GRANULAR LAUNDRY DETERGENT COMPOSITIONS COMPRISING ZWITTERIONIC POLYAMINES

Abstract: The present invention relates to laundry detergent compositions which provide enhance hydrophilic soil cleaning benefits, said compositions comprising : a) from about 0.01% by weight, of a zwitterionic hexamethylene diamine; b) from about 0.01% by weight, of a surfactant system comprising one or more surfactants selected from the group consisting of nonionic, anionic, cationic, zwitterionic, ampholytic surfactants, and mixtures thereof; and c) the balance carriers and adjunct ingredients. The preferred embodiment of the present includes laundry detergent compositions in the form of a water soluble or dispersible tablet.

Description: GRANULAR LAUNDRY DETERGENT COMPOSITIONS COMPRISING ZWITTERIONIC POLYAMINES CROSS REFERENCE This Application claims the benefit of U S Provisional Application No 60/184.271. filed on February 23, 2000 FIELD OF THE INVENTION The present invention relates to granular laundry detergent compositions which provide enhanced hydrophilic soil, inter a a. clay, removal benefits The laundry detergent compositions of the present invention combme a zwitterionic hexamethylene diamme with a surfactant system to produce either a granular free flowing or tablet composition The present invention further relates to methods for cleaning fabric having heavy clay soil deposits BACKGROUND OF THE INVENTION Fabπc, especially clothing, can become soiled with a variety of foreign substances ranging from hydrophobic stains (grease, oil) to hydrophilic stains (clay) The level of cleaning which is necessary to remove said foreign substances depends to a large degree upon the amount of stain present and the degree to which the foreign substance has contacted the fabπc fibers Grass stains usually involve direct abrasive contact with vegetative matter thereby producmg highly penetrating stains Clay soil stains, although in some instances contacting the fabπc fibers with less force, nevertheless provide a different type of soil removal problem du to the high degree of charge associated with the clay itself This high surface charge density may act to repel some laundry adjunct mgredients, inter aha, clay dispersants, thereby resisting any appreciable solublizing of the clay mto the laundry liquor A surfactant per se is not all that is necessarv to remove unwanted clay soils and stains In fact, not all surfactants work equally well on all types of stains In addition to surfactants, poiyamine hydrophilic soil dispersants are added to laundr\ detergent compositions to "carry away" clay soils from the fabπc surface and to remove the possibility that the clay soil will be re- deposited upon the fabπc However, unless the clay can be initially dispersed away from the fabnc fiber, especially in the case of hydrophilic fibers, inter alia, cotton, the soils can not be effectively removed from the fabric There is a long felt need in the art for granular laundry detergent compositions which can effectively solublize embedded clay and other hydrophilic soils from fabπc There has further been a long felt need for a method for cleaiung hydrophilic soils from fabπc wherem the hydrophilic soils are effectively solubhzed into the laundry liquor SUMMARY OF THE INVENTION The present invention meets the aforementioned needs in that it has been surpπsingly discovered that certain zwittenonic hexamethylene diamines in combmation with a surfactant system compπsmg provides enhanced removal of clay and other hydrophilic soils from fabπc The first aspect of the present invention relates to a laundry detergent composition compπsmg a) from about 0 01%, preferably from about 0 1%, more preferably from about 1%, most preferably from about 3% to about 20%, preferably to about 10%, more preferably to about 5% by weight, of a zwittenonic hexamethylene diamine having the formula wherem R is an alkyleneoxy umt having the formula — (R'O) 2 wherem R 1 is C 2 -C linear alkylene, C 3 -C branched alkylene, and mixtures thereof, R 2 is hydrogen, an anionic umt, and mixtures thereof, the mdex x has the value of from about 15 to about 35, Q is a quatermzmg umt independently selected from the group consistmg of -Cg linear alkyl, C 3 -C 8 branched alkyl, benzyl, and mixtures thereof, X is a water soluble anion m sufficient amount to provide electronic neutrality, b) from about 0 01%, preferably from about 0 1% more preferably from about 1%, most preferably from about 10% to about 80% by weight, preferably to about 60%, most preferably to about 30% by weight, of a surfactant system compπsmg one or more surfactants selected from the group consistmg of nomomc. anionic, catiomc, zwittenonic. ampholytic surfactants, and mixtures thereof, and c) the balance earners and adjunct mgredients The present mvention further relates to laundry detergent compositions m the form of a solid tablet or pill wherein the zwittenonic hexamethylene diamine has surpnsmglv been discovered to serve as a process aid or tablet binder in addition to providing supenor cleaning properties The present mvention also relates to a method for removmg hydrophilic stams from fabnc by contacting fabnc m need of cleaning with an aqueous solution compπsmg at least lppm (0 0001%), preferably at least 5 ppm (0 0005%). more preferably at least lOppm (0 001%) of one or more zwittenomc hexamethylene diamines These and other objects, features and advantages will become apparent to those of ordinary skill in the art from a readmg of the following detailed descnption and the appended claims All percentages, ratios and proportions herein are by weight, unless otherwise specified All temperatures are m degrees Celsius (° C) unless otherwise specified All documents cited are m relevant part, incorporated herem by reference DETAILED DESCRIPTION OF THE INVENTION The present mvention relates to the surpnsing discovery that the combmation of a zwittenomc diamme having a hexamethylene backbone and a surfactant system provides enhanced benefits for removal of clay soil from fabnc especially clothing It has also been surpnsingly discovered that the presence of one or more quaternized hexamethylene diamines havmg at least one anionic unit capped alkyleneoxy backbone substitution provides a formulation aid when processmg granular, especially tablet, laundry detergent compositions As desenbed herein below, the quaternary ammonium hexamethylene diamme and surfactant system can be combmed with a wide vanety of adjunct mgredients to provide granular laundry detergent compositions havmg mcreased clay removal properties The laundry detergent compositions of the present mvention may take any form, for example, granular, powder, or tablet, a prefened form, further desenbed herem below, is tablet form The following is a detailed descnption of the require elements of the present mvention Zwittenomc Hexamethylene Diamines The granular laundry detergent compositions of the present mvention compnse from about 0 01%, preferably from about 0 1%. more preferably from about 1%, most preferably from about 3% to about 20%, preferably to about 10%. more preferably to about 5% by weight, of a zwittenonic hexamethylene diamine havmg the formula wherem R is an alkyleneoxy unit havmg the formula — (R^xR 2 wherem R 1 is C -C 4 linear alkylene, C 3 -C 4 branched alkylene. and mixtures thereof, preferably ethylene R is hydrogen, an amomc unit, and mixtures thereof Non-limiting examples of anionic umts mclude -(CH 2 ) p C0 2 M, -(CH 2 ) q S0 3 M, -(CH 2 ) q OS0 3 M. -(CH 2 ) q CH(S0 2 M)-CH 2 S0 3 M, - (CH 2 ) q CH(OS0 2 M)CH 2 OS0 3 M -(CH 2 ) q CH(S0 3 M)CH 2 S0 3 M, -(CH 2 ) p P0 3 M, -P0 3 M, and mixtures thereof, wherem M is hydrogen or a water soluble cation in sufficient amount to satisfy charge balance Preferred anionic umts are -(CH 2 ) p C0 2 M, -S0 3 M, more preferably -S0 3 M The mdices p and q are mtegers from 0 to 6 Preferably from about 85%, more preferably from about 90%), most preferably from about 95% of all R 2 umts which compnse an aggregate sample of the zwittenonic polyamme have R 2 units which are anionic umts It will be understood by the formulator that some molecules will be fully capped with anionic units, while some molecules may have two R 2 umts which are hydrogen However, most preferably from about 95% of all R umts present will be capped with one or more amomc umts desenbed herem The mdex x has the value of from about 15 to about 35 and represents the average number of alkyleneoxy umts which are present Depending upon the method by which the formulator chooses to form the alkyleneoxy umts. the wider or narrower the range of alkyleneoxy umts present Preferably the range of alkyleneoxy umts m plus or mmus two umts. more preferably plus or mmus one umt Most preferably each R group compπses the same number of alkyleneoxy umts The mdex x is preferably from 20 to 30 A prefened value for x is 24. especially when R 1 compπses entirely ethyleneoxy umts Q is a quaternizing umt mdependently selected from the group consistmg of Ci-Cg lmear alkyl, C 3 -C 8 branched alkyl. benzyl, and mixtures thereof, preferably methyl or benzyl, most preferably methyl X is a water soluble anion in sufficient amount to provide electronic neutrality To a great degree, the counter ion X will be derived from the unit which is used to perform the quaternization For example, if methyl chlonde is used as the quaternizing agent, chlorme (chlonde ion) will be the counter ion X Bromme (bromide ion) will be the dominant counter ion m the case where benzyl bromide is the quaternizing reagent A prefened zwittenomc hexamethylene diamine according to the present invention has the formula wherem X can comprise any suitable counteπon EXAMPLE 1 Synthesis of hexamethylene diamine. ethoxylate (E24). sulfated to approximately >90%. methyl quaternary ammonium methosulfate Ethoxylation of hexamethylene diamme to Average E24 per NH - The ethoxylation is conducted m a 2 gallon stirred stainless steel autoclave equipped for temperature measurement and control, pressure measurement, vacuum and inert gas purging, sampling, and for introduction of ethylene oxide as a liquid A ~20 lb net cylinder of ethylene oxide (ARC) is set up to deliver ethylene oxide as a liquid by a pump to the autoclave with the cylmder placed on a scale so that the weight change of the cylmder could be monitored A 195 5 g portion of hexamethylene diamme (HMD) (m w 116, (Aldπch), 1 68 moles. 3 36 moles mtrogen, 6 7 moles ethoxylatable (NH) sites, is added to the autoclave The autoclave is then sealed and purged of air (by applymg vacuum to mmus 28" Hg followed by pressuπzation with mtrogen to 250 psia, then ventmg to atmospheπc pressure) The autoclave contents are heated to 80 °C while applymg vacuum After about one hour, the autoclave is charged with mtrogen to about 250 psia while coolmg the autoclave to about 105 °C Ethylene oxide is then added to the autoclave incrementally over time while closely monitoring the autoclave pressure, temperature, and ethylene oxide flow rate The ethylene oxide pump is turned off and coolmg is applied to limit any temperature increase resulting from any reaction exotherm The temperature is maintained between 100 and 110 °C while the total pressure is allowed to gradually mcrease dunng the course of the reaction After a total of 296 grams of ethylene oxide (6 7 moles) has been charged to the autoclave, the temperature is mcreased to 110 °C and the autoclave is allowed to stir for an additional 2 hours At this point, vacuum is applied to remove any residual unreacted ethylene oxide Next, vacuum is contmuously applied while the autoclave is cooled to about 50 °C while introducing 145 2 g of a 25% sodium methoxide in methanol solution (0 67 moles, to achieve a 10% catalyst loadmg based upon ethoxylatable sites functions) The methoxide solution is removed from the autoclave under vacuum and then the autoclave temperature controller setpomt is mcreased to 100 °C A device is used to momtor the power consumed by the agitator The agitator power is momtored along w th the temperature and pressure Agitator power and temperature values gradually mcrease as methanol is removed from the autoclave and the viscosity of the mixture increases and stabilizes in about 1 5 hours indicating that most of the methanol has been removed The mixture is further heated and agitated under vacuum for an additional 30 mmutes Vacuum is removed and the autoclave is cooled to 105 °C while it is bemg charged with mtrogen to 250 psia and then vented to ambient pressure The autoclave is charged to 200 psia with mtrogen Ethylene oxide is agam added to the autoclave incrementally as before while closely monitoring the autoclave pressure, temperature, and ethylene oxide flow rate while mamtainmg the temperature between 100 and 110 °C and limiting any temperature mcreases due to reaction exotherm After the addition of 4048 g of ethylene oxide ( 92 mol, resultmg in a total of 24 moles of ethylene oxide per mole of ethoxylatable sites on HMD), the temperature is mcreased to 110 °C and the mixture stared for an additional 2 hours The reaction mixture is then collected mto a 22 L three neck round bottomed flask purged with mtrogen The strong alkali catalyst is neutralized by slow addition of 64 6 g methanesulfomc acid (0 67 moles) with heatmg (100 °C) and mechanical stirring The reaction mixture is then removed of residual ethylene oxide and deodoπzed by spargmg an inert gas (argon or mtrogen) mto the mixture through a gas dispersion frit while agitating and heatmg the mixture to 120 °C for 1 hour The final reaction product is cooled slightly and stored m a glass container purged with mtrogen Quatermzation of HMD E24 to 90 mol%> (2 mol N per mol polymer) - Into a weighed, 1000ml, 3 neck round bottom flask fitted with argon inlet, condenser, addition funnel, thermometer, mechanical stirring and argon outlet (connected to a bubbler) is added HMD E024 (723 33g, 0 333 mol N, 98% active, m w -4340) under argon The mixture is stirred at room temperature until the polymer has dissolved The mixture is then cooled to 5°C using an ice bath Dimethyl sulfate (126 13 g. Imol. 99%. m w 126 13) is slowly added usmg an addition funnel over a penod of 15 minutes The ice bath is removed and the reaction is allowed to πse to room temperature After 48 hrs the reaction is complete The reaction mixture is dissolved m 500g water and adjusted to pH>7 usmg IN NaOH followed by transfer to a plastic container for storage Sulfation of HMD E24 to 90% - Under argon, the reaction mixture from the quatermzation step is cooled to 5°C usmg an ice bath (HMD E24, 90+mol% quat, 0 59 mol OH) Chlorosulfonic acid (72g, 0 61 mol. 99%. mw-116 52) is slowly added usmg an addition funnel The temperature of the reaction mixture is not allowed to rise above 10°C The ice bath is removed and the reaction is allowed to rise to room temperature After 6 hrs the reaction is complete The reaction is again cooled to 5°C and sodium methoxide (264g, 1 22 mol. Aldnch, 25% m methanol. m w -54 02) is slowly added to the rapidly stirced mixture The temperature of the reaction mixture is not allowed to rise above 10°C The reaction mixture is transfened to a smgle neck round bottom flask Purified water (1300ml) is added to the reaction mixture and the methylene chlonde, methanol and some water is stripped off on a rotary evaporator at 50°C The clear, light yellow solution is transfened to a bottle for storage The final product pH is checked and adjusted to ~9 usmg IN NaOH or IN HC1 as needed SURFACTANT SYSTEM The laundry detergent compositions of the present mvention compnse a surfactant system The surfactant systems of the present mvention may comprise any type of detersive surfactant, non-limiting examples of which mclude one or more mid-cham branched alkyl sulfate surfactants, one or more mid-cham branched alkyl alkoxy sulfate surfactants, one or more mid-cham branched aryl sulfonate surfactants, one or more non mid-cham branched sulphonates. sulphates, catiomc surfactants, zwittenomc surfactants, ampholytic surfactants, and mixtures thereof The total amount of surfactant present in the compositions of the present mvention is from about 0 01% by weight, preferably from about 0 1% more preferably from about 1% to about 60%, preferably to about 30% by weight, of said composition Nonhmiting examples of surfactants useful herem mclude a) Cn-Cig alkyl benzene sulfonates (LAS), b) C 6 -Cιg mid-cham branched aryl sulfonates (BLAS), c) Cιo-C 20 primary, α or ω-branched. and random alkyl sulfates (AS), d) Cι 4 -C 20 mid-cham branched alkyl sulfates (BAS), e) Cio-Cis secondary (2.3) alkyl sulfates as described in U S 3.234,258 Morris, issued February 8. 1966, U S 5.075,041 Lutz, issued December 24, 1991. U S 5,349,101 Lutz et al , issued September 20. 1994, and U S 5,389,277 Pneto. issued February 14. 1995 each incorporated herem by reference, f) Cio-Ci alkyl alkoxy sulfates (AE X S) wherein preferably x is from 1-7, g) Cι 4 -C 2 o mid-chain branched alkyl alkoxy sulfates (BAE x S), h) Cio-Cig alkyl alkoxy carboxylates preferably comprising 1-5 ethoxy umts, I) C12-C 1 8 alkyl ethoxylates. Cβ-Cπ alkyl phenol alkoxylates wherem the alkoxylate umts are a mixture of ethyleneoxy and propyleneoxy umts. Cι 2 -Gg alcohol and C 6 -Cι 2 alkyl phenol condensates with ethylene oxide/propylene oxide block polymers inter aha Pluromc ® ex BASF which are disclosed U S 3.929,678 Laughlm et al , issued December 30. 1975, incorporated herem by reference, j) C ]4 -C 22 mid-cham branched alkyl alkoxylates, BAE x , k) Alkylpolysacchandes as disclosed m U S 4,565.647 Llenado, issued January 26, 1986, incorporated herem by reference, 1) Polyhydroxy fatty acid amides havmg the formula O R 8 . II I R 7 -C— N-Q wherem R is C 5 -C 3 ι alkyl, R 8 is selected from the group consistmg of hydrogen, C]-C 4 alkyl, Cι-C hydroxyalkyl, Q is a polyhydroxyalkyl moiety havmg a lmear alkyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative thereof, prefened alkoxy is ethoxy or propoxy. and mixtures thereof, prefened Q is deπved from a reducmg sugar m a reductive animation reaction, more preferably Q is a glycityl moiety. Q is more preferably selected from the group consistmg of -CH 2 (CHOH) n CH 2 OH, -CH(CH 2 OH)(CHOH) n ιCH 2 OH, - CH 2 (CHOH) 2 (CHOR')(CHOH) CH 2 OH, and alkoxylated derivatives thereof, wherem n is an mteger from 3 to 5, inclusive, and R' is hydrogen or a cyclic or aliphatic monosacchande, which are desenbed m U S 5,489.393 Connor et al . issued February 6, 1996, and U S 5.45,982 Murch et al , issued October 3, 1995, both incorporated herem by reference A non-limiting example of a nomonic surfactant suitable for use in the present mvention has the formula [(RO R >2O™) y τR> J ] D wherein R is C 7 -C 2 ι linear alkyl, C 7 -C 2 ι branched alkyl, C 7 -C ] linear alkenyl, C 7 -C 2 ι branched alken> 1. and mixtures thereof R 1 is ethylene. R 2 ιs C 3 -C 4 linear alkyl. C 3 -C 4 branched alkyl, and mixtures thereof, preferably R 2 is 1,2-propylene Nomonic surfactants which compnse a mixture of R and R umts preferably compnse from about 4 to about 12 ethylene umts in combination with from about 1 to about 4 1,2-propylene umts The units may be alternating, or grouped together m any combination suitable to the formulator Preferably the ratio of R 1 umts to R 2 units is from about 4 1 to about 8 1 Preferably an R 2 umts (l e 1.2-propylene) is attached to the mtrogen atom followed by the balance of the chain compnsing from 4 to 8 ethylene umts R 2 is hydrogen. -C 4 linear alkyl. C 3 -C 4 branched alkyl. and mixtures thereof, preferably hydrogen or methyl, more preferably hydrogen R 4 is hydrogen, Cι-C 4 lmear alkyl. C 3 -C branched alkyl, and mixtures thereof, preferably hydrogen When the index m is equal to 2 the mdex n must be equal to 0 and the R umt is absent and is mstead replaced by a -[(R 1 0) x (R 2 0) y R 3 ] umt The mdex m is 1 or 2. the mdex n is 0 or 1. provided that when m is equal to 1. n is equal to 1. and when m is 2 n is 0, preferably m is equal to 1 and n is equal to one, resultmg m one - [(R 1 0) x (R 2 0) y R 3 ] unit and R 4 bemg present on the mtrogen The mdex x is from 0 to about 50, preferably from about 3 to about 25. more preferably from about 3 to about 10 The mdex y is from 0 to about 10, preferably 0, however when the mdex y is not equal to 0, y is from 1 to about 4 Preferably all of the alkyleneoxy umts are ethyleneoxy umts Those skilled in the art of ethoxylated polyoxyalkylene alkyl amide surface active agents will recognized that the values for the mdices x and y are average values and the true values may range over several values dependmg upon the process used to alkoxylate the amides The mid-chain branched alkyl sulfate surfactants of the present mvention have the formula R R 1 R 2 I I I CH 3 CH 2 (CH 2 ) w CH(CH 2 ) x CH(CH 2 ) v CH(CH 2 ) z OS0 3 M the alkyl alkoxy sulfates have the formula R R 1 R 2 I I I CH 3 CH 2 (CH 2 )^H(CH 2 ) H(CH 2 ) y CH(CH 2 ) z (OR 3 ) m OS0 3 M the alkyl alkoxylates have the formula R R 1 R 2 I I I 3 CH 3 CH 2 (CH 2 ) w CH(CH 2 ) x CH(CH 2 ) y CH(CH 2 ) z (OR 3 ) m OH wherem R, R 1 . and R 2 are each independently hydrogen, Cι-C 3 alkyl. and mixtures thereof, provided at least one of R. R 1 . and R 2 is not hydrogen, preferably R, R 1 , and R 2 are methyl, preferably one of R, R 1 , and R 2 is methyl and the other umts are hydrogen The total number of carbon atoms in the mid-cham branched alkyl sulfate and alkyl alkoxy sulfate surfactants is from 14 to 20. the index w is an mteger from 0 to 13. x is an integer from 0 to 13, y is an mteger from 0 to 13. z is an mteger of at least 1, provided w + x + y + z is from 8 to 14 and the total number of carbon atoms m a surfactant is from 14 to 20, R 3 is Cι-C 4 linear or branched alkylene. preferably ethylene. 1,2-propylene. 1.3-propylene, 1,2-butylene, 1,4-butylene, and mixtures thereof However, a prefened embodiment of the present mvention compnses from 1 to 3 umts wherem R 3 is 1.2-propylene, 1,3-propylene, or mixtures thereof followed by the balance of the R 3 umts compnsmg ethylene umts Another prefened embodiment compπses R 3 umts which are randomly ethylene and 1,2-propylene umts The average value of the index m is at least about 0 01 When the mdex m has low values, the surfactant system compnses mostly alkyl sulfates with a small amount of alkyl alkoxy sulfate surfactant Some tertiary carbon atoms may be present m the alkyl cham. however, this embodiment is not desired M denotes a cation, preferably hydrogen, a water soluble cation, and mixtures thereof Non-limiting examples of water soluble cations mclude sodium, potassium, lithium, ammonium, alkyl ammonium, and mixtures thereof BLEACHING SYSTEM The laundry detergent compositions of the present invention may optionally mclude a bleaching system Non-limiting examples of bleaching systems mclude hypohalite bleaches, peroxygen bleachmg systems, or transition metal ml peroxygen systems Peroxygen systems typically comprise a "bleaching agent" (source of hydrogen peroxide) and an "initiator " or "catalyst", however, pre-formed bleaching agents are mcluded Catalysts for peroxygen systems can mclude transition metal systems In addition, certam transition metal complexes are capable of providmg a bleaching system without the presence of a source of hydrogen peroxide Compositions of the present mvention which contain a bleaching system, compnse a) from about 0 01 % by weight of a zwittenomc hexamethylene diamme according to the present mvention, b) from about 0 01 % by weight, preferably from about 0 1 % more preferably from about 1% to about 60%, preferably to about 30% by weight, of a surfactant system, said surfactant system compnsmg I) from 0 01 %, preferably from about 0 1 % more preferably from about 1 % to about 100%), preferably to about 80% by weight, preferably to about 60%. most preferably to about 30% by weight, of one or more amomc surfactants, said amomc surfactants selected form the group consistmg of linear alkyl benzene sulphonates. mid-cham branched alkyl benzene sulphonates, linear alkyl sulfates. mid-cham branched sulfates, lmear alkyleneoxy sulfates, mid-cham branched alkyleneoxy sulfates. and mixtures thereof, u) optionally, from 0 01%, preferably from about 0 1% more preferably from about 1% to about 100%, preferably to about 80% by weight, preferably to about 60%, most preferably to about 30% by weight, of one or more nonionic surfactants selected from the group consistmg of alcohols, alcohol ethoxylates, polyoxyalkylene alkylamides, and mixtures thereof, c) from about 1%, preferably from about 5% to about 80%, preferably to about 50% by weight, of a peroxygen bleaching system compπsmg I) from about 40%, preferably from about 50%, more preferably from about 60% to about 100%, preferably to about 95%, more preferably to about 80% by weight, of the bleaching system, a source of hydrogen peroxide, n) optionally from about 0 1 %, preferably from about 0 5% to about 60%, preferably to about 40% by weight, of the beaching system, a beach activator, m) optionally from about 1 ppb (0 0000001%), more preferably from about 100 ppb (0 00001%), yet more preferably from about 500 ppb (0 00005%), still more preferably from about 1 ppm (0 0001%) to about 99 9%, more preferably to about 50%, yet more preferably to about 5%, still more preferably to about 500 ppm (0 05%) by weight of the composition, of a transition-metal bleach catalyst, IV) optionally from about 0 1 % by weight, of a pre-formed peroxygen bleaching agent, and d) the balance earners and other adjunct mgredients Bleachmg Agents - Hydrogen peroxide sources are desenbed m detail m the herem incorporated Kirk Othmer's Encyclopedia of Chemical Technology, 4th Ed (1992, John Wiley & Sons). Vol 4, pp 271-300 "Bleachmg Agents (Survey)", and mclude the vanous forms of sodium perborate and sodium percarbonate, mcludmg vanous coated and modified forms Sources of hydrogen peroxide which are suitable for use m the compositions of the present mvention mclude, but are not limited to, perborates, percarbonates, perphosphates, persulfates, and mixtures thereof Prefened sources of hydrogen peroxide are sodium perborate monohydrate, sodium perborate tetrahydrate, sodium percarbonate and sodium persulfate, more preferably are sodium perborate monohydrate, sodium perborate tetrahydrate, and sodium percarbonate When present the source of hydrogen peroxide is present at a level of from about 40%, preferably from about 50%, more preferably from about 60% to about 100%, preferably to about 95%, more preferably to about 80% by weight, of the bleaching system Embodiments which are bleach compnsmg pre-soak compositions may compnse from 5% to 99% of the source of hydrogen peroxide A prefened percarbonate bleach compnses dry particles havmg an average particle size m the range from about 500 micrometers to about 1,000 micrometers, not more than about 10% by weight of said particles bemg smaller than about 200 micrometers and not more than about 10% by weight of said particles bemg larger than about 1,250 micrometers Optionally, the percarbonate can be coated with a silicate, borate or water-soluble surfactants Bleach Activators Preferably, the source of hydrogen peroxide (peroxygen bleach component) m the composition is formulated with an activator (peracid precursor) The activator is present at levels of from about 0 01%, preferably from about 0 5%, more preferably from about 1% to about 15%, preferably to about 10%, more preferably to about 8%, by weight of the composition Also, bleach activators will compnse from about 0 1% to about 60% by weight, of the beaching system When the herem desenbed bleachmg system compnses 60% by weight, of an activator (the maximal amount) and said composition (bleaching composition, laundry detergent, or otherwise) compnses 15%o by weight of said activator (the maximal amount by weight), said composition will compnse 25% by weight of a bleaching system (60%> of which is bleach activator, 40% a source of hydrogen peroxide) However, this is not meant to restnet the formulator to a 60 40 ratio of activator to hydrogen peroxide source Preferably the mole ratio of peroxygen bleaching compound (as AvO) to bleach activator m the present invention generally ranges from at least 1 1, preferably from about 20 1, more preferably from about 10 1 to about 1 1, preferably to about 3 1 Preferred activators are selected from the group consistmg of tetraacetyl ethylene diamme (TAED). benzoylcaprolactam (BzCL), 4-mtrobenzoylcaprolactam, 3-chlorobenzoylcaprolactam, benzoyloxybenzenesulphonate (BOBS), nonanoyloxybenzenesulphonate (NOBS), phenyl benzoate (PhBz), decanoyloxybenzenesulphonate (C I Q-OBS), benzoylvalerolactam (BZVL), octanoyloxybenzenesulphonate (Cg-OBS), perhydrolyzable esters and mixtures thereof, most preferably benzoylcaprolactam and benzoylvalerolactam Particularly preferred bleach activators m the pH range from about 8 to about 9 5 are those selected havmg an OBS or VL leaving group Prefened hydrophobic bleach activators mclude, but are not limited to, nonanoyloxybenzenesulphonate (NOBS), 4-[N-(nonaoyl) ammo hexanoyloxy] -benzene sulfonate sodium salt (NACA-OBS) an example of which is desenbed m U S Patent No 5,523,434, dodecanoyloxybenzenesulphonate (LOBS or C12-OBS), 10-undecenoyloxybenzenesulfonate (UDOBS or Ci i -OBS with unsaturation m the 10 position), and decanoyloxybenzoic acid (DOBA) Prefened bleach activators are those desenbed m U S 5,698,504 Chπstie et al , issued December 16, 1997, U S 5,695,679 Chπstie et al issued December 9, 1997, U S 5,686,401 Willey et al . issued November 11, 1997, U S 5,686.014 Hartshorn et al , issued November 11, 1997, U S 5,405,412 Willey et al , issued Apnl 11, 1995, U S 5,405,413 Willey et al , issued Apnl 11, 1995, U S 5,130,045 Mitchel et al , issued July 14, 1992, and U S 4,412,934 Chung et al , issued November 1, 1983, and copendmg patent applications U S Seπal Nos 08/709,072, 08/064,564, acyl lactam activators, as desenbed m U S 5.698,504, U S 5,695,679 and U S 5.686,014, each of which is cited herem above, are very useful herem, especially the acyl caprolactams (see for example WO 94-28102 A) and acyl valerolactams, U S 5,503,639 Willey et al . issued Apnl 2, 1996 all of which are incorporated herem by reference Quaternary substituted bleach activators may also be included The present cleaning compositions preferably compnse a quaternary substituted bleach activator (QSBA) or a quaternary substituted peracid (QSP), more preferably, the former Prefened QSBA structures are further desenbed m U S 5.686,015 Willey et al . issued November 11, 1997, U S 5,654,421 Taylor et al , issued August 5, 1997, U S 5,460,747 Gosselink et al , issued October 24, 1995, U S 5.584,888 Miracle et al , issued December 17, 1996, and U S 5,578,136 Taylor et al , issued November 26, 1996, all of which are incorporated herem by reference Highly preferred bleach activators useful herem are amide-substituted as desenbed m U S 5,698,504, U S 5,695,679, and U S 5,686,014 each of which are cited herem above Prefened examples of such bleach activators mclude (6-octanamιdocaproyl) oxybenzenesulfonate, (6-nonanamιdocaproyl)oxybenzenesulfonate, (6-decanamιdocaproyl)oxybenzenesulfonate and mixtures thereof Other useful activators, disclosed m U S 5,698.504, U S 5,695,679, U S 5,686,014 each of which is cited herem above and U S 4,966,723Hodge et al , issued October 30, 1990, mclude benzoxazin-type activators, such as a Cβt ring to which is fused m the 1,2-posιtιons a moiety -C(0)OC(R 1 )=N- Depending on the activator and precise application, good bleaching results can be obtained from bleaching systems havmg with m-use pH of from about 6 to about 13, preferably from about 9 0 to about 10 5 Typically, for example, activators with electron-withdrawing moieties are used for near-neutral or sub-neutral pH ranges Alkalis and buffenng agents can be used to secure such pH Transition Metal Bleach Catalyst The laundry detergent compositions of the present mvention optionally compnses a bleachmg system which contams one or more bleach catalysts Selected bleach catalysts inter aha 5,12-dιmethyl-l,5,8,12-tertaaza-bιcyclo[6 6 2]hexadecane manganese (II) chlonde may be formulated mto bleachmg systems which do not require a source of hydrogen peroxide or peroxygen bleach The compositions compnse from about 1 ppb (0 0000001%), more preferably from about 100 ppb (0 00001%), yet more preferably from about 500 ppb (0 00005%), still more preferably from about 1 ppm (0 0001 .) to about 99 9%>, more preferably to about 50%., yet more preferably to about 5%, still more preferably to about 500 ppm (0 05%) by weight of the composition, of a transition-metal bleach catalyst Non-hmitmg examples of suitable manganese-based catalysts are disclosed in U.S 5.576.282 Miracle et al . issued November 19, 1996, U S 5.246.621 Favre et al , issued September 21. 1993. U S 5,244.594 Favre et al . issued September 14, 1993, U S 5.194,416 Jureller et al . issued March 16, 1993. U S 5,114.606 van Vhet et al . issued May 19. 1992, U S 4.430.243 Bragg, issued February 7, 1984, U S 5,114,611 van Krahngen. issued May 19, 1992, U S 4,728,455 Rerek, issued March 1, 1988. U S 5,284,944 Madison, issued February 8, 1994, U S 5.246,612 van Dijk et al . issued September 21, 1993, U S 5,256,779 Kerschner et al , issued October 26, 2993. U S 5.280,117 Kerschner et al , issued January 18. 1994, U S 5,274,147 Kerschner et al , issued December 28, 1993, U S 5.153,161 Kerschner et al , issued October 6, 1992. and U S 5,227,084 Martens et al , issued July 13, 1993. and European Pat App Pub Nos 549.271 Al. 549,272 Al, 544.440 A2. and 544,490 Al Non-limiting examples of suitable cobalt-based catalysts are disclosed m U S 5,597,936 Perkins et al , issued January 28, 1997, U S 5,595,967 Miracle et al , issued January 21, 1997, U S 5,703,030 Perkins et al , issued December 30, 1997, U S Patent 4,810,410 Diakun et al, issued March 7,1989, M L Tobe, "Base Hydrolysis of Transition-Metal Complexes", Adv Inorg Bioinorg Mech . (1983), 2, pages 1-94, J Chem Ed (1989), 66 (12), 1043-45, The Synthesis and Charactenzation of Inorganic Compounds, W L Jolly (Prentice-Hall, 1970), pp 461-3. Inorg Chem . 1_8, 1497-1502 (1979), Inorg Chem . 21, 2881-2885 (1982), Inorg Chem . 18. 2023-2025 (1979), Inorg Synthesis, 173-176 (1960), and Journal of Physical Chemistry. 56, 22-25 (1952) Further examples of preferred macrocyclic ligand compπsmg bleach catalysts are desenbed m WO 98/39406 Al published September 11, 1998 and included herem by reference Suitable examples of these bleach catalysts mclude Dιchloro-5,12-dιmethyl-l,5.8.12-tetraazabιcyclo[6 6 2]hexadecane manganese(II) Dιaquo-5,12-drmethyl-l,5,8,12-tetraazabιcyclo[6 6 2]hexadecane manganese(II) hexafluorophosphate Aquo-hydroxy-5,12-dιmethyl-1.5.8,12-tetraazabιcyclo[6 6 2]hexadecane manganese(III) hexafluorophosphate Dιaquo-5,12-dιmethyl-l,5,8,12-tetraazabιcyclo[6 6 2]hexadecane manganese(II) tetrafluoroborate Dιchloro-5.12-drmethyl-l,5,8.12-tetraazabιcyclo[6 6 2]hexadecane manganese(III) hexafluorophosphate Dιchloro-5.12-dι-n-butyl-l,5.8,12-tetraaza bιcyclo[6 6 2]hexadecane manganese(II) Dιchloro-5,12-dιbenzyl-1.5,8,12-tetraazabιcyclo[6 6 2]hexadecane manganese(II) Dιchloro-5-n-butyl-12-methyl-1.5,8,12-tetraaza- bιcyclo[6 6 2]hexadecane manganese(II) Dιchloro-5-n-octyl-12-methyl-1.5.8,12-tetraaza- bιcyclo[6 6 2]hexadecane manganese(II) Dιchloro-5-n-butyl-12-methyl-1.5.8.12-tetraaza- bιcyclo[6 6 2]hexadecane manganese(II) Pre-formed Bleachmg Agents The bleachmg systems of the present invention may optionally further compnse from 0 1%. preferably from 1%>, more preferably from 5% to about 10%, preferably to about 7% by weight, of one or more pre-formed bleaching agents Pre-formed bleachmg matenals typically have the general formula 0 II HO— O— C— R-Y wherem R is a C]-C 22 alkylene, Cι-C 2 substituted alkylene, phenylene, C 6 -C 22 substituted phenylene. and mixtures thereof. Y is hydrogen, halogen, alkyl, aryl. -C(0)OH. -C(0)OOH. and mixtures thereof The organic percarboxylic acids usable in the present invention can contain either one or two peroxy groups and can be either aliphatic or aromatic When the organic percarboxylic acid is aliphatic, the unsubstituted acid has the general formula 0 HO— O— C— (CH 2 ) n -Y wherein Y can be hydrogen, methyl, methyl chloride, carboxylate, percarboxylate, and n is an mteger havmg the value from 1 to 20 When the organic percarboxylic acid is aromatic, the unsubstituted acid has the general formula wherem Y can be hydrogen, alkyl. haloalkyl, carboxylate, percarboxylate, and mixtures thereof Typical monoperoxy percarboxylic acids useful herem mclude alkyl percarboxylic acids and aryl percarboxylic acids such as l) peroxybenzoic acid and ring-substituted peroxybenzoic acids, e g , peroxy-o- naphthoic acid, n) aliphatic, substituted aliphatic and arylalkyl monoperoxy acids, e g peroxylaunc acid, peroxysteanc acid, and N.N-phthaloylaminoperoxycaproic acid (PAP) Typical diperoxy percarboxylic acids useful herem mclude alkyl diperoxy acids and aryldiperoxy acids, such as in) 1.12 -diperoxydodecanedioic acid, IV) 1,9-dιperoxyazelaιc acid, v) diperoxybrassyhc acid, diperoxysebacic acid and diperoxyisophtha c acid, vi) 2-decyldιperoxybutane-1.4-dιoιc acid. vn) 4.4'-sulfonybιsperoxybenzoιc acid A non-hmitmg example of a highly preferred pre-formed bleach includes 6-nonylamιno-6- oxoperoxycaproic acid (NAPAA) as described m U S Pat No 4,634,551 Bums et al , issued Jan 6, 1987 mcluded herem by reference As well as the herem desenbed peroxygen bleaching compositions, the compositions of the present mvention may also compnse as the bleachmg agent a chlorine-type bleaching matenal Such agents are well known m the art. and mclude for example sodium dichloroisocyanurate ("NaDCC") However, chloπne-type bleaches are less prefened for compositions which compnse enzymes The compositions of the present invention may further comprise one or more photobleachmg agents Photobleachmg and photo disinfectmg compositions are suitably desenbed m U S 3,094.536 issued June 18. 1963, U S 3,927,967 issued December 23, 1975, U S 4,033.718 issued July 5, 1977, U S 4,166.718 issued September 4, 1979. U S 4,240,920 issued December 23, 1980, U S 4,255,273 issued March 10. 1981. U S 4,256,597 issued March 17, 1981. U S 4,318,883 issued March 9, 1982. U S 4.368.053 issued January 11, 1983, U S 4,497,741 issued February 5, 1985, U S 4.648,992 issued March 10, 1987, U S 5,679,661 Willey, issued October 21, 1997, and U S 5.916,481 Willey. issued June 29, 1999 all of which are incorporated herem by reference ADJUNCT INGREDIENTS The following are non-limiting examples of adjunct mgredients useful m the laundry compositions of the present invention, said adjunct mgredients mclude builders, optical bnghteners. soil release polymers, dye transfer agents, dispersents, enzymes, suds suppressers, dyes, perfumes, colorants, filler salts, hydrotropes, photoactivators, fluorescers, fabπc conditioners, hydrolyzable surfactants, preservatives, anti-oxidants. chelants. stabilizers, anti- shnnkage agents, anti-wnnkle agents, germicides, fungicides, anti conosion agents, and mixtures thereof Builders - The laundry detergent compositions of the present invention preferably compnse one or more detergent builders or builder systems When present, the compositions will typically compnse at least about 1% builder, preferably from about 5%, more preferably from about 10% to about 80%. preferably to about 50%, more preferably to about 30% by weight, of detergent builder Inorganic or P -containing detergent builders mclude, but are not limited to, the alkali metal, ammonium and alkanolammonium salts of polyphosphates (exemplified by the tnpolyphosphates, pyrophosphates. and glassy polymeric meta-phosphates), phosphonates, phytic acid, silicates, carbonates (including bicarbonates and sesquicarbonates). sulphates, and aluminosihcates However, non-phosphate builders are required in some locales Importantly, the compositions herem function surpnsingly well even m the presence of the so-called "weak" builders (as compared with phosphates) such as citrate, or m the so-called "underbuilt" situation that may occur with zeolite or layered silicate builders Examples of silicate bmlders are the alkali metal silicates, particularly those havmg a S1O2 Na2θ ratio in the range 1 6 1 to 3 2 1 and layered silicates, such as the layered sodium silicates desenbed m U S 4,664,839 Rieck, issued May 12, 1987 NaSKS-6 is the trademark for a crystalline layered silicate marketed by Hoechst (commonly abbreviated herem as "SKS-6") Unlike zeolite builders, the Na SKS-6 silicate builder does not contain aluminum NaSKS-6 has the delta-Na2Sιθ5 morphology form of layered silicate It can be prepared by methods such as those desenbed m German DE-A-3,417,649 and DE-A-3,742,043 SKS-6 is a highly prefened layered silicate for use herem, but other such layered silicates, such as those havmg the general formula NaMSι x θ2 x +ι y^O wherem M is sodium or hydrogen, x is a number from 1 9 to 4. preferably 2, and y is a number from 0 to 20, preferably 0 can be used herem Vanous other layered silicates from Hoechst include NaSKS-5, NaSKS-7 and NaSKS-11, as the alpha, beta and gamma forms As noted above, the delta-Na2Sιθ5 (NaSKS-6 form) is most prefened for use herem Other silicates may also be useful such as for example magnesium silicate, which can serve as a enspemng agent m granular formulations, as a stabilizing agent for oxygen bleaches, and as a component of suds control systems Examples of carbonate builders are the alkaline earth and alkah metal carbonates as disclosed in German Patent Application No 2.321.001 published on November 15, 1973 Aluminosi cate builders are useful in the present invention Aluminosihcate builders are of great importance m most cuπently marketed heavy duty granular detergent compositions, and can also be a significant builder ingredient in liquid detergent formulations Aluminosilicate builders include those havmg the empirical formula [M z (zA10 2 ) y ] xH 2 0 wherem z and y are mtegers of at least 6. the molar ratio of z to y is m the range from 1 0 to about 0 5. and x is an mteger from about 15 to about 264 Useful aluminosihcate ion exchange matenals are commercially available These aluminosihcates can be crystalline or amorphous in structure and can be naturally-occurring aluminosihcates or synthetically deπved A method for producmg aluminosilicate ion exchange matenals is disclosed m U S 3,985,669, Krummel et al, issued October 12, 1976 Prefened synthetic crystalline aluminosihcate ion exchange matenals useful herem are available under the designations Zeolite A, Zeolite P (B), Zeolite MAP and Zeolite X In an especially prefened embodiment, the crystalline aluminosihcate ion exchange matenal has the formula Na 12 [(A10 2 ) 12 (Sι0 2 ) 12 ] xH 2 0 wherem x is from about 20 to about 30, especially about 27 This matenal is known as Zeolite A Dehydrated zeolites (x = 0 - 10) may also be used herem Preferably, the aluminosihcate has a particle size of about 0 1-10 microns in diameter Organic detergent bmlders suitable for the purposes of the present invention mclude, but are not restricted to, a wide vaπety of polycarboxylate compounds As used herem, "polycarboxylate" refers to compounds havmg a plurality of carboxylate groups, preferably at least 3 carboxylates Polycarboxylate bmlder can generally be added to the composition m acid form, but can also be added m the form of a neutrahzed salt When utilized m salt form, alkali metals, such as sodium, potassium, and lithium, or alkanolammonium salts are prefened Included among the polycarboxylate bmlders are a vaπety of categones of useful matenals One important category of polycarboxylate builders encompasses the ether polycarboxy- lates, mcludmg oxydisuccmate. as disclosed m U S 3,128.287 Berg, issued Apnl 7, 1964, and U S 3.635,830 Lamberti et al . issued January 18, 1972 See also "TMS/TDS" bmlders of U S 4,663,071 Bush et al , issued Ma> 5, 1987 Suitable ether polycarboxylates also mclude cyclic compounds, particularly alicyclic compounds, such as those desenbed m U S 3,923,679 Rapko, issued December 2, 1975, U S 4.158.635 Cmtchfield et al . issued June 19, 1979, U S 4,120.874 Cmtchfield et al , issued October 17, 1978, and U S 4,102,903 Cmtchfield et al , issued July 25, 1978 Other useful detergency builders mclude the ether hydroxypolvcarboxylates, copolvmers of maleic anhydride with ethylene or vmyl methyl ether, 1. 3, 5-tπhydroxy benzene-2, 4, 6- tnsulphomc acid, and carboxymethyloxysuccinic acid, the various alkali metal, ammonium and substituted ammonium salts of polyacetic acids such as ethylenediamine tetraacetic acid and mtπlotnacetic acid, as well as polycarboxylates such as melhtic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene 1.3,5-tπcarboxyhc acid, carboxymethyloxysuccinic acid, and soluble salts thereof Citrate builders, e g . citnc acid and soluble salts thereof (particularly sodium salt), are polycarboxylate builders of particular importance for heavy duty liquid detergent formulations due to their availability from renewable resources and their biodegradabihty Citrates can also be used m granular compositions, especially m combmation with zeolite and or layered silicate builders Oxydisuccmates are also especially useful in such compositions and combmations Also suitable m the detergent compositions of the present mvention are the 3,3-dιcarboxy- 4-oxa-l,6-hexanedιoates and the related compounds disclosed m U S 4.566,984, Bush, issued January 28, 1986 Useful succinic acid builders mclude the C5-C20 alkyl and alkenyl succimc acids and salts thereof A particularly prefened compound of this type is dodecenylsuccinic acid Specific examples of succmate builders mclude laurylsucc nate, myπstylsuccmate, palmitylsuccmate, 2-dodecenylsuccιnate (prefened). 2-pentadecenylsuccιnate. and the like Laurylsucc nates are the prefened builders of this group, and are desenbed m European Patent Application 86200690 5/0,200,263, published November 5, 1986 Other suitable polycarboxylates are disclosed m U S 4,144.226. Cmtchfield et al , issued March 13, 1979 and m U S 3,308,067, Diehl, issued March 7, 1967 See also Diehl U S Patent 3,723,322 Fatty acids, e g , C12-C1 g monocarboxyhc acids, can also be incorporated mto the compositions alone, or m combination with the aforesaid bmlders, especially citrate and/or the succmate builders, to provide additional builder activity Such use of fatty acids will generally result in a diminution of sudsing, which should be taken into account by the formulator In situations where phosphorus-based builders can be used, and especially in the formulation of bars used for hand-laundering operations, the vanous alkali metal phosphates such as the well-known sodium tπpolyphosphates, sodium pyrophosphate and sodium orthophosphate can be used Phosphonate builders such as ethane- 1 -hydroxy- 1.1 -diphosphonate and other known phosphonates (see, for example, U S Patents 3.159,581, 3,213,030. 3,422,021. 3,400,148 and 3.422,137) can also be used Dispersants A descnption of other suitable polyalkyleneimine dispersants which may be optionally combined with the bleach stable dispersants of the present mvention can be found m U S 4.597.898 Vander Meer. issued July 1, 1986. European Patent Application 111,965 Oh and Gossehnk, published June 27. 1984. European Patent Application 111,984 Gosselrnk, published June 27, 1984. European Patent Application 112,592 Gosse nk, published July 4, 1984, U S 4.548.744 Connor, issued October 22, 1985, and U S 5,565.145 Watson et al . issued October 15. 1996, all of which are included herem by reference However, any suitable clay/soil dispersant or anti-redepostion agent can be used in the laundry compositions of the present invention In addition, polymeric dispersing agents which mclude polymenc polycarboxylates and polyethylene glycols, are suitable for use in the present mvention Polymenc polycarboxylate matenals can be prepared by polymeπzmg or copolymenzing suitable unsaturated monomers, preferably m their acid form Unsaturated monomenc acids that can be polymeπzed to form suitable polymenc polycarboxylates mclude acrylic acid, maleic acid (or maleic anhydnde), fumanc acid, ltaconic acid, acomtic acid, mesaconic acid, citracomc acid and methylenemalomc acid The presence m the polymeric polycarboxylates herem or monomenc segments, containing no carboxylate radicals such as vinylmethyl ether, styrene. ethylene. etc is suitable provided that such segments do not constitute more than about 40% by weight Particularly suitable polymenc polycarboxylates can be denved from acrylic acid Such acrylic acid-based polymers which are useful herem are the water-soluble salts of polymeπzed acrylic acid The average molecular weight of such polymers in the acid form preferably ranges from about 2,000 to 10,000, more preferably from about 4,000 to 7.000 and most preferably from about 4,000 to 5,000 Water-soluble salts of such acrylic acid polymers can mclude, for example, the alkali metal, ammonium and substituted ammonium salts Soluble polymers of this type are known matenals Use of polyacrylates of this type m detergent compositions has been disclosed, for example, m U S 3,308,067 Diehl, issued March 7. 1967 Acryhc/maleic-based copolymers may also be used as a prefened component of the dispersing/anti-redeposition agent Such matenals mclude the water-soluble salts of copolymers of acrylic acid and maleic acid The average molecular weight of such copolymers m the acid form preferably ranges from about 2.000, preferably from about 5,000, more preferably from about 7.000 to 100,000. more preferably to 75,000, most preferably to 65,000 The ratio of acrylate to maleate segments m such copolymers will generally range from about 30 1 to about 1 1. more preferably from about 10 1 to 2 1 Water-soluble salts of such acrylic acid/maleic acid copolymers can mclude. for example, the alkah metal, ammonium and substituted ammonium salts Soluble acrylate/maleate copolymers of this type are known matenals which are desenbed m European Patent Application No 66915. published December 15. 1982, as well as m EP 193,360, published September 3. 1986, which also desenbes such polymers compnsmg hydroxypropylacrylate Still other useful dispersmg agents mclude the maleic/acry c/vmyl alcohol terpolymers Such materials are also disclosed in EP 193.360, including, for example, the 45/45/10 terpolymer of acrylic/maleic/vmyl alcohol Another polymeric matenal which can be mcluded is polyethylene glycol (PEG) PEG can exhibit dispersmg agent performance as well as act as a clay soil removal-antiredeposition agent Typical molecular weight ranges for these purposes range from about 500 to about 100,000, preferably from about 1,000 to about 50,000, more preferably from about 1,500 to about 10,000 Polyaspartate and polyglutamate dispersmg agents may also be used, especially m conjunction with zeolite builders Dispersing agents such as polyaspartate preferably have a molecular weight (avg ) of about 10,000 Soil Release Agents The compositions accordmg to the present mvention may optionally compnse one or more soil release agents If utilized, soil release agents will generally compnse from about 0 01%, preferably from about 0 1%. more preferably from about 0 2%> to about 10%, preferably to about 5%, more preferably to about 3% by weight, of the composition Polymenc soil release agents are charactenzed by havmg both hydrophilic segments, to hydrophihze the surface of hydrophobic fibers, such as polyester and nylon, and hydrophobic segments, to deposit upon hydrophobic fibers and remam adhered thereto through completion of the laundry cycle and, thus, serve as an anchor for the hydrophilic segments This can enable stams oecunng subsequent to treatment with the soil release agent to be more easily cleaned in later washing procedures The following, all mcluded herem by reference, desenbe soil release polymers suitable for use m the present mvention U S 5,843,878 Gosselrnk et al , issued December 1, 199, U.S 5,834.412 Rohrbaugh et al . issued November 10. 1998, U S 5,728,671 Rohrbaugh et al , issued March 17. 1998, U S 5,691.298 Gosselrnk et al , issued November 25, 1997, U S 5.599,782 Pan et al , issued February 4. 1997, U S 5,415.807 Gosselrnk et al , issued May 16, 1995, U S 5,182.043 Monall et al , issued January 26, 1993. U S 4.956.447 Gosselrnk et al , issued September 11. 1990. U S 4.976.879 Maldonado et al issued December 11. 1990, U S 4,968,451 Scheibel et al . issued November 6, 1990. U S 4,925.577 Borcher, Sr et al , issued May 15, 1990. U S 4,861.512 Gossehnk, issued August 29. 1989, U S 4,877,896 Maldonado et al , issued October 31, 1989, U S 4,771.730 Gossehnk et al , issued October 27, 1987, U S 711.730 Gosselrnk et al , issued December 8. 1987. U S 4.721,580 Gosselrnk issued January 26. 1988, U S 4.000.093 Nicol et al . issued December 28, 1976, U S 3,959.230 Hayes, issued May 25. 1976, U S 3,893,929 Basadur. issued July 8, 1975, and European Patent Application 0 219 048, published April 22, 1987 by Kud et al Further suitable soil release agents are described m U S 4.201,824 Voilland et al , U S 4.240.918 Lagasse et al , O 4.525,524 Tung et al , U S 4,579,681 Ruppert et al . U S 4,220,918, U S 4,787.989, EP 279,134 A, 1988 to Rhone-Poulenc Chemie, EP 457.205 A to BASF (1991), and DE 2,335,044 to Umlever N V , 1974, all incorporated herem by reference LAUNDRYDETERGENTTABLETS A preferred embodiment of the present relates to laundry detergent tablets wherem the herem desenbed zwittenomc hexamethylene diamines can be used as a processmg aid or binder The detergent tablets of the present invention can be prepared simply by mixing the solid mgredients together and compressing the mixture m a conventional tablet press as used, for example, m the pharmaceutical industry Preferably the principal ingredients, in particular gelling surfactants, are used m particulate form Any liquid mgredients, for example the surfactant or suds suppresser, can be incorporated m a conventional manner mto the solid particulate mgredients The ingredients such as bmlder and surfactant can be spray-dned m a conventional manner and then compacted at a suitable pressure The detergent tablet embodiments can be made in any size or shape and can, if desired, be surface treated before coatmg, accordmg to the present mvention In the core of the tablet is mcluded a surfactant and a builder which normally provides a substantial part of the cleaning power of the tablet The term "builder" is mtended to mean all matenals which tend to remove certam ions, inter aha. calcium ion from solution, either by ion exchange, complexing, sequestratmg or precipitating said ions The particulate material used for making the tablet embodiment of the present invention can be made by any means which forms particles, particulation, inter aha. or forms granules An example of such a process is spray drying (m a co-cunent or counter cunent spray drying tower) which typically gives low bulk densities 600g/l or lower Particulate matenals of higher density can be prepared by granulation and densification in a high shear batch mixer/granulator or by a contmuous granulation and densification process (e g usmg Lodige ® CB and/or Lodige® KM mixers) Other suitable processes mclude fluid bed processes, compaction processes (e g roll compaction), extrusion, as well as any particulate matenal made by any chemical process like flocculation. crystallization sentermg. etc Individual particles can also be any other particle, granule, sphere or grain It has been surprisingly discovered that the zwittenomc hexamethylene diamines of the present invention can be added to the tablet detergent admixture as a process aid or binder The diamine and particulate matenals may be mixed together by any conventional means The mgredients can be admixed in a batch process Batchmg can be performed m suitable mixer, inter aha, a concrete mixer, Nauta mixer, nbbon mixer Alternatively the mixing process may be earned out contmuously by metering each component by weight on to a movmg belt, and blending them m one or more dmm(s) or mιxer(s) A non-gelling bmder, if desirable, can be sprayed on to the mix of some, or all of, the particulate matenals Other liquid mgredients may also be sprayed on to the mix of particulate matenals either separately or premixed For example, perfume and shinies of optical bnghteners may be sprayed A finely divided flow aid (dustmg agent such as zeolites, carbonates, silicas) can be added to the particulate matenals after spraymg the bmder, preferably towards the end of the process, to make the mix less sticky The tablets may be manufactured by usmg any compactmg process, such as tablettmg, bnquettmg, or extmsion, preferably tablettmg Suitable equipment mclude a standard smgle stroke or a rotary press (such as Courtoy ® , Korch®, Manesty®. or Bonals®) The tablets prepared accordmg to this mvention preferably have a diameter of between 40mm and 60mm, and a weight between 25 and 100 g The ratio of height to diameter (or width) of the tablets is preferably greater than 1 3, more preferably greater than 1 2 The compaction pressure used for preparing these tablets need not exceed 5000 kN/m 2 , preferably not exceed 3000 kN/ 2 . and most preferably not exceed 1000 kN/m 2 In addition to the zwittenomc diamines of the present mvention. other suitable non-gelling binders mclude synthetic organic polymers such as polyethylene glycols, polyvmylpyno dones, polyacrylates and water-soluble acrvlate copolymers The handbook of Pharmaceutical Excipients second edition, has the following bmders classification acacia, alginic acid, carbomer, carboxy methyl cellulose sodium, dextrm. ethyl cellulose, gelatm, guar gum, hydrogenated vegetable oil type I, hydroxyethyl cellulose, hydroxypropyl methylcellulose. liquid glucose, magnesium aluminum silicate, maltodextnn, methyl cellulose, polymethacrylates, povidone, sodium algmate, starch and zem Most preferable bmders also have an active cleaning function in the laundry wash such as cationic polymers, 1 e ethoxylated hexamethylene diamine quaternary compounds, bishexamethylene tnamines, or others such as pentaammes. ethoxylated polyethylene amines, maleic acrylic polymers The non-gelling bmder matenals are preferably sprayed on and hence have an appropnate meltmg pomt temperature below 70°C and preferably below 50°C so as not to damage or degrade the other active mgredients in the matnx Most prefened are non-aqueous liquid bmders (1 e not in aqueous solution) which may be sprayed m molten form However, they may also be solid bmders incorporated mto the matrix by dry addition but which have bmding properties within the tablet The tablets of the present mvention compnse from about 0 1% to about 15%, preferably to about 5%>, more preferably to about 2% by weight, of a non-gelling bmder When the bmder is non-laundry active, said bmder will typically compnse less than about 2% by weight, of the tablet It is prefened that gelling bmders. such as noniomc surfactants are avoided in their liquid or molten form Noniomc surfactants and other gelling bmders are not excluded from the compositions, but it is prefened that they be processed into the detergent tablets as components of particulate matenals. and not as liquids In a prefened embodiment of the present mvention, the tablets may then be coated so that the tablet does not absorb moisture, or absorbs moisture at only a very slow rate The coatmg is also strong so that moderate mechanical shocks to which the tablets are subjected dunng handling, packing and shipping result m no more than very low levels of breakage or attntion Finally the coatmg is preferably bnttle so that the tablet breaks up when subjected to stronger mechanical shock Furthermore it is advantageous if the coatmg matenal is dissolved under alkaline conditions, or is readily emulsified by surfactants This contributes to avoidmg the problem of visible residue m the wmdow of a front-loading washing machme dunng the wash cycle, and also avoids deposition of un-dissolved particles or lumps of coatmg matenal on the laundry load Non-limitmg examples of suitable coatmg matenals mclude dicarboxylic acids, for example, dicarboxylic acids selected from the group consistmg of oxalic acid, malonic acid, succinic acid, glutanc acid, adipic acid, pime c acid, subenc acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tπdecanedioic acid and mixtures thereof The coatmg matenal has a meltmg pomt preferably of from 40°C to 200°C In another prefened embodiment of the present invention the tablets further compnses an effervescent Effervescency as defined herein means the evolution of bubbles of gas from a liquid, as the result of a chemical reaction between a soluble acid source and an alkah metal carbonate, to produce carbon dioxide gas Examples of acid and carbonate sources and other effervescent systems may be found m (Pharmaceutical Dosage Forms Tablets Volume 1 Page 287 to 291) An effervescent may be added to the tablet mix m addition to the detergent mgredients The addition of this effervescent to the detergent tablet improves the dismtegration time of the tablet The amount will preferably be between 5%, preferably from 10% to 20% by weight, of the tablet Preferably the effervescent should be added as an agglomerate of the different particles or as a compact, and not as separated particles Due to the gas created by the effervescence potential m the tablet, the tablet can have a higher D F S and still have the same dismtegration time as a tablet without effervescency When the D F S of the tablet with effervescency is kept the same as a tablet without, the dismtegration of the tablet with effervescency will be faster Further dispersion aid could be provided by using compounds such as sodium acetate or urea A list of suitable dispersion aid may also be found m Pharmaceutical Dosage Forms Tablets, Volume 1. Second edition. Edited by H A Lieberman et all, ISBN 0-8247-8044-2 METHOD OF USE The present invention further relates to a method for removmg hydrophilic soils form fabnc, preferably clothing, said method compnsmg the step of contactmg fabπc m need of cleaning with an aqueous solution of a laundry detergent composition compnsmg a) from about 0 01 % by weight of a zwittenomc hexamethylene diamine according to the present mvention, b) from about 0 01% by weight, preferably from about 0 1% more preferably from about 1% to about 60%, preferably to about 30% by weight, of a surfactant system, said surfactant system compnsmg l) from 0 01%, preferably from about 0 1% more preferably from about 1% to about 100%, preferably to about 80%> by weight, preferably to about 60%. most preferably to about 30% by weight, of one or more amomc surfactants, said amomc surfactants selected form the group consistmg of lmear alkyl benzene sulphonates, mid-cham branched alkyl benzene sulphonates, lmear alkyl sulfates, mid-cham branched sulfates, l ear alkyleneoxy sulfates, mid-cham branched alkyleneoxy sulfates, and mixtures thereof, n) optionally, from 0 01%, preferably from about 0 1% more preferably from about 1% to about 100%, preferably to about 80% by weight, preferably to about 60%. most preferably to about 30%> by weight, of one or more noniomc surfactants selected from the group consistmg of alcohols, alcohol ethoxylates, polyoxyalkylene alkylamide, and mixtures thereof, c) optionally, from about 1%, preferably from about 5% to about 80%, preferably to about 50% by weight, of a peroxygen bleaching system compnsmg l) from about 40%, preferably from about 50%, more preferably from about 60% to about 100%, preferably to about 95%, more preferably to about 80%. by weight, of the bleaching system, a source of hydrogen peroxide, n) optionally from about 0 1%, preferably from about 0 5% to about 60%. preferably to about 40%> by weight, of the beaching system, a beach activator, in) optionally from about 1 ppb (0 0000001%), more preferably from about 100 ppb (0 00001%), yet more preferably from about 500 ppb (0 00005%), still more preferably from about 1 ppm (0 0001%) to about 99 9%>, more preferably to about 50%, yet more preferably to about 5%, still more preferably to about 500 ppm (0 05%) by weight of the composition, of a transition-metal bleach catalyst, IV) optionally from about 0 1% by weight, of a pre-formed peroxygen bleachmg agent, and d) the balance earners and other adjunct mgredients Preferably the aqueous solution compnses at least about 0 01 %>, preferably at least about % by weight, of said laundry detergent composition The compositions of the present invention can be suitably prepared by any process chosen by the formulator, non-limiting examples of which are desenbed in U S 5,691,297 Nassano et al . issued November 11, 1997, U S 5,574,005 Welch et al , issued November 12. 1996. U S 5.569.645 Dinniwell et al , issued October 29, 1996, U S 5,565,422 Del Greco et al . issued October 15, 1996, U S 5,516.448 Capeci et al , issued May 14. 1996. U S 5,489,392 Capeci et al . issued Febmary 6, 1996, U S 5,486,303 Capeci et al . issued January 23, 1996 all of which are incorporated herem by reference The following is a non-limiting example of laundry detergent compositions accordmg to the present mvention m the form of a laundry tablet TABLE I weight % 1 Amomc surfactant agglomeration compπsmg 38% surfactant, 22% zeolite, 40%> sodium carbonate 2 Nomonic surfactant agglomeration compnsmg 26% surfactant. 48% zeolite, 26%> sodium carbonate 3 Catiomc surfactant agglomeration compnsmg 24% surfactant, 64% zeolite, 12%> sodium sulphate 4 Bleach activator system compnsmg 81% TAED, 17% acryhc/maleic copolymer (acid form), 2% moisture 5 Encapsulated zmc phthalocyanme (10%) accordmg to U S 4,033,718, Holcombe et al , issued July 5, 1977 6 Zeolite 7 Admixture comprising 11 5% sihcone oil ex Dow Corning and 88 5% starch 8 Layered silicate compnsmg 78% SKS-6 ex Hoechst and 22% citnc acid 9 Dye transfer inhibitor agglomerate compnses 21 %> PVNO/PVPVI. 61 % zeolite and 18% sodium carbonate 10 Perfume encapsulate compnses 50%o perfume and 50% starch 11 C 12 -C15 alkyl ethoxy (7 0) alcohol and 17% by weight, of polyethylene glycol havmg an average molecular weight of about 4000 12 Polyethylene glycol havmg an average molecular weight of 200 13 Accordmg to Example 1 14 Soil release polymer accordmg to U S 5,415,807 Gosselrnk et al , issued May 16, 1995 15 Balance to 100% can, for example, include mmors like, processmg aids, additional water, and fillers, mcludmg CaCθ3, talc, silicates, etc

Claims: WHAT IS CLAIMED IS A hydrophilic soil dispersant and processmg aid havmg the formula wherem R is an alkyleneoxy unit havmg the formula — (R'o i 2 wherem R 1 is C 2 -C 4 lmear alkylene, C 3 -C 4 branched alkylene, and mixtures thereof, R 2 is hydrogen, an amomc umt. and mixtures thereof, the index x has the value of from 15 to 35, Q is a quatermzmg umt mdependently selected from the group consistmg of -Cg lmear alkyl, C 3 -C 8 branched alkyl. benzyl, and mixtures thereof, X is a water soluble anion m sufficient amount to provide electronic neutrality A compound accordmg to Claim 1 wherem R is an ethyleneoxy umt havmg the formula (CH 2 CH 2 0) 2 R 2 is hydrogen, -S0 3 M, or mixtures thereof. M is selected form the group consistmg of alkah metal salts, alkaline earth metal salts, ammonium salts, transition metal salts, and mixtures thereof, the mdex x represents an average number of ethyleneoxy umts, said average ranging from 20 to 30 umts per backbone mtrogen substitution A compound accordmg to either Claim 2 or 3 havmg the formula A granular laundry detergent composition compnsmg a) from 0 01 % by weight, of a zwittenomc hexamethylene diamme havmg the formula wherem R is an alkyleneoxy umt havmg the formula — (R'O)^ 2 wherem R 1 is C 2 -C 4 lmear alkylene, C 3 -C 4 branched alkylene, and mixtures thereof, R 2 is hydrogen, an amomc umt, and mixtures thereof, the mdex x has the value of from 15 to 35, Q is a quatemizmg unit mdependently selected from the group consistmg of -Cg lmear alkyl, C 3 -C δ branched alkyl, benzyl, and mixtures thereof, X is a water soluble amon m sufficient amount to provide electromc neutrality, b) from 0 01% by weight, of a surfactant system compnsmg one or more surfactants selected from the group consistmg of nomomc, amomc, catiomc, zwittenomc, ampholytic surfactants, and mixtures thereof, and c) the balance earners and adjunct mgredients A composition accordmg to Claim 4 wherem said surfactant system compnses l) from 0 01 % by weight, of a surfactant selected from the group consistmg of alkyl sulfate surfactants, alkoxy sulfate surfactants, mid-cham branched alkyl sulfate surfactants, mid-cham branched alkoxy sulfate surfactants, mid-cham branched aryl sulfonate surfactants, and mixtures thereof, n) from 0 01% by weight, of one or more aryl sulphonate amomc surfactants. m) from 0 01 % by weight, of one or more nomomc surfactants A composition according to either of Claim 4 or 5 further compnsmg from 1% to 80% by weight, of a detergent bmlder A composition accordmg to any of Claims 4-6 further comprising from 1%> bv weight, of a peroxygen bleaching system compnsmg l) from 40%) by weight, of said bleaching system, a source of hydrogen peroxide, n) optionally from 0 1% by weight, of said beachmg system, a beach activator in) optionally from 1 ppb (0 0000001%) by weight of said beaching system, of a transition-metal bleach catalyst, and IV) optionally from 0 1 % by weight, of said beachmg system, a pre-formed peroxygen bleaching agent A laundry detergent composition in the form of a tablet compnsmg a) from 0 01 % by weight, of a zwittenomc hexamethylene diamine havmg the formula wherem R is an alkyleneoxy unit havmg the formula — (R'o i 2 wherem R 1 is C 2 -C 4 lmear alkylene, C 3 -C 4 branched alkylene, and mixtures thereof. R 2 is hydrogen, an amomc umt, and mixtures thereof, the mdex x has the value of from 15 to 35, Q is a quatermzmg umt mdependently selected from the group consistmg of Cι-C 8 lmear alkyl, C 3 -Cg branched alkyl. benzyl, and mixtures thereof, X is a water soluble anion in sufficient amount to provide electromc neutrality, b) from 0 01%, preferably from 0 1% more preferably from 1% to 100%, preferably to 80% by weight, preferably to 60%, most preferably to 30% by weight, of a surfactant system compnsmg one or more surfactants selected from the group consistmg of nomomc, amomc. cationic, zwittenomc, ampholytic surfactants, and mixtures thereof. c) from 1% to 80% by weight, of a detergent bmlder, d) from 0 1% by weight, of a bmder or processmg aid, and e) the balance earners and adjunct mgredients A composition accordmg to Claim 8 wherem said diamme has the formula

Inventors: PRICE KENNETH NATHAN, PRICE, KENNETH, NATHAN
Applicants: PROCTER & GAMBLE, THE PROCTER & GAMBLE COMPANY
Application year: 2001
Main classification: C11D1
IPC codes: C11D1, C11D3, C11D17