11135 69 PCT/US97/15977Example 1The following compact high density (0.96Kg/1) dishwashing detergent compositionsA to H were prepared in accord with the invention:A B C D E F G HSTPP - - 54.30 51.40 51.4 - - 50,90Citrate 35.0 17.05 - - - 46.10 40.20 -Carbonate - 17.50 14.0 14.0 14.0 8.0 32.10Bicarbonate - - - - - 25.40 - -Silicate 32.00 14.81 14.81 10.0 10.0 1.04 25.0 3.10Metasilicate - 2.50 - 4.5 4.5 - - -PB1 1.95 9.74 ‘ 7.79 7.79 7.79 — - -PB4 8.65 - - - - - - -Percarbonate - - - - - 6.70 1 1.80 4.80Tergitol 2.0 2.0 2.0 2.0 1.5 2.0 2.0 3.0SLF 18B 1.50 2.0 1.45 2.0 1.50 2.60 1.90 5.30TAED 5.22 2.39 - - - 2.21 - 1.40HEDP — 1.0 - - - - - -DETPMP 0.65 - — - - - -Mn TACN - - - - - - 0.008 -PAAC - - 0.008 0.01 0.007 - - ‘ -BzP - - - - 1.40 - - -Paraffin 0.50 0.55 0.47 0.50 0.50 0.60 - -Protease 2.20 2.20 0.90 1.62 1.40 0.80 1.80 0.30Amylase 1.50 1.50 0.76 1.50 1.70 1.10 2.10 0.80BTA 0.30 0.30 0.30 0.30 0.30 - 0.30 0.30MA/AA - - - - - - 4.20 -480N 3.27 6.0 - - - - 0.90Perfume 0.20 0.20 0.20 0.20 0.20 0.20 0.10 0.10Sulphate 7.0 20.0 5.0 2.20 5.0 12.00 4.60 2.0misc/water tobalancepH (1% 10.8 11.0 10.8 11.3 11.3 9.6 10.8 10.9solution)CA 02264916 1999-03-05WO 98/11185 70 PCT/US97/15977Example 2The following granular dishwashing detergent compositions examples I to P of bulkdensity 1.02Kg/L were prepared in accord with the invention:I J K L M N O PSTPP 30.00 30.00 33.0 30.5 29.62 31.10 26.6 17.60Carbonate 30.50 30.50 31.0 30.0 23.00 39.40 4.20 45.0Silicate 7.40 7.40 7.50 7.21 13.30 3.36 43.70 12.44Metasilicate - - 4.50 5.10Percarbonate - - - - - 4.0 -PB1 4.40 4.25 4.50 4.50 - - -NaDCC - - - - 2.00 - 1.60 1.0Tergitol 1.0 1.5 1.5 1.0 2.0 1.0 1.0 1.0SLF 18B - 1.0 0.75 0.75 1.90 0.70 0.60 -Plurafac 1 .20 0.35TAED 1.00 - - - - 0.80 '-PAAC - 0.004 ‘ 0.004 0.004 - - -BzP - - - 1.40 - - -Paraffin 0.25 0.25 0.25 0.25 - - -Protease 1.10 0.45 0.81 0.85 - 0.30 -Amylase 0.38 0.38 0.70 0.76 — ‘ 0.80 —BTA 0.15 0.15 0.15 _0.15 - - -Perfume 0.20 0.20 0.20 0.20 0.10 0.20 0.20Sulphate 22.0 22.0 16.0 18.50 30.08_ 19.34 23.1 23.6Misc/waterto balancepH (1% 10.80 10.80 11.3 11.3 10.70 11.5 12.7 10.9solution)CA 02264916 1999-03-05wo 93/11135 PCT/US97/15977Example 3The following tablet detergent composition examples Q to V in accord with thepresent invention were prepared by compression of a granular dishwashing detergentcomposition at a pressure of 13KN/cm2 using a standard 12 head rotary press:Q R S T U VSTPP - 48.80 49.20 30.0 - 46.80Citrate 26.40 - - - 31.10 -Carbonate - 5.0 14.0 15.40 14.40 23.0Silicate 26.40 14.80 15.0 12.60 17.70 2.40Protease 1 1.76 2.20‘ 1.26 1.0 1.60 0.40Amylase 1.20 1.50 1.50 0.85 2.0 0.30PB1 1.56 7.69 12.20 10.60 15.70 -PB4 6.92‘ - - - - 14.40Tergitol 2.0 2,0 2.0 2.0 2.0 2.0SLF 18B 2.0 2.0 2.0 2.0 1.0 6.30PAAC - - 0.016 0.009 - -Mn'1"ACN - - - - 0.007 -TAED 4.33 2.50 - - . 1.30 1.84HEDP 0.67 - - 0.7 - 0.40DETPMP 0.65 - - - - -Paraffin 0.42 0.50 0.5 0.55 - -BTA 0.24 0.30 0.3 0.33 - -PA30 3.2 - - - - -MA/AA - - - - 4.51 0.55Perfume - - 0.05 0.05 0.20 0.2Sulphate - 24.05 13.0 8.0 18.7 10.68 10.0Misc/water to balance 'weight of tablet 25g 25g 20g 30g 18g 20gpH (1% solution) 10.60 10.60 10.7 10.7 10.9 11.2

Claims (13)

WHAT IS CLAIMED IS:

1. An automatic dishwashing detergent composition comprising a) one or more high cloud point nonionic surfactants having a cloud point of greater than 40°C;
b) an amount of water-soluble salt to provide conductivity in deionised water measured at 25°C of greater than 3 milli Siemens/cm.

2. An automatic dishwashing detergent composition according to claim 1 wherein the nonionic surfactant comprises greater than 8 carbon atoms.

3. An automatic dishwashing detergent composition according to either of claims 1 or 2 wherein the nonionic surfactant is an alkoxylated surfactant comprising alkoxylated groups selected from ethyleneoxy, propyleneoxy and butyleneoxy groups.

4. An automatic dishwashing detergent composition according to any of claims 1 to 3 wherein the nonionic surfactant on average comprises greater than 6 moles of ethyleneoxide.

5. An automatic dishwashing detergent composition according to any of claims 1 to 5 wherein the nonionic surfactant has a cloud point of greater than 50°C.

6. An automatic dishwashing detergent composition according to any of claims 1 to 5 wherein the nonionic surfactant is an ethoxylated surfactant derived from the reaction of a monohydroxy alcohol or alkylphenol comprising from 8 to 20 carbon atoms andon average from 6 to 15 moles of ethyleneoxide per mole of alcohol or alkyl phenol.

7. An automatic dishwashing detergent composition according to any of claims 1 to 6 wherein the water-soluble salt is a water-soluble sulphate, silicate, carbonate or bicarbonate salt.

8. An automatic dishwashing detergent composition according to any of claims 1 to 7 additionally comprising a suds suppresser.

9. An automatic dishwashing detergent composition according to claim 8 wherein the suds suppresser is a low cloud point nonionic surfactant.

10. An automatic dishwashing detergent composition according to claim 9 wherein the low cloud point nonionic surfactant has the general formula:
R1O[CH2CH(CH3)O]x[CH2CH2O]y[CH2CH(OH)R2] (I) wherein R1 is a linear or branched, aliphatic hydrocarbon radical having from 4 to 12 carbon atoms including mixtures thereof; R2 is a linear or branched aliphatic hydrocarbon radical having from 2 to 10 carbon atoms including mixtures thereof; x is an integer having an average value of from 0.5 to 1.5; and y is an integer having a value of least 20.

11. An automatic dishwashing detergent composition according to any of claims 1 to 10 wherein the conductivity in deionised water measured at 25°C is greater than 4 milli Siemens/cm.

12. A method of washing dishware in an automatic dishwasher by contacting the dishware with a solution comprising a high cloud point nonionic surfactant having a cloud point of greater than 40°C and an amount of water-soluble salt which provides conductivity of greater than 3 milli Siemens/cm at temperatures less than 40°C.

13. Use of an automatic dishwashing detergent composition according to any of claims 1 to 11 for cleaning greasy soils from dishware.