AU6935700A

AU6935700A - Color safe laundry methods employing zwitterionic formulation components

Info

Publication number: AU6935700A
Application number: AU69357/00A
Authority: AU
Inventors: Robert Richard Dykstra; Patti Jean Kellett
Original assignee: Procter and Gamble Co
Current assignee: Procter and Gamble Co
Priority date: 1999-08-27
Filing date: 2000-08-25
Publication date: 2001-03-26
Also published as: JP2003508589A; TR200200457T2; AR028165A1; EP1206518A1; CZ2002687A3; MA25544A1; BR0013643A; MXPA02002126A; WO2001016278A1; CN1382206A; CA2381924A1

Description

WO 01/16278 PC'T/USU/2zi1 COLOR SAFE LAUNDRY METHODS EMPLOYING ZWITTERIONIC FORMULATION COMPONENTS 5 Field of the Invention The present invention relates to zwitterionic organic catalyst compound bleach systems and methods for using such bleach systems to provide increased color safety during laundering of 10 fabrics, especially colored fabrics. More particularly, this invention relates to bleach systems comprising zwitterionic, quaternary imine bleach boosting compounds, zwitterionic, quaternary oxaziridinium bleaching species and mixtures thereof, and methods employing such bleach systems in the laundering of fabrics, especially colored fabrics. 15 Background of the Invention Oxygen bleaching agents have become increasingly popular in recent years in household and personal care products to facilitate stain and soil removal. Bleaches are particularly desirable for their stain-removing, dingy fabric cleanup, whitening and sanitization properties. Oxygen bleaching agents have found particular acceptance in laundry products such as detergents, in 20 automatic dishwashing products and in hard surface cleansers. Oxygen bleaching agents, however, are somewhat limited in their effectiveness. Some frequently encountered disadvantages include color damage on fabrics and damage to laundry appliances, specifically rubber hoses these appliances may contain. In addition, oxygen bleaching agents tend to be extremely temperature rate dependent. Thus, the colder the solution in which they are employed, 25 the less effective the bleaching action. Temperatures in excess of 60 oC are typically required for effectiveness of an oxygen bleaching agent in solution. To solve the aforementioned temperature rate dependency, a class of compounds known as "bleach activators" has been developed. Bleach activators, typically perhydrolyzable acyl compounds having a leaving group such as oxybenzenesulfonate, react with the active oxygen 30 group, typically hydrogen peroxide or its anion, to form a more effective peroxyacid oxidant. It is the peroxyacid compound which then oxidizes the stained or soiled substrate material. However, bleach activators are also somewhat temperature dependent. Bleach activators are more effective at warm water temperatures of from about 40 oC to about 60 oC. In water temperatures of less than about 40 oC, the peroxyacid compound loses some of its bleaching effectiveness. 1 U.S. Patent Nos. 5,576,282 and 5,817,614 both to Miracle et al. disclose attempts at developing bleach systems comprising zwitterionic organic catalyst compounds which are effective in lower temperature water conditions and are relatively safe on colors. Although the bleach systems disclosed in this patent provide enhanced color-safety over traditional organic 5 catalyst bleach systems, such as cationic, organic catalyst bleach systems examples of which are disclosed in U.S. Patent Nos. 5,360,568, 5,360,569, 5,370,826 and 5,482,515 all to Madison et al., consumers desire more color-safe bleach products. A serious disadvantage associated with methods of using conventional organic catalysts, examples of which are described in U.S. Patent Nos. 5,360,568, 5,360,569 and 5,370,826 all to 10 Madison et al., and U.S. Patent Nos. 5,576,282 and 5,817,614, both to Miracle et al., is that such organic catalysts are used at too high an in-use concentration. For example, the method used in U.S. Patent No. 5,482,515 describes a method wherein the oxygen transfer agent (an organic catalyst compound) is present from about 0.01 ppm to 300 ppm, with the preferred concentration range from 5 ppm to about 100 ppm per liter of medium. Such a concentration can result in 15 unacceptable color damage to fabric dyes. In addition, such a high concentration can lead to too much available oxygen ("AvO") consumption, leading to an altered performance profile (i.e., changing the balance between peracid bleaching and organic catalyst bleaching). It may be possible to increase stain bleaching performance with increased organic catalyst concentration but only at the cost of dye damage and at some point the dye damage becomes unacceptable. 20 Accordingly, there is a need to maximize the ratio of stain bleaching performance to dye damage of the organic catalyst bleach systems. In light of the foregoing, it is evident that there still exists a need for zwitterionic organic catalyst compound bleach systems and laundry methods employing such zwitterionic organic catalyst compound bleach systems that provide effective bleaching in lower temperature water 25 conditions and provide superior color-safety properties compared to the laundry methods employing the organic catalyst bleach systems disclosed in the prior art, as discussed above; and there is a need to maximize the ratio of stain bleaching performance to dye damage of the organic catalyst bleach systems. 30 Summary of the Invention The present invention fulfills the need discussed above. The present invention provides zwitterionic organic catalyst compound bleach systems and methods for laundering fabrics, especially colored fabrics, employing such bleach systems. The zwitterionic organic catalyst compounds of the present invention, and bleach systems 35 comprising such zwitterionic organic catalyst compounds provide increased bleaching 2 WU U1/10275 FIT/UNUU Z.JZI effectiveness in lower temperature wash applications while providing improved color safety, resulting in increased bleaching effectiveness and color safety as compared to conventional zwitterionic and cationic organic catalyst bleach systems. The zwitterionic organic catalyst compound bleach systems of the present invention act in conjunction with or without, preferably 5 with, conventional peroxygen bleaching sources to provide the above-mentioned increased bleaching effectiveness and superior fabric color safety. More particularly, this invention relates to zwitterionic organic catalyst compounds such as zwitterionic, quaternary imine bleach boosting compounds, zwitterionic, quaternary oxaziridinium bleaching species, bleach systems comprising such zwitterionic organic catalyst 10 compounds and laundry methods employing such bleach systems. Nonlimiting examples of the benefits provided by the zwitterionic organic catalyst compounds and bleach systems employing same include superior bleaching effectiveness even in lower temperature water, and improved color safety. In one aspect of the present invention, a zwitterionic organic catalyst bleach system which 15 demonstrates effective bleaching in lower water temperature and provides a superior color-safety profile compared to the conventional organic catalyst bleach systems is provided. In accordance with another aspect of the present invention, a zwitterionic organic catalyst bleach system comprising one or more zwitterionic organic catalyst compounds, as described hereinafter, in conjunction with or without a peroxygen source is provided. 20 In accordance with yet another aspect of the present invention, a zwitterionic organic catalyst bleach system comprising one or more zwitterionic organic catalyst compounds, as described hereinafter, in conjunction with a peracid is provided. In accordance with still yet another aspect of the present invention, a method for laundering a fabric, especially a colored fabric, in need of laundering comprising contacting the 25 fabric with a laundry solution comprising one or more zwitterionic organic catalyst compound bleach systems described herein is provided. In accordance with even still yet another aspect of the present invention, a bleach system of the present invention as made by the process comprising: a) providing a wash solution; and 30 b) adding to said wash solution a bleach composition comprising an amount of zwitterionic organic catalyst compound of the present invention such that the resulting concentration of the zwitterionic organic catalyst compound in said wash solution is from about 0.001 ppm to about 5 ppm, is provided. Accordingly, it is an object of the present invention to provide: zwitterionic organic 35 catalyst compound bleach systems , which demonstrate improved performance even in lower 3 WO 01/16278 PCT/US00/23321 temperature water solutions and improved color safety; and a method for laundering a fabric, especially a colored fabric, using one or more of the zwitterionic organic catalyst compound bleach systems described herein. These and other objects, features and advantages of the present invention will be 5 recognized by one of ordinary skill in the art from the following description and the appended claims. All percentages, ratios and proportions herein are on a weight basis unless otherwise indicated. All documents cited herein are hereby incorporated by reference. 10 Detailed Description of the Invention The present invention discloses highly useful zwitterionic organic catalyst compounds, bleach systems comprising such zwitterionic organic catalyst compounds, and methods for laundering fabrics, especially colored fabrics, employing such bleach systems. The zwitterionic organic catalyst compounds of the present invention, and bleach systems 15 comprising such zwitterionic organic catalyst compounds provide increased bleaching effectiveness in lower temperature wash applications while providing improved color safety, resulting in increased bleaching effectiveness and color safety as compared to conventional cationic and zwitterionic organic catalyst bleach systems. The zwitterionic organic catalyst compound bleach systems of the present invention act in conjunction with or without, preferably 20 with conventional peroxygen bleaching sources to provide the above-mentioned increased bleaching effectiveness and superior fabric color safety. DEFINITIONS "Peroxygen source" as used herein means materials that generate peroxygen compounds, which can include the peroxygen compounds themselves. Examples include, but are not limited 25 to, bleach activators, peracids, percarbonate, perborate, hydrogen peroxide, bleach boosting compounds, and/or bleaching species (e.g., oxaziridiniums). "Peroxygen compounds" as used herein includes peracids and peroxides (e.g., hydrogen peroxide, alkyl hydroperoxides, etc. "Peracid" as used herein means a peroxyacid such as peroxycarboxylic acid and/or 30 peroxymonosulfuric acid (tradname OXONE) and their salts. ZWITTERIONIC ORGANIC CATALYST COMPOUNDS The zwitterionic organic catalyst compounds and bleach systems comprising such zwitterionic organic catalyst compounds of the present invention bleach system preferably are employed in methods for laundering fabrics, especially colored fabrics, in need of laundering. 35 Such methods typically encompass bleaching a stained substrate, preferably a colored fabric, in an 4 WO 01/16278 PCT/US00/23321 aqueous medium with a peroxygen source and with a zwitterionic organic catalyst compound whose structure is as defined hereinafter wherein the aqueous medium contains active oxygen from the peroxygen compound from about 0.05 to about 250 ppm per liter of medium, and the zwitterionic organic catalyst compound from 0.001 ppm to about 2 ppm, preferably from about 5 0.01 ppm to about 2 ppm, more preferably from about 0.1 ppm to about 1.5 ppm, and most preferably from about 0.2 ppm to about 1 ppm. In the bleaching systems of the present invention, when present, the molar ratio of said peroxygen compound to zwitterionic organic catalyst compound is preferably greater than 1:1, more preferably the molar ratio ranges from about 30,000:1 to about 10:1, even more preferably 10 from about 10,000:1 to about 50:1, yet even more preferably from about 5,000:1 to about 100:1, still even more preferably from about 3,500:1 to about 150:1. The molar ratio of peroxygen compound to zwitterionic organic catalyst compound does influence the color safety properties of a bleach system. However, the ppm concentration of the zwitterionic organic catalyst compound in the bleach system is the primary factor in establishing 15 the bleach systems' color safety properties. A product can deliver, for example, in an aqueous medium a 1 ppm concentration of a zwitterionic organic catalyst compound with a molecular weight of 300, and a 66 ppm concentration of NOBS (35 ppm pernonanoic acid assuming 100% perhydrolysis) and a 66 ppm concentration of percarbonate (21 ppm hydrogen peroxide) to give a molar ratio of peroxygen 20 compound to zwitterionic organic catalyst compound of 246:1. A product which delivers 240 ppm of TAED (forming 160 ppm of peracetic acid) and 865 ppm of percarbonate (forming 281 ppm of hydrogen peroxide) gives a molar ratio of peroxygen compound to zwitterionic organic catalyst of 3142:1. At 0.25 ppm of zwitterionic organic catalyst compound, the molar ratio would be 12568:1. 25 In addition to the molar ratios of peroxygen compound to zwitterionic organic catalyst compound, the bleach systems of the present invention can be characterized by the molar ratio of a peracid to zwitterionic organic catalyst compound. Preferably, the molar ratio of peracid to zwitterionic organic catalyst compound is greater than 1:1, more preferably about 5,000:1 to about 5:1, still even more preferably from about 2,000:1 to about 10:1, and even from about 30 1,000:1 to 15:1. The preferred molar ratios of peracid to zwitterionic organic catalyst compound vary with the wash conditions. For example, under European wash conditions (typically comprising from about 4500 ppm to 5000 ppm of detergent components in the wash water), the preferred molar ratio of peracid to zwitterionic organic catalyst compound is from about 2,000:1 to about 150:1. 35 Whereas, under North American wash conditions (typically comprising from about 850 ppm to 5 WO 01/16278 PCI'/U5UU/23321 about 1000 ppm of detergent components in the wash water), the preferred molar ratio of peracid to zwitterionic organic catalyst compound is from about 150:1 to about 5:1. Yet in addition to the molar ratios of peracid to zwitterionic organic catalyst compound, the bleach system of the present invention can be characterized by the molar ratio of a 5 hydrophobic peracid to zwitterionic organic catalyst compound, preferably a hydrophobic zwitterionic organic catalyst compound. Preferably the molar ratio of the hydrophobic peracid to zwitterionic organic catalyst compound is from about 500:1 to about 15:1, more preferably about 350:1 to about 20:1, still even more preferably from about 200:1 to about 25:1, and even more preferably from about 100:1 to about 35:1. 10 Preferably, the zwitterionic organic catalyst compounds of the present invention, more preferably the iminium-based zwitterionic organic catalyst compounds of the present invention, include, but are not limited to, bleach boosting compounds. I. Bleach Boosting Compounds - The bleach boosting compounds, preferably iminium based bleach boosting compounds, of the present invention include, but are not limited to, 15 aryliminium zwitterions, which have a net charge of from about +3 to about -3. Aryliminium Zwitterions - The aryliminium zwitterions, which have a net charge of from about +3 to about -3, are represented by the formula [II]:

R

5 6

TO

R N [II] 20 where R 5

-R

7 are independently selected from substituted or unsubstituted radicals selected from the group consisting of H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, heterocyclic ring, silyl, nitro, halo, cyano, sulfonato, alkoxy, keto, carboxylic, and carboalkoxy radicals; also present in this formula is the radical represented by the formula: 25 8 - To Zp where ZP is covalently bonded to To, and Zp- is selected from the group consisting of -CO2-, -SO3-, -OSO3-, -SO 2- and -OSO 2- and p is either 1, 2 or 3; To is selected from the group 30 consisting of substituted or unsubstituted, saturated or unsaturated alkyl, cycloalkyl, aryl, alkaryl, aralkyl, and heterocyclic ring. 6 WO I01/16278 cI7UUU/23321I Preferably, the aryliminium zwitterions, which have a net charge of from about +3 to about -3, are represented by the formula [XII]: 28 G R [26 R27 n To 25 R 5 [XII] where m is 1 to 3 when G is present and m is 1 to 4 when G is not present; and n is an integer from 0 to 4; each R 2 6 is independently selected from a substituted or unsubstituted radical selected from the group consisting of H, alkyl, cycloalkyl, aryl, fused aryl, heterocyclic ring, 10 fused heterocyclic ring, nitro, halo, cyano, sulfonato, alkoxy, keto, carboxylic, and carboalkoxy radicals, and any two vicinal R 2 6 substituents may combine to form a fused aryl, fused carbocyclic or fused heterocyclic ring; R 2 5 may be a substituted or unsubstituted radical selected from the group consisting of H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, heterocyclic ring, silyl, nitro, halo, cyano, sulfonato, alkoxy, keto, carboxylic, and carboalkoxy radicals; also present in 15 this formula is the radical represented by the formula: To~~ where Zp- is covalently bonded to To, and Zp- is selected from the group consisting of 20 -CO2-, -SO3-, -OSO3-, -SO 2- and -OSO 2 - and p is either 1, 2 or 3; To is selected from the group consisting of: 29 I -(C)q 1 29 R wherein q is an integer from 1 to 8; R 2 9 is independently selected from substituted or 25 unsubstituted radicals selected from the group consisting of linear or branched H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, alkylene, heterocyclic ring, alkoxy, arylcarbonyl, carboxyalkyl and amide groups; G is selected from the group consisting of: (1) -0- ; (2) -N(R 3 0)-; and (3) N(R 30

R

3 1 )-; R 2 7 , R 28 , R 3 0 and R 3 1 are substituted or unsubstituted radicals independently selected from the group consisting of H, oxygen, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, 7 WO 01/16278 PCUT/USUU/2i321 alkylenes, heterocyclic ring, alkoxys, arylcarbonyl groups, carboxyalkyl groups and amide groups; any of R 2 5 , R 2 6 , R 2 7 , R 2 8 , R 3 0 and R 3 1 may be joined together with any other of R 2 5 ,

R

2 6 , R 2 7 , R 2 8 , R 3 0 and R 31 to form part of a common ring; any geminal R 27 - R 2 8 may combine to form a carbonyl; any vicinal R 2 7 - R 31 may join to form unsaturation; and wherein 5 any one group of substituents R 27 - R 31 may combine to form a substituted or unsubstituted fused unsaturated moiety. More preferred aryliminium zwitterions, which have a net charge of from about +3 to about -3, as represented by the formula [XII], include those of formula [XII] where R 2 5 is H or methyl, and for the radical represented by the formula: 10 e Zp- is -C02-, -SO 3 - or -OS03-, and p is 1 or 2. Most preferably, the aryliminium zwitterions are represented by the formula [XIIa]: I e R OS03 R 44 42 15 R [XIIa] wherein R 4 1

-R

4 4 may be independently selected from a substituted or unsubstituted radical selected from the group consisting of H, linear or branched, substituted or unsubstituted alkyl, 20 cycloalkyl, alkaryl, aryl, aralkyl, alkylene, alkoxy,radicals, provided that any of R 4 1

-R

4 4 may be joined together with any other of R 4 1

-R

4 4 to form part of a common ring; more preferred, at least one, even more preferably two of R 4 1

-R

44 is H. Most preferably, R 4 1 and/or R 44 is a linear or branched C 1 - C16 alkyl or cycloalkyl, even more preferably the sum of the carbon atoms within

R

4 1 and R 44 is from 5-15, most preferably 6-13. 25 II. Bleaching Species - The bleaching species (oxaziridiniums) may also be used directly in accordance with the present invention. The bleaching species of the present invention include, but are not limited to, oxaziridinium zwitterions, which have a net charge of from about +3 to about -3. The aryliminium zwitterions of the present invention act in conjunction with a peroxygen 30 source, when present, to increase bleaching effectiveness. Without being bound by theory, it is believed that the aryliminium zwitterions react with the peroxygen source to form a more active bleaching species, a zwitterionic quaternary oxaziridinium compound, as represented by the following reaction by way of example: 8 WU 01/10278 1C I/UNUU/Z i21 R

R

1' 2 2- RCO R2 N 0 ' CE

R

0 RC RC 2 The zwitterionic oxaziridinium compounds can have an increased or preferred activity at lower temperatures relative to the peroxygen compound. Oxaziridinium Zwitterions - The oxaziridinium zwitterions, which have a net charge of 5 from about +3 to about -3, are represented by formula [IV]: RN 0 P R6 [IV] where R 5

'-R

7 ' are independently selected from substituted or unsubstituted radicals selected from 10 the group consisting of H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, heterocyclic ring, silyl, nitro, halo, cyano, sulfonato, alkoxy, keto, carboxylic, and carboalkoxy radicals; also present in this formula is the radical represented by the formula: - T'o-Zp 15 where Z'p,- is covalently bonded to T'o, and Z'p- is selected from the group consisting of -CO2, SO 3 -, -OSO3", -SO 2- and -OSO 2 - and p is either 1, 2 or 3; T'o is selected from the group consisting of substituted or unsubstituted, saturated or unsaturated alkyl, cycloalkyl, aryl, alkaryl, aralkyl, and heterocyclic ring. 20 Preferably, the oxaziridinium zwitterions, which have a net charge of from about +3 to about -3, are represented by formula [XIV]: 28' GR 26, G R2 7 ' [R]6 I ? 250 0 R [XIV] wherein m is 1 to 3 when G is present and m is 1 to 4 when G is not present; and n is an integer 25 from 0 to 4; each R 2 6 ' is independently selected from a substituted or unsubstituted radical 9 WO 01/16278 YLIT/UUU/1ZLJI selected from the group consisting of H, alkyl, cycloalkyl, aryl, fused aryl, heterocyclic ring, fused heterocyclic ring, nitro, halo, cyano, sulfonato, alkoxy, keto, carboxylic, and carboalkoxy radicals, and any two vicinal R 26 ' substituents may combine to form a fused aryl, fused carbocyclic or fused heterocyclic ring; R 2 5' may be a substituted or unsubstituted radical selected 5 from the group consisting of H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, heterocyclic ring, silyl, nitro, halo, cyano, sulfonato, alkoxy, keto, carboxylic, and carboalkoxy radicals; and also present in this formula is the radical represented by the formula: e 10 - To-Z'p where Z'p- is covalently bonded to T'o, and Z'p,- is selected from the group consisting of -CO2, SO 3 , -OSO3-, -SO 2- and -OSO2-, and a is either 1 or 2; T'o is selected from the group consisting of: 15

R

2 9 ' I -(C)q 29' R wherein q is an integer from 1 to 8; R 29 ' is independently selected from substituted or unsubstituted radicals selected from the group consisting of linear or branched H, alkyl, 20 cycloalkyl, alkaryl, aryl, aralkyl, alkylene, heterocyclic ring, alkoxy, arylcarbonyl, carboxyalkyl and amide groups, provided that all R 2 9 ' groups are not independently selected to be H; G is selected from the group consisting of: (1) -0- ; (2) -N(R 3 0 ')-; and (3) -N(R 3 0

'R

3 1')-; R 27 ', R 2 8 ',

R

30 ' and R 3 1 ' are substituted or unsubstituted radicals independently selected from the group consisting of H, oxygen, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, alkylenes, heterocyclic ring, 25 alkoxys, arylcarbonyl groups, carboxyalkyl groups and amide groups; any of R 2 5 ', R 26 ' , R 2 7 ',

R

2 8

'

,

R

30 ' and R 3 1 ' may be joined together with any other of R 2 5 ' , R 2 6 ' , R 2 7 ', R 28' , R 30 ' and

R

3 1' to form part of a common ring; any geminal R 2 7' - R 2 8 ' may combine to form a carbonyl; any vicinal R 27 ' - R 3 1 ' may join to form unsaturation; and wherein any one group of substituents

R

2 7

'

- R 3 1 ' may combine to form a substituted or unsubstituted fused unsaturated moiety. 30 More preferred oxaziridinium zwitterions, which have a net charge of from about +3 to about -3, as represented by the formula [XIV], include those of formula [XIV] where R 25 ' is H or methyl, and for the radical represented by the formula: 10 WO 01/16278 PCT/US00/23321

-

To-Z' Z'P- is -C0 2 -, -SO 3 - or -0S03-, and p is 1 or 2. 5 Most preferably, the oxaziridinium zwitterions are represented by the formula [XIVa]:

OSO

e R44

N

4 RC 43 R4 O iR R 0 [XIVa] 10 wherein R 4 1

-R

44 may be independently selected from a substituted or unsubstituted radical selected from the group consisting of H, linear or branched, substituted or unsubstituted alkyl, cycloalkyl, alkaryl, aryl, aralkyl, alkylene, alkoxy,radicals, provided that any of R 4 1

-R

4 4 may be joined together with any other of R 4 1

-R

44 to form part of a common ring; more preferred, least one, even more preferably two of R 4 1

-R

44 is H. Most preferably, R 4 1 and/or R 4 4 is a linear or 15 branched Cl - C16 alkyl or cycloalkyl, even more preferably the sum of the carbon atoms within

R

4 1 and R 4 4 is from 5-15, most preferably 6-13. Concentration of Organic Catalyst Compounds - The zwitterionic organic catalyst compounds (bleach boosting compounds and bleaching species) of the present invention may be and preferably are added to a wash solution, typically aqueous wash solution, in levels of from 20 about 0.00001% (0.0001 ppm) to about 10% (100 ppm) by weight of the composition, and preferably from about 0.0001% (0.001 ppm) to about 1% (10 ppm) by weight of the composition, more preferably from about 0.001% (0.01 ppm) to about 0.5% (5 ppm), even more preferably from about 0.004% (0.04 ppm) to about 0.25% (2.5 ppm). Most preferably from about 0.01% (0.1 ppm) to about 0.1% (1 ppm). 25 The conversion values (in ppm) are provided for exemplary purposes, based on an in-use product concentration of 1000 ppm. A 1000 ppm wash solution of a product containing 0.2% organic catalyst compound by weight results in a organic catalyst compound concentration of 2 ppm. Similarly, a 3500 ppm wash solution of a product containing 0.2% organic catalyst compound by weight results in a organic catalyst compound concentration of 6.5 ppm. 30 DECOMPOSITION OF ORGANIC CATALYSTS The organic catalysts, specifically the bleach boosting compounds of the present invention are susceptible to decomposition by various decomposition pathways including, but not 11 WO UI/1oZ78 YrL 1/UUU/JZ.ZI limited to, the aromatization pathway. The aromatization (decomposition) reaction of 6 membered ring boosters is well known in the art, as exemplified, without being limited by theory, in Hanquet et al., Tetrahedron 1993, 49, pp. 423-438. Other means of decomposition include, but are not limited to, attack on the bleach boosting compound and/or on the bleaching species by 5 nucleophiles, including but not limited to attack by hydroxide anion, perhydroxide anion, carboxylate anion, percarboxylate anion and other nucleophiles present under in-wash conditions. METHODS FOR DELAYED (CONTROLLED) ADDITION OF ORGANIC CATALYST COMPOUNDS It has surprisingly been found with organic catalyst compounds of limited lifetime, that 10 the addition of organic catalyst compounds by a delivery means to a wash solution after a fabric has been added to a wash solution, especially a wash solution that contains a peroxygen source, provides enhanced bleaching compared to the addition of such organic catalyst compounds to the wash solution before a fabric has been added to the wash solution. It is believed, without being limited by theory, that the organic catalyst compound undergoes decomposition in the wash 15 solution prior to the introduction of the fabric load. One method for improving the performance of organic catalyst compounds is to delay the addition of the organic catalyst compound of the present invention to the wash solution. Another method of improving the performance of organic catalyst compounds is to use an organic catalyst compound with increased stability to the wash conditions. Methods for delayed (controlled) addition of organic catalyst compounds are more 20 fully described in copending and co-owned U.S. Provisional Patent Application entitled "Controlled Availability of Formulation Components, Compositions and Laundry Methods Employing Same" filed August 27, 1999 (P&G Attorney Docket Number 7749P). BLEACH SYSTEMS COMPRISING ZWITTERIONIC ORGANIC CATALYST COMPOUNDS In addition to the use of zwitterionic organic catalyst compounds discussed above, the 25 zwitterionic organic catalyst compounds of the present invention may be employed in conjunction with or without, preferably with a peroxygen source in other bleach systems, regardless of their form. For example, the zwitterionic organic catalyst compounds may be employed in a laundry additive product. In the bleach systems of the present invention, the peroxygen source may be present in levels of from about 0.1% to about 60% by weight of the composition, and preferably 30 from about 1% to about 40% by weight of the composition. In a composition, the organic catalyst compound may be present from about 0.00001% to about 10% by weight of the system, and preferably from about 0.0001% to about 1% by weight of the system, more preferably from about 0.001% to about 0.5%, even more preferably from about 0.004% to about 0.25%. Most preferably from about 0.01% to about 0.1%. 12 WU UI/IOL/5 r 1/U3UU/Laj j1 The bleach systems of the present invention may be advantageously employed in laundry applications, hard surface cleaning, automatic dishwashing applications, as well as cosmetic applications such as dentures, teeth, hair and skin. However, due to the unique advantages of increased color safety and increased effectiveness in cold and possibly warm water solutions due 5 to possible increased stability, the organic catalyst compounds of the present invention are ideally suited for laundry applications such as the bleaching of fabrics through the use of bleach containing detergents or laundry bleach additives. Furthermore, the bleach boosting compounds of the present invention may be employed in both granular and liquid compositions. The zwitterionic organic catalyst compounds and bleach systems comprising the organic 10 catalyst compounds can be used as antimicrobial agents and disinfectants. Accordingly, the bleach systems of the present invention may include various additional ingredients which are desirable in laundry applications. Such ingredients include detersive surfactants, bleach catalysts, builders, chelating agents, enzymes, polymeric soil release agents, brighteners and various other ingredients. Compositions including any of these various additional 15 ingredients preferably have a pH of from about 6 to about 12, preferably from about 8 to about 10.5 in a 1% solution of the bleach system. The bleach systems preferably include at least one detersive surfactant, at least one chelating agent, at least one detersive enzyme and preferably has a pH of about 6 to about 12, preferably from 8 to about 10.5 in a 1% solution of the bleach system. 20 In another embodiment of the present invention, a method for laundering a fabric, especially a colored fabric, in need of laundering is provided. The preferred method comprises contacting the fabric with a laundry solution. The fabric may comprise most any fabric capable of being laundered in normal consumer use conditions. The laundry solution comprises a bleach system comprising one or more zwitterionic organic catalyst compounds of the present invention, 25 as fully described herein. The water temperatures preferably range from about 0 OC to about 50 oC or higher. The water to fabric ratio is preferably from about 1:1 to about 15:1. The laundry solution may further include at least one additional ingredient selected from the group consisting of detersive surfactants, chelating agents, detersive enzymes and mixtures thereof. Preferably, the laundry solution has a pH of about 6 to about 12, preferably from about 8 30 to about 10.5 in a 1% solution of the bleach system. The bleach systems of the present invention typically and preferably comprise a peroxygen source. Peroxygen sources are well-known in the art and the peroxygen source employed in the present invention may comprise any of these well known sources, including peroxygen compounds as well as compounds which under consumer use conditions provide an 35 effective amount of peroxygen in situ. The peroxygen source may include a hydrogen peroxide 13 WO 01/16278 PCT/US00/23321 source, the in situ formation of a peracid anion through the reaction of a hydrogen peroxide source and a bleach activator, preformed peracid compounds or mixtures of suitable peroxygen sources. Of course, one of ordinary skill in the art will recognize that other sources of peroxygen may be employed without departing from the scope of the invention. Preferably, the peroxygen 5 source is selected from the group consisting of: (i) preformed peracid compounds selected from the group consisting of percarboxylic acids and salts, percarbonic acids and salts, perimidic acids and salts, peroxymonosulfuric acids and salts, and mixtures thereof, and (ii) hydrogen peroxide sources selected from the group consisting of perborate 10 compounds, percarbonate compounds, perphosphate compounds and mixtures thereof, and a bleach activator. When present, peroxygen sources (peracids and/or hydrogen peroxide sources) will typically be at levels of from about 1%, preferably from about 5% to about 30%, preferably to about 20% by weight of the composition. If present, the amount of bleach activator will typically 15 be from about 0.1%, preferably from about 0.5% to about 60%, preferably to about 40% by weight, of the bleach system comprising the bleaching agent-plus-bleach activator. a. Preformed Peracids - The preformed peracid compound as used herein is any convenient compound which is stable and which under consumer use conditions provides an effective amount of peracid anion. The organic catalysts of the present invention may of course 20 be used in conjunction with a preformed peracid compound selected from the group consisting of percarboxylic acids and salts, percarbonic acids and salts, perimidic acids and salts, peroxymonosulfuric acids and salts, and mixtures thereof, examples of which are described in U.S. Patent No. 5,576,282 to Miracle et al. One class of suitable organic peroxycarboxylic acids have the general formula: O II 25 Y-R-C-O-OH wherein R is an alkylene or substituted alkylene group containing from 1 to about 22 carbon atoms or a phenylene or substituted phenylene group, and Y is hydrogen, halogen, alkyl, aryl, C(O)OH or -C(O)OOH. Organic peroxyacids suitable for use in the present invention can contain either one or 30 two peroxy groups and can be either aliphatic or aromatic. When the organic peroxycarboxylic acid is aliphatic, the unsubstituted peracid has the general formula: O II

Y-(CH

2 )n-C-O-OH 14 WO 01/16278 T lU inI/.Z l where Y can be, for example, H, CH 3 , CH 2 C1, C(O)OH, or C(O)OOH; and n is an integer from 0 to 20. When the organic peroxycarboxylic acid is aromatic, the unsubstituted peracid has the general formula: O II

Y-C

6

H

4 -C-0-OH 5 wherein Y can be, for example, hydrogen, alkyl, alkylhalogen, halogen, C(O)OH or C(0)OOH. Typical monoperoxy acids useful herein include alkyl and aryl peroxyacids such as: (i) peroxybenzoic acid and ring-substituted peroxybenzoic acid, e.g. peroxy-a naphthoic acid, monoperoxyphthalic acid (magnesium salt hexahydrate), and o carboxybenzamidoperoxyhexanoic acid (sodium salt); 10 (ii) aliphatic, substituted aliphatic and arylalkyl monoperoxy acids, e.g. peroxylauric acid, peroxystearic acid, N-nonanoylaminoperoxycaproic acid (NAPCA), N,N-(3 octylsuccinoyl)aminoperoxycaproic acid (SAPA) and N,N-phthaloylaminoperoxycaproic acid (PAP); (iii) amidoperoxyacids, e.g. monononylamide of either peroxysuccinic acid (NAPSA) 15 or of peroxyadipic acid (NAPAA). Typical diperoxyacids useful herein include alkyl diperoxyacids and aryldiperoxyacids, such as: (iv) 1,12-diperoxydodecanedioic acid; (v) 1,9-diperoxyazelaic acid; 20 (vi) diperoxybrassylic acid; diperoxysebacic acid and diperoxyisophthalic acid; (vii) 2-decyldiperoxybutane-1,4-dioic acid; (viii) 4,4'-sulfonylbisperoxybenzoic acid. Such bleaching agents are disclosed in U.S. Patent 4,483,781, Hartman, issued November 20, 1984, U.S. Patent 4,634,551 to Bums et al., European Patent Application 0,133,354, Banks et 25 al. published February 20, 1985, and U.S. Patent 4,412,934, Chung et al. issued November 1, 1983. Sources also include 6-nonylamino-6-oxoperoxycaproic acid as fully described in U.S. Patent 4,634,551, issued January 6, 1987 to Burns et al. Persulfate compounds such as for example OXONE, manufactured commercially by E.I. DuPont de Nemours of Wilmington, DE can also be employed as a suitable source of peroxymonosulfuric acid. 30 b. Hydrogen Peroxide Sources - The hydrogen peroxide source may be any suitable hydrogen peroxide source and present at such levels as fully described in U.S. Patent No. 5,576,282. For example, the hydrogen peroxide source may be selected from the group consisting of perborate compounds, percarbonate compounds, perphosphate compounds and mixtures thereof. 15 VI Ulf IUA/O LJO % 1 VaUUIJJA3I Hydrogen peroxide sources are described in detail in the herein incorporated Kirk Othmer's Encyclopedia of Chemical Technology, 4th Ed (1992, John Wiley & Sons), Vol. 4, pp. 271-300 "Bleaching Agents (Survey)", and include the various forms of sodium perborate and sodium percarbonate, including various coated and modified forms. 5 The preferred source of hydrogen peroxide used herein can be any convenient source, including hydrogen peroxide itself. For example, perborate, e.g., sodium perborate (any hydrate but preferably the mono- or tetra-hydrate), sodium carbonate peroxyhydrate or equivalent percarbonate salts, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, or sodium peroxide can be used herein. Also useful are sources of available oxygen such as persulfate bleach (e.g., 10 OXONE, manufactured by DuPont). Sodium perborate monohydrate and sodium percarbonate are particularly preferred. Mixtures of any convenient hydrogen peroxide sources can also be used. A preferred percarbonate bleach comprises dry particles having an average particle size in the range from about 500 micrometers to about 1,000 micrometers, not more than about 10% by 15 weight of said particles being smaller than about 200 micrometers and not more than about 10% by weight of said particles being larger than about 1,250 micrometers. Optionally, the percarbonate can be coated with a silicate, borate or water-soluble surfactants. Percarbonate is available from various commercial sources such as FMC, Solvay and Tokai Denka. Compositions of the present invention may also comprise as the bleaching agent a 20 chlorine-type bleaching material. Such agents are well known in the art, and include for example sodium dichloroisocyanurate ("NaDCC"). However, chlorine-type bleaches are less preferred for compositions which comprise enzymes. b. Bleach Activators - Preferably, the peroxygen source in the composition is formulated with an activator (peracid precursor). The activator is present at levels of from about 25 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. A bleach activator as used herein is any compound which when used in conjunction with a hydrogen peroxide source leads to the in situ production of the peracid corresponding to the bleach activator. Various non limiting examples of activators are fully disclosed in U.S. Patent No. 5,576,282, U.S. Patent 30 4,915,854 and U.S. Patent 4,412,934. See also U.S. 4,634,551 for other typical bleaches and activators useful herein. Preferred activators are selected from the group consisting of tetraacetyl ethylene diamine (TAED), benzoylcaprolactam (BzCL), 4-nitrobenzoylcaprolactam, 3-chlorobenzoylcaprolactam, benzoyloxybenzenesulphonate (BOBS), nonanoyloxybenzenesulphonate (NOBS), phenyl 35 benzoate (PhBz), decanoyloxybenzenesulphonate (C 10 -OBS), benzoylvalerolactam (BZVL), 16 WU UI/1lZ7 r- 1/UUUIz.a33z1 octanoyloxybenzenesulphonate (C 8 -OBS), perhydrolyzable esters and mixtures thereof, most preferably benzoylcaprolactam and benzoylvalerolactam. Particularly preferred bleach activators in the pH range from about 8 to about 9.5 are those selected having an OBS or VL leaving group. Preferred hydrophobic bleach activators include, but are not limited to, 5 nonanoyloxybenzenesulphonate (NOBS), 4-[N-(nonanoyl) amino hexanoyloxy]-benzene sulfonate sodium salt (NACA-OBS) an example of which is described in U.S. Patent No. 5,523,434, lauroyloxybenzenesulphonate (LOBS or C 12 -OBS), 10 undecenoyloxybenzenesulfonate (UDOBS or C 1 1 -OBS with unsaturation in the 10 position), and decanoyloxybenzoic acid (DOBA). 10 Preferred bleach activators are those described in U.S. 5,698,504 Christie et al., issued December 16, 1997; U.S. 5,695,679 Christie 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 April 11, 1995; U.S. 5,405,413 Willey et al., issued April 11, 1995; U.S. 5,130,045 Mitchel et al., issued July 14, 1992; and U.S. 4,412,934 Chung et 15 al., issued November 1, 1983, and copending patent applications U. S. Serial Nos. 08/709,072, 08/064,564, all of which are incorporated herein by reference. The mole ratio of peroxygen bleaching compound (as AvO) to bleach activator in 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. 20 Quaternary substituted bleach activators may also be included. The present bleach systems preferably comprise a quaternary substituted bleach activator (QSBA) or a quaternary substituted peracid (QSP); more preferably, the former. Preferred QSBA structures are further described in 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. 25 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 herein by reference. Highly preferred bleach activators useful herein are amide-substituted as described in U.S. 5,698,504, U.S. 5,695,679, and U.S. 5,686,014 each of which are cited herein above. Preferred examples of such bleach activators include: (6-octanamidocaproyl) 30 oxybenzenesulfonate, (6-nonanamidocaproyl)oxybenzenesulfonate, (6-decanamido caproyl)oxybenzenesulfonate and mixtures thereof. Other useful activators, disclosed in U.S. 5,698,504, U.S. 5,695,679, U.S. 5,686,014 each of which is cited herein above and U.S. 4,966,723Hodge et al., issued October 30, 1990, include benzoxazin-type activators, such as a C 6

H

4 ring to which is fused in the 1,2-positions a 35 moiety -- C(O)OC(R 1 )=N-. 17 VTLj vA1u1UlO r% L/UaUU/A4JJA Depending on the activator and precise application, good bleaching results can be obtained from bleaching systems having with in-use pH of from about 6 to about 13, preferably from about 9.0 to about 10.5. Typically, for example, activators with electron-withdrawing moieties are used for near-neutral or sub-neutral pH ranges. Alkalis and buffering agents can be 5 used to secure such pH. Acyl lactam activators, as described in U.S. 5,698,504, U.S. 5,695,679 and U.S. 5,686,014, each of which is cited herein above, are very useful herein, especially the acyl caprolactams (see for example WO 94-28102 A) and acyl valerolactams (see U.S. 5,503,639 Willey et al., issued April 2, 1996 incorporated herein by reference). 10 d. Organic Peroxides, especially Diacyl Peroxides - In addition to the bleaching agents described above, the bleach systems of the present invention can optionally include organic peroxides. Organic peroxides are extensively illustrated in Kirk Othmer, Encyclopedia of Chemical Technology, Vol. 17, John Wiley and Sons, 1982 at pages 27-90 and especially at pages 63-72, all incorporated herein by reference. If a diacyl peroxide is used, it will preferably be one 15 which exerts minimal adverse impact on spotting/filming. e. Metal-containing Bleach Catalysts - The bleach systems can also optionally include metal-containing bleach catalysts, preferably manganese and cobalt-containing bleach catalysts. One type of metal-containing bleach catalyst is a catalyst system comprising a transition metal cation of defined bleach catalytic activity, such as copper, iron, titanium, ruthenium 20 tungsten, molybdenum, or manganese cations, an auxiliary metal cation having little or no bleach catalytic activity, such as zinc or aluminum cations, and a sequestrate having defined stability constants for the catalytic and auxiliary metal cations, particularly ethylenediaminetetraacetic acid, ethylenediaminetetra (methylenephosphonic acid) and water-soluble salts thereof. Such catalysts are disclosed in U.S. 4,430,243 Bragg, issued February 2, 1982. 25 i. Manganese Metal Complexes - If desired, the compositions herein can be catalyzed by means of a manganese compound. Such compounds and levels of use are well known in the art and include, for example, the manganese-based catalysts 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 30 Jureller et al., issued March 16, 1993; U.S. 5,114,606 van Vliet et al., issued May 19, 1992; and European Pat. App. Pub. Nos. 549,271 Al, 549,272 Al, 544,440 A2, and 544,490 Al; Preferred examples of these catalysts include MnIV 2 (u-O) 3 (1,4,7-trimethyl-1, 4 ,7-triazacyclononane) 2 (PF 6

)

2 , MnIl2(u-O) (u-OAc) 2 (1,4,7-trimethyl-1,4,7-triazacyclononane) 2 (C10 4

)

2 , MnIV 4 (u 0)6(1,4,7-triazacyclononane) 4 (C10 4

)

4 , MnIIIMnlV 4 (u-O) 1 (u-OAc) 2 -(1,4,7-trimethyl- 1,4,7 35 triazacyclononane) 2 (C10 4

)

3 , MnIV(1,4,7-trimethyl-1, 4 ,7-triazacyclononane)-

(OCH

3

)

3

(PF

6 ), 18 WU U/1IL5 YL 1/U3UU/L3J1,Z and mixtures thereof. Other metal-based bleach catalysts include those disclosed in U.S. 4,430,243 included by reference herein above and U.S. 5,114,611 van Kralingen, issued May 19, 1992. The use of manganese with various complex ligands to enhance bleaching is also reported in the following: U.S. 4,728,455 Rerek, issued March 1, 1988; U.S. 5,284,944 Madison, issued 5 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. ii. Cobalt Metal Complexes - Cobalt bleach catalysts useful herein are known, 10 and are described, for example, in U.S. 5,597,936 Perkins et al., issued January 28, 1997; U.S. 5,595,967 Miracle et al., January 21, 1997; U.S. 5,703,030 Perkins et al., issued December 30, 1997; and M. L. Tobe, "Base Hydrolysis of Transition-Metal Complexes", Adv. Inorg. Bioinorg. Mech., (1983), 2, pages 1-94. The most preferred cobalt catalyst useful herein are cobalt pentaamine acetate salts having the formula [Co(NH 3

)

5 OAc ] Ty, wherein "OAc" represents an 15 acetate moiety and "Ty" is an anion, and especially cobalt pentaamine acetate chloride, [Co(NH 3

)

5 OAc]C1 2 ; as well as [Co(NH 3

)

5 OAc](OAc) 2 ; [Co(NH 3

)

5 OAc](PF 6

)

2 ; [Co(NH 3

)

5 OAc](SO 4 ); [Co(NH 3

)

5 OAc](BF 4

)

2 ; and [Co(NH 3

)

5 OAc](NO 3

)

2 (herein "PAC"). These cobalt catalysts are readily prepared by known procedures, such as taught for example in U.S. 5,597,936, U.S. 5,595,967, U.S. 5,703,030, cited herein above, the Tobe article 20 and the references cited therein, and in U.S. Patent 4,810,410, to Diakun et al, issued March 7,1989, J. Chem. Ed. (1989), 66 (12), 1043-45; The Synthesis and Characterization of Inorganic Compounds, W.L. Jolly (Prentice-Hall; 1970), pp. 461-3; Inorg. Chem., 18, 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). 25 iii. Transition Metal Complexes of Macropolycyclic Rigid Ligands Compositions herein may also suitably include as bleach catalyst a transition metal complex of a macropolycyclic rigid ligand. The phrase "macropolycyclic rigid ligand" is sometimes abbreviated as "MRL" in discussion below. The amount used is a catalytically effective amount, suitably about 1 ppb or more, for example up to about 99.9%, more typically about 0.001 ppm or 30 more, preferably from about 0.05 ppm to about 500 ppm (wherein "ppb" denotes parts per billion by weight and "ppm" denotes parts per million by weight). Suitable transition metals e.g., Mn are illustrated hereinafter. "Macropolycyclic" means a MRL is both a macrocycle and is polycyclic. "Polycyclic" means at least bicyclic. The term "rigid" as used herein herein includes "having a superstructure" and "cross-bridged". "Rigid" has 35 been defined as the constrained converse of flexibility: see D.H. Busch., Chemical Reviews., 19 VVu u/10/ 5 rt IY L1UW3Z.JZI (1993), 93, 847-860, incorporated by reference. More particularly, "rigid" as used herein means that the MRL must be determinably more rigid than a macrocycle ("parent macrocycle") which is otherwise identical (having the same ring size and type and number of atoms in the main ring) but lacking a superstructure (especially linking moieties or, preferably cross-bridging moieties) found 5 in the MRL's. In determining the comparative rigidity of macrocycles with and without superstructures, the practitioner will use the free form (not the metal-bound form) of the macrocycles. Rigidity is well-known to be useful in comparing macrocycles; suitable tools for determining, measuring or comparing rigidity include computational methods (see, for example, Zimmer, Chemical Reviews, (1995), 95(38), 2629-2648 or Hancock et al., Inorganica Chimica 10 Acta, (1989), 164, 73-84. Preferred MRL's herein are a special type of ultra-rigid ligand which is cross-bridged. A "cross-bridge" is nonlimitingly illustrated in 1.11 hereinbelow. In 1.11, the cross-bridge is a CH2CH2- moiety. It bridges N 1 and N 8 in the illustrative structure. By comparison, a "same side" bridge, for example if one were to be introduced across N and N 12 in 1.11, would not be 15 sufficient to constitute a "cross-bridge" and accordingly would not be preferred. Suitable metals in the rigid ligand complexes include Mn(II), Mn(III), Mn(IV), Mn(V), Fe(II), Fe(III), Fe(IV), Co(I), Co(II), Co(III), Ni(I), Ni(II), Ni(III), Cu(I), Cu(II), Cu(III), Cr(II), Cr(III), Cr(IV), Cr(V), Cr(VI), V(III), V(IV), V(V), Mo(IV), Mo(V), Mo(VI), W(IV), W(V), W(VI), Pd(II), Ru(II), Ru(III), and Ru(IV). Preferred transition-metals in the instant transition 20 metal bleach catalyst include manganese, iron and chromium. More generally, the MRL's (and the corresponding transition-metal catalysts) herein suitably comprise: (a) at least one macrocycle main ring comprising four or more heteroatoms; and (b) a covalently connected non-metal superstructure capable of increasing the rigidity of the 25 macrocycle, preferably selected from (i) a bridging superstructure, such as a linking moiety; (ii) a cross-bridging superstructure, such as a cross-bridging linking moiety; and (iii) combinations thereof. The term "superstructure" is used herein as defined in the literature by Busch et al., see, 30 for example, articles by Busch in "Chemical Reviews". Preferred superstructures herein not only enhance the rigidity of the parent macrocycle, but also favor folding of the macrocycle so that it coordinates to a metal in a cleft. Suitable superstructures can be remarkably simple, for example a linking moiety such as any of those illustrated in Fig. 1 and Fig. 2 below, can be used. 20 WO 01/16278 I /u~oo/zJ3zi

(CH

2 )n Fig. 1 wherein n is an integer, for example from 2 to 8, preferably less than 6, typically 2 to 4, or T

(CH

2 ) (CH2)n Z 5 Fig. 2 wherein m and n are integers from about 1 to 8, more preferably from 1 to 3; Z is N or CH; and T is a compatible substituent, for example H, alkyl, trialkylammonium, halogen, nitro, sulfonate, or the like. The aromatic ring in 1.10 can be replaced by a saturated ring, in which the atom in Z connecting into the ring can contain N, O, S or C. 10 Suitable MRL's are further nonlimitingly illustrated by the following compound: 3 2 45 5N 14N a N 6 131 121 N87 19 10 Fig. 3 This is a MRL in accordance with the invention which is a highly preferred, cross bridged, methyl-substituted (all nitrogen atoms tertiary) derivative of cyclam. Formally, this 15 ligand is named 5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane using the extended von Baeyer system. See "A Guide to IUPAC Nomenclature of Organic Compounds: Recommendations 1993", R. Panico, W.H. Powell and J-C Richer (Eds.), Blackwell Scientific Publications, Boston, 1993; see especially section R-2.4.2.1. Transition-metal bleach catalysts of Macrocyclic Rigid Ligands which are suitable for use 20 in the invention compositions can in general include known compounds where they conform with the definition herein, as well as, more preferably, any of a large number of novel compounds expressly designed for the present laundry or cleaning uses, and non-limitingly illustrated by any of the following: Dichloro-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane Manganese(II) 25 Diaquo-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane Manganese(II) 21 wU uI/10/o5 rL I/USUUIL 3zI Hexafluorophosphate Aquo-hydroxy-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane Manganese(III) Hexafluorophosphate Diaquo-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane Manganese(II) 5 Tetrafluoroborate Dichloro-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane Manganese(III) Hexafluorophosphate Dichloro-5,12-di-n-butyl-1,5,8,12-tetraaza bicyclo[6.6.2]hexadecane Manganese(II) Dichloro-5,12-dibenzyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane Manganese(II) 10 Dichloro-5-n-butyl-12-methyl-1,5,8,12-tetraaza- bicyclo[6.6.2]hexadecane Manganese(II) Dichloro-5-n-octyl-12-methyl-1,5,8,12-tetraaza- bicyclo[6.6.2]hexadecane Manganese(II) Dichloro-5-n-butyl-12-methyl-1,5,8,12-tetraaza- bicyclo[6.6.2]hexadecane Manganese(II). (f) Other Bleach Catalysts - The compositions herein may comprise one or more other bleach catalysts. Preferred bleach catalysts are zwitterionic bleach catalysts, which are described 15 in U.S. Patent No. 5,576,282 (especially 3-(3,4-dihydroisoquinolinium) propane sulfonate. Other bleach catalysts include cationic bleach catalysts are described in U.S. Patent Nos. 5,360,569, 5,442,066, 5,478,357, 5,370,826, 5,482,515, 5,550,256, and WO 95/13351, WO 95/13352, and WO 95/13353. As a practical matter, and not by way of limitation, the compositions and cleaning 20 processes herein can be adjusted to provide on the order of at least one part per hundred million of the active bleach catalyst species in the aqueous washing medium, and will preferably provide from about 0.01 ppm to about 25 ppm, more preferably from about 0.05 ppm to about 10 ppm, and most preferably from about 0.1 ppm to about 5 ppm, of the bleach catalyst species in the wash liquor. In order to obtain such levels in the wash liquor of an automatic washing process, typical 25 compositions herein will comprise from about 0.0005% to about 0.2%, more preferably from about 0.004% to about 0.08%, of bleach catalyst, especially manganese or cobalt catalysts, by weight of the cleaning compositions. Preferably, the peroxygen source is selected from hydrogen peroxide sources selected from the group consisting of perborate compounds, percarbonate compounds, perphosphate 30 compounds and mixtures thereof, and a bleach activator. Preferably, the bleach activator is selected from the group consisting of hydrophobic bleach activators as disclosed herein. The purpose of such a bleach system is to mitigate unwanted decomposition of the organic catalyst, and to allow the peracid to achieve bleaching performance on a fabric in need of 22 WU U1/1OZ'78 r I/U5UU/L..331 cleaning, such as a stained fabric, in a wash solution prior to the availability of the organic catalyst. The period of time between the peracid becoming active in a wash solution and the organic catalyst compounds becoming active can be in the range of from about 1 second to about 5 24 hours. Alternatively, since the organic catalyst compounds are relatively stable in the wash solution, the peracid can become active in the wash solution after the organic catalyst compound becomes active or available. The purpose of a delayed addition bleach system (which may or may not be used in conjunction with this invention) is to allow the peracid to achieve maximum bleaching 10 performance on a fabric in need of cleaning, such as a stained fabric, in a wash solution prior to the introduction of the organic catalyst compound. In other words, a bleach system comprising a organic catalyst compound which becomes active in a wash solution after a fabric in need of cleaning has been added to the wash solution. Alternatively, since the organic catalyst compounds can have increased stability, a bleach system comprising an organic catalyst 15 compound which becomes active in a wash solution prior to a fabric in need of cleaning has been added to the wash solution may be used. A preferred bleach system in accordance with the present invention is a bleach system comprising: 20 (a) a peroxygen source; and (b) a zwitterionic organic catalyst compound; wherein the zwitterionic organic catalyst compound becomes active in a wash solution containing said bleach system a period of time after said peroxygen source becomes active. The peroxygen 25 source, like discussed above, is preferably selected from the group consisting of: (i) preformed peracid compounds selected from the group consisting of percarboxylic acids and salts, percarbonic acids and salts, perimidic acids and salts, peroxymonosulfuric acids and salts, and mixtures thereof, and 30 (ii) hydrogen peroxide sources selected from the group consisting of perborate compounds, percarbonate compounds, perphosphate compounds and mixtures thereof, and a bleach activator. The bleach systems of the present invention also preferably comprise, in addition to one or more organic catalysts, described hereinbefore, one or more cleaning adjunct materials, 35 preferably compatible with the organic catalyst(s) and/or any enzymes present in the bleach 23 WU 01/10278 YLL):U UIW2JJZ1 system. The term "compatible", as used herein, means the bleach system materials do not reduce the bleaching activity of the organic catalyst and/or any enzymatic activity of any enzyme present in the bleach system to such an extent that the organic catalyst and/or enzyme is not effective as desired during normal use situations. The term "cleaning adjunct materials", as used herein, 5 means any liquid, solid or gaseous material selected for the particular type of bleach system desired and the form of the product (e.g., liquid; granule; powder; bar; paste; spray; tablet; gel; foam composition), which materials are also preferably compatible with the protease enzyme(s) and bleaching agent(s) used in the composition. Granular compositions can also be in "compact" form and the liquid compositions can also be in a "concentrated" form. 10 The specific selection of cleaning adjunct materials are readily made by considering the surface, item or fabric to be cleaned, and the desired form of the composition for the cleaning conditions during use (e.g., through the wash detergent use). Examples of suitable cleaning adjunct materials include, but are not limited to, surfactants, builders, bleaches, bleach activators, bleach catalysts, other enzymes, enzyme stabilizing systems, chelants, optical brighteners, soil 15 release polymers, dye transfer agents, dispersants, suds suppressors, dyes, perfumes, colorants, filler salts, hydrotropes, photoactivators, fluorescers, fabric conditioners, hydrolyzable surfactants, preservatives, anti-oxidants, anti-shrinkage agents, anti-wrinkle agents, germicides, fungicides, color speckles, silvercare, anti-tarnish and/or anti-corrosion agents, alkalinity sources, solubilizing agents, carriers, processing aids, pigments and pH control agents as described in U.S. Patent Nos. 20 5,705,464, 5,710,115, 5,698,504, 5,695,679, 5,686,014 and 5,646,101. Specific bleach system materials are exemplified in detail hereinafter. If the cleaning adjunct materials are not compatible with the protease variant(s) in the bleach systems, then suitable methods of keeping the cleaning adjunct materials and the protease variant(s) separate (not in contact with each other) until combination of the two components is 25 appropriate can be used. Suitable methods can be any method known in the art, such as gelcaps, encapulation, tablets, physical separation, etc. Such bleach systems include detergent compositions for cleaning hard surfaces, unlimited in form (e.g., liquid, granular, paste, foam, spray, etc.); detergent compositions for cleaning fabrics, unlimited in form (e.g., granular, liquid, bar formulations, etc.); dishwashing 30 compositions (unlimited in form and including both granular and liquid automatic dishwashing); oral bleach systems, unlimited in form (e.g., dentifrice, toothpaste and mouthwash formulations); and denture bleach systems, unlimited in form (e.g., liquid, tablet). The fabric bleach systems of the present invention are mainly intended to be used in the wash cycle of a washing machine; however, other uses can be contemplated, such as pretreatment 35 product for heavily-soiled fabrics, or soaking product; the use is not necessarily limited to the 24 WO 01/16278 PLI/USUU/IZJJZI washing-machine context, and the compositions of the present invention can be used alone or in combination with compatible handwash compositions. The bleach systems may include from about 1% to about 99.9% by weight of the composition of the cleaning adjunct materials. 5 As used herein, "non-fabric bleach systems" include hard surface bleach systems, dishwashing compositions, oral bleach systems, denture bleach systems and personal cleansing compositions. When the bleach systems of the present invention are formulated as compositions suitable for use in a laundry machine washing method, the compositions of the present invention 10 preferably contain both a surfactant and a builder compound and additionally one or more cleaning adjunct materials preferably selected from organic polymeric compounds, bleaching agents, additional enzymes, suds suppressors, dispersants, lime-soap dispersants, soil suspension and anti-redeposition agents and corrosion inhibitors. Laundry compositions can also contain softening agents, as additional cleaning adjunct materials. 15 The compositions of the present invention can also be used as detergent additive products in solid or liquid form. Such additive products are intended to supplement or boost the performance of conventional detergent compositions and can be added at any stage of the cleaning process. When formulated as compositions for use in manual dishwashing methods the 20 compositions of the invention preferably contain a surfactant and preferably other cleaning adjunct materials selected from organic polymeric compounds, suds enhancing agents, group II metal ions, solvents, hydrotropes and additional enzymes. If needed the density of the laundry detergent compositions herein ranges from 400 to 1200 g/litter, preferably 500 to 950 g/litter of composition measured at 20 0 C. 25 The "compact" form of the bleach systems herein is best reflected by density and, in terms of composition, by the amount of inorganic filler salt; inorganic filler salts are conventional ingredients of detergent compositions in powder form; in conventional detergent compositions, the filler salts are present in substantial amounts, typically 17-35% by weight of the total composition. In the compact compositions, the filler salt is present in amounts not exceeding 15% 30 of the total composition, preferably not exceeding 10%, most preferably not exceeding 5% by weight of the composition. The inorganic filler salts, such as meant in the present compositions are selected from the alkali and alkaline-earth-metal salts of sulfates and chlorides. A preferred filler salt is sodium sulfate. Liquid bleach systems according to the present invention can also be in a "concentrated 35 form", in such case, the liquid bleach systems according the present invention will contain a lower 25 WO 01/16278 PCT/UMSUII/23321 amount of water, compared to conventional liquid detergents. Typically the water content of the concentrated liquid bleach system is preferably less than 40%, more preferably less than 30%, most preferably less than 20% by weight of the bleach system. Cleaning Adjunct Materials 5 While not essential for the purposes of the present invention, several conventional adjuncts illustrated hereinafter are suitable for use in the instant bleach systems and may be desirably incorporated in preferred embodiments of the invention, for example to assist or enhance cleaning performance, for treatment of the substrate to be cleaned, or to modify the aesthetics of the bleach system as is the case with perfumes, colorants, dyes or the like. The 10 precise nature of these additional components, and levels of incorporation thereof, will depend on the physical form of the composition and the nature of the cleaning operation for which it is to be used. Unless otherwise indicated, the bleach systems of the invention may for example, be formulated as granular or powder-form all-purpose or "heavy-duty" washing agents, especially laundry detergents; liquid, gel or paste-form all-purpose washing agents, especially the so-called 15 heavy-duty liquid types; liquid fine-fabric detergents; hand dishwashing agents or light duty dishwashing agents, especially those of the high-foaming type; machine dishwashing agents, including the various tablet, granular, liquid and rinse-aid types for household and institutional use; liquid cleaning and disinfecting agents, including antibacterial hand-wash types, laundry bars, mouthwashes, denture cleaners, car or carpet shampoos, bathroom cleaners; hair shampoos 20 and hair-rinses; shower gels and foam baths and metal cleaners; as well as cleaning auxiliaries such as bleach additives and "stain-stick" or pre-treat types. Surfactants - The compositions of the present invention preferably contain a detersive surfactant. The detersive surfactant is typically selected from the group consisting of anionic, nonionics, cationics, ampholytics, zwitterionics, and mixtures thereof. By selecting the type and 25 amount of detersive surfactant, along with other adjunct ingredients disclosed herein, the present detergent compositions can be formulated to be used in the context of laundry cleaning or in other different cleaning applications, particularly including dishwashing. The particular surfactants used can therefore vary widely depending upon the particular end-use envisioned. Suitable surfactants are described below. Examples of suitable nonionic, anionic, cationic amphoteric and 30 zwitterionic surfactants are given in "Surface Active Agents and Detergents" (Vol. I and II by Schwartz, Perry and Berch). A variety of such surfactants are also generally disclosed in U.S. Patent 3,929,678, issued December 30, 1975 to Laughlin, et al. at Column 23, line 58 through Column 29, line 23. 26 WO 01/16278 PCT/USUU/23I321 The surfactant is typically present at a level of from about 0.1%, preferably about 1%, more preferably about 5% by weight of the bleach systems to about 99.9%, preferably about 80%, more preferably about 35%, most preferably 30% about by weight of the bleach systems. Anionic Surfactants - Anionic surfactants useful in the present invention are preferably 5 selected from the group consisting of, linear alkylbenzene sulfonate, alpha olefin sulfonate, paraffin sulfonates, alkyl ester sulfonates, alkyl sulfates, alkyl alkoxy sulfate, alkyl sulfonates, alkyl alkoxy carboxylate, alkyl alkoxylated sulfates, sarcosinates, taurinates, and mixtures thereof. An effective amount, typically from about 0.5% to about 90%, preferably about 5% to about 60%, more preferably from about 10 to about 30%, by weight of anionic detersive surfactant can be 10 used in the present invention. Alkyl sulfate surfactants are another type of anionic surfactant of importance for use herein. In addition to providing excellent overall cleaning ability when used in combination with polyhydroxy fatty acid amides (see below), including good grease/oil cleaning over a wide range of temperatures, wash concentrations, and wash times, dissolution of alkyl sulfates can be 15 obtained, as well as improved formulability in liquid detergent formulations are water soluble salts or acids of the formula ROSO 3 M wherein R preferably is a C 10

-C

2 4 hydrocarbyl, preferably an alkyl or hydroxyalkyl having a C 10

-C

20 alkyl component, more preferably a C 12 C 18 alkyl or hydroxyalkyl, and M is H or a cation, e.g., an alkali (Group IA) metal cation (e.g., sodium, potassium, lithium), substituted or unsubstituted ammonium cations such as methyl-, 20 dimethyl-, and trimethyl ammonium and quaternary ammonium cations, e.g., tetramethyl ammonium and dimethyl piperdinium, and cations derived from alkanolamines such as ethanolamine, diethanolamine, triethanolamine, and mixtures thereof, and the like. Typically, alkyl chains of C 12

-

16 are preferred for lower wash temperatures (e.g., below about 50 0 C) and

C

16

-

18 alkyl chains are preferred for higher wash temperatures (e.g., above about 50'C). 25 Alkyl alkoxylated sulfate surfactants are another category of useful anionic surfactant. These surfactants are water soluble salts or acids typically of the formula RO(A)mSO3M wherein R is an unsubstituted C 10

-C

24 alkyl or hydroxyalkyl group having a C 10

-C

24 alkyl component, preferably a C 12

-C

2 0 alkyl or hydroxyalkyl, more preferably C 1 2

-C

18 alkyl or hydroxyalkyl, A is an ethoxy or propoxy unit, m is greater than zero, typically between about 0.5 and about 6, 30 more preferably between about 0.5 and about 3, and M is H or a cation which can be, for example, a metal cation (e.g., sodium, potassium, lithium, etc.), ammonium or substituted ammonium cation. Alkyl ethoxylated sulfates as well as alkyl propoxylated sulfates are contemplated herein. Specific examples of substituted ammonium cations include methyl-, dimethyl-, trimethyl-ammonium and quaternary ammonium cations, such as tetramethyl 35 ammonium, dimethyl piperidinium and cations derived from alkanolamines, e.g. 27 WO 01/16278 rLI /1UU/ALjji monoethanolamine, diethanolamine, and triethanolamine, and mixtures thereof. Exemplary surfactants are C 12

-C

18 alkyl polyethoxylate (1.0) sulfate, C 12

-C

18 alkyl polyethoxylate (2.25) sulfate, C 12

-C

18 alkyl polyethoxylate (3.0) sulfate, and C 12

-C

18 alkyl polyethoxylate (4.0) sulfate wherein M is conveniently selected from sodium and potassium. Surfactants for use 5 herein can be made from natural or synthetic alcohol feedstocks. Chain lengths represent average hydrocarbon distributions, including branching. Additionally and preferably, the surfactant may be a midchain branched alkyl sulfate, midchain branched alkyl alkoxylate, or midchain branched alkyl alkoxylate sulfate. These surfactants are further described in No. 60/061,971, Attorney docket No 6881P October 14, 1997, 10 No. 60/061,975, Attorney docket No 6882P October 14, 1997, No. 60/062,086, Attorney docket No 6883P October 14, 1997, No. 60/061,916, Attorney docket No 6884P October 14, 1997, No. 60/061,970, Attorney docket No 6885P October 14, 1997, No. 60/062,407, Attorney docket No 6886P October 14, 1997,. Other suitable mid-chain branched surfactants can be found in U.S. Patent applications Serial Nos. 60/032,035 (Docket No. 6401P), 60/031,845 (Docket No. 6402P), 15 60/031,916 (Docket No. 6403P), 60/031,917 (Docket No. 6404P), 60/031,761 (Docket No. 6405P), 60/031,762 (Docket No. 6406P) and 60/031,844 (Docket No. 6409P). Mixtures of these branched surfactants with conventional linear surfactants are also suitable for use in the present compositions. Another preferred anionic surfactant are the so-called modified alkyl benzene sulfonate 20 surfactants, or MLAS. Some suitable MLAS surfactants, methods of making them and exemplary compositions are further described in copending U.S. Patent applications Serial Nos. 60/053,319 (Docket No. 6766P), 60/053,318 (Docket No. 6767P), 60/053,321 (Docket No. 6768P), 60/053,209 (Docket No. 6769P), 60/053,328 (Docket No. 6770P), 60/053,186 (Docket No. 6771P), 60/055,437 (Docket No. 6796P), 60/105,017 (Docket No. 7303P), and 60/104,962 25 (Docket No. 7304P). Examples of suitable anionic surfactants are given in "Surface Active Agents and Detergents" (Vol. I and II by Schwartz, Perry and Berch). Nonionic Detergent Surfactants - Suitable nonionic detergent surfactants are generally disclosed in U.S. Patent 3,929,678, Laughlin et al., issued December 30, 1975, at column 13, line 30 14 through column 16, line 6, incorporated herein by reference. Exemplary, non-limiting classes of useful nonionic surfactants include: amine oxides, alkyl ethoxylate, alkanoyl glucose amide, alkyl betaines, sulfobetaine and mixtures thereof Amine oxides are semi-polar nonionic surfactants and include water-soluble amine oxides containing one alkyl moiety of from about 10 to about 18 carbon atoms and 2 moieties selected 35 from the group consisting of alkyl groups and hydroxyalkyl groups containing from about 1 to 28 WU UI/1075 YL I1/UNUU/.L3JzI about 3 carbon atoms; water-soluble phosphine oxides containing one alkyl moiety of from about 10 to about 18 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from about 1 to about 3 carbon atoms; and water-soluble sulfoxides containing one alkyl moiety of from about 10 to about 18 carbon atoms and a moiety 5 selected from the group consisting of alkyl and hydroxyalkyl moieties of from about I to about 3 carbon atoms. Semi-polar nonionic detergent surfactants include the amine oxide surfactants having the formula 0

R

3 (OR4)xN(R )2 10 wherein R 3 is an alkyl, hydroxyalkyl, or alkyl phenyl group or mixtures thereof containing from about 8 to about 22 carbon atoms; R 4 is an alkylene or hydroxyalkylene group containing from about 2 to about 3 carbon atoms or mixtures thereof; x is from 0 to about 3; and each R 5 is an alkyl or hydroxyalkyl group containing from about 1 to about 3 carbon atoms or a polyethylene oxide group containing from about 1 to about 3 ethylene oxide groups. The R 5 groups can be 15 attached to each other, e.g., through an oxygen or nitrogen atom, to form a ring structure. These amine oxide surfactants in particular include C 10

-C

18 alkyl dimethyl amine oxides and C 8

-C

12 alkoxy ethyl dihydroxy ethyl amine oxides. Preferably the amine oxide is present in the composition in an effective amount, more preferably from about 0.1% to about 20%, even more preferably about 0.1% to about 15%, even more preferably still from about 0.5% to about 20 10%,by weight. The polyethylene, polypropylene, and polybutylene oxide condensates of alkyl phenols. In general, the polyethylene oxide condensates are preferred. These compounds include the condensation products of alkyl phenols having an alkyl group containing from about 6 to about 12 carbon atoms in either a straight chain or branched chain configuration with the alkylene oxide. 25 In a preferred embodiment, the ethylene oxide is present in an amount equal to from about 5 to about 25 moles of ethylene oxide per mole of alkyl phenol. Commercially available nonionic surfactants of this type include Igepal® CO-630, marketed by the GAF Corporation; and Triton® X-45, X-114, X-100, and X-102, all marketed by the Rohm & Haas Company. These compounds are commonly referred to as alkyl phenol alkoxylates, (e.g., alkyl phenol ethoxylates). 30 The condensation products of aliphatic alcohols with from about 1 to about 25 moles of ethylene oxide. The alkyl chain of the aliphatic alcohol can either be straight or branched, primary or secondary, and generally contains from about 8 to about 22 carbon atoms. Particularly preferred are the condensation products of alcohols having an alkyl group containing from about 10 to about 20 carbon atoms with from about 2 to about 18 moles of ethylene oxide per mole of 29 alcohol. Examples of commercially available nonionic surfactants of this type include Tergitol® 15-S-9 (the condensation product of C 1 1

-C

1 5 linear secondary alcohol with 9 moles ethylene oxide), Tergitol® 24-L-6 NMW (the condensation product of C 12

-C

14 primary alcohol with 6 moles ethylene oxide with a narrow molecular weight distribution), both marketed by Union 5 Carbide Corporation; Neodol® 45-9 (the condensation product of C 14

-C

1 5 linear alcohol with 9 moles of ethylene oxide), Neodol® 23-6.5 (the condensation product of C 12

-C

1 3 linear alcohol with 6.5 moles of ethylene oxide), Neodol® 45-7 (the condensation product of C 14

-C

15 linear alcohol with 7 moles of ethylene oxide), Neodol® 45-4 (the condensation product of C 14

-C

1 5 linear alcohol with 4 moles of ethylene oxide), marketed by Shell Chemical Company, and 10 Kyro® EOB (the condensation product of C 13

-C

15 alcohol with 9 moles ethylene oxide), marketed by The Procter & Gamble Company. Other commercially available nonionic surfactants include Dobanol 91-8® marketed by Shell Chemical Co. and Genapol UD-080® marketed by Hoechst. This category of nonionic surfactant is referred to generally as "alkyl ethoxylates." 15 The preferred alkylpolyglycosides have the formula R20(CnH2nO)t(glycosyl)x wherein R 2 is selected from the group consisting of alkyl, alkyl-phenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups contain from about 10 to about 18, preferably from about 12 to about 14, carbon atoms; n is 2 or 3, preferably 2; t is from 0 20 to about 10, preferably 0; and x is from about 1.3 to about 10, preferably from about 1.3 to about 3, most preferably from about 1.3 to about 2.7. The glycosyl is preferably derived from glucose. To prepare these compounds, the alcohol or alkylpolyethoxy alcohol is formed first and then reacted with glucose, or a source of glucose, to form the glucoside (attachment at the 1-position). The additional glycosyl units can then be attached between their 1-position and the preceding 25 glycosyl units 2-, 3-, 4- and/or 6-position, preferably predominantly the 2-position. Fatty acid amide surfactants having the formula: O 611 7 R6'CN(R )2 wherein R 6 is an alkyl group containing from about 7 to about 21 (preferably from about 9 to about 17) carbon atoms and each R 7 is selected from the group consisting of hydrogen, C 1

-C

4 30 alkyl, C 1

-C

4 hydroxyalkyl, and -(C 2

H

4 0)xH where x varies from about 1 to about 3. Preferred amides are C 8

-C

2 0 ammonia amides, monoethanolamides, diethanolamides, and isopropanolamides. 30 VVLJ UOII1UL O L, I/ UGUUIhJOI I Preferably the nonionic surfactant, when present in the composition, is present in an effective amount, more preferably from about 0.1% to about 20%, even more preferably about 0.1% to about 15%, even more preferably still from about 0.5% to about 10%,by weight. Polyhydroxy Fatty Acid Amide Surfactant - The detergent compositions hereof may also 5 contain an effective amount of polyhydroxy fatty acid amide surfactant. By "effective amount" is meant that the formulator of the composition can select an amount of polyhydroxy fatty acid amide to be incorporated into the compositions that will improve the cleaning performance of the detergent composition. In general, for conventional levels, the incorporation of about 1%, by weight, polyhydroxy fatty acid amide will enhance cleaning performance. 10 The detergent compositions herein will typically comprise about 1% weight basis, polyhydroxy fatty acid amide surfactant, preferably from about 3% to about 30%, of the polyhydroxy fatty acid amide. The polyhydroxy fatty acid amide surfactant component comprises compounds of the structural formula: O 211 R2CNZ R 15 wherein: R 1 is H, C 1

-C

4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl, or a mixture thereof, preferably C 1

-C

4 alkyl, more preferably C 1 or C 2 alkyl, most preferably C 1 alkyl (i.e., methyl); and R 2 is a C 5

-C

3 1 hydrocarbyl, preferably straight chain C 7

-C

19 alkyl or alkenyl, more preferably straight chain C 9

-C

17 alkyl or alkenyl, most preferably straight chain C 1 1 -C 15 alkyl or alkenyl, or mixtures thereof; and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl 20 chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof. Z preferably will be derived from a reducing sugar in a reductive amination reaction; more preferably Z will be a glycityl. Suitable reducing sugars include glucose, fructose, maltose, lactose, galactose, mannose, and xylose. As raw materials, high dextrose corn syrup, high fructose corn syrup, and high maltose corn syrup can be 25 utilized as well as the individual sugars listed above. These corn syrups may yield a mix of sugar components for Z. It should be understood that it is by no means intended to exclude other suitable raw materials. Z preferably will be selected from the group consisting of -CH 2 (CHOH)n-CH 2 OH, -CH(CH 2 OH)-(CHOH)n- 1 -CH 2 OH, -CH 2

-(CHOH)

2

(CHOR')(CHOH)

CH

2 OH, and alkoxylated derivatives thereof, where n is an integer from 3 to 5, inclusive, and R' 30 is H or a cyclic or aliphatic monosaccharide. Most preferred are glycityls wherein n is 4, particularly -CH 2

-(CHOH)

4

-CH

2 OH. R' can be, for example, N-methyl, N-ethyl, N-propyl, N-isopropyl, N-butyl, N-2-hydroxy ethyl, or N-2-hydroxy propyl. 31 WU U1/1IZ1/5 rL I/U3UUIZJA1

R

2 -CO-N< can be, for example, cocamide, stearamide, oleamide, lauramide, myristamide, capricamide, palmitamide, tallowamide, etc. Z can be 1-deoxyglucityl, 2-deoxyfructityl, 1-deoxymaltityl, 1-deoxylactityl, 1 deoxygalactityl, 1 -deoxymannityl, 1-deoxymaltotriotityl, etc. 5 Methods for making polyhydroxy fatty acid amides are known in the art. In general, they can be made by reacting an alkyl amine with a reducing sugar in a reductive amination reaction to form a corresponding N-alkyl polyhydroxyamine, and then reacting the N-alkyl polyhydroxyamine with a fatty aliphatic ester or triglyceride in a condensation/amidation step to form the N-alkyl, N-polyhydroxy fatty acid amide product. Processes for making compositions 10 containing polyhydroxy fatty acid amides are disclosed, for example, in G.B. Patent Specification 809,060, published February 18, 1959, by Thomas Hedley & Co., Ltd., U.S. Patent 2,965,576, issued December 20, 1960 to E. R. Wilson, and U.S. Patent 2,703,798, Anthony M. Schwartz, issued March 8, 1955, and U.S. Patent 1,985,424, issued December 25, 1934 to Piggott, each of which is incorporated herein by reference. 15 Diamines - The preferred liquid detergent compositions, such as light duty liquid, LDL compositions, useful in the methods of the present invention may further comprise one or more diamines, preferably an amount of diamine such that the ratio of anionic surfactant present to the diamine is from about 40 : 1 to about 2: 1. Said diamines provide for increased removal of grease and greasy food material while maintaining suitable levels of suds. 20 The diamines suitable for use in the compositions of the present invention have the formula: R20 R20 N-X-N R20- ,R20 wherein each R 2 0 is independently selected from the group consisting of hydrogen, C 1

-C

4 linear or branched alkyl, alkyleneoxy having the formula: 25

-(R

2 10)yR 22 wherein R 2 1 is C 2

-C

4 linear or branched alkylene, and mixtures thereof; R 2 2 is hydrogen, C 1

-C

4 alkyl, and mixtures thereof; y is from 1 to about 10; X is a unit selected from: 30 i) C 3

-C

10 linear alkylene, C 3

-C

1 0 branched alkylene, C 3

-C

10 cyclic alkylene, C 3 C 10 branched cyclic alkylene, an alkyleneoxyalkylene having the formula:

-(R

21 0)yR 2 1 wherein R 2 1 and y are the same as defined herein above; 32 VVU U 1/10I 5 YL I/ UUU/.3.JZI ii) C 3

-C

1 0 linear, C 3

-C

10 branched linear, C 3

-C

10 cyclic, C 3

-C

10 branched cyclic alkylene, C 6

-C

1 0 arylene, wherein said unit comprises one or more electron donating or electron withdrawing moieties which provide said diamine with a pKa greater than about 8; and 5 iii) mixtures of (i) and (ii) provided said diamine has a pKa of at least about 8. The preferred diamines of the present invention have a pK 1 and pK 2 which are each in the range of from about 8 to about 11.5, preferably in the range of from about 8.4 to about 11, more preferably from about 8.6 to about 10.75. For the purposes of the present invention the term 10 "pKa" stands equally well for the terms "pK 1 " and "pK 2 " either separately or collectively. The term pKa as used herein throughout the present specification in the same manner as used by those of ordinary skill in the art. pKa values are readily obtained from standard literature sources, for example, "Critical Stability Constants: Volume 2, Amines" by Smith and Martel, Plenum Press, N.Y. and London, (1975). 15 As an applied definition herein, the pKa values of the diamines are specified as being measured in an aqueous solution at 250 C having an ionic strength of from about 0.1 to about 0.5 M. As used herein, the pKa is an equilibrium constant dependent upon temperature and ionic strength, therefore, value reported by literature references, not measured in the above described manner, may not be within full agreement with the values and ranges which comprise the present 20 invention. To eliminate ambiguity, the relevant conditions and/or references used for pKa's of this invention are as defined herein or in "Critical Stability Constants: Volume 2, Amines". One typical method of measurement is the potentiometric titration of the acid with sodium hydroxide and determination of the pKa by suitable methods as described and referenced in "The Chemist's Ready Reference Handbook" by Shugar and Dean, McGraw Hill, NY, 1990. 25 Preferred diamines for performance and supply considerations are 1,3 bis(methylamino)cyclohexane, 1,3-diaminopropane (pKl=10.5; pK 2 =8.8), 1,6-diaminohexane (pK l =ll; pK 2 =10), 1,3-diaminopentane (Dytek EP) (pKl=10.5; pK 2 =8.9), 2-methyl 1,5 diaminopentane (Dytek A) (pKl= 1 1.2; pK 2 =10.0). Other preferred materials are the primary/primary diamines having alkylene spacers ranging from C 4

-C

8 . In general, primary 30 diamines are preferred over secondary and tertiary diamines. The following are non-limiting examples of diamines suitable for use in the present invention. 1-N,N-dimethylamino-3-aminopropane having the formula: 33 WO 01/16278 FLTl/U~UbUiz31L N NH2 1,6-diaminohexane having the formula:

H

2

NNH

2 5 1,3-diaminopropane having the formula:

H

2 N - NH 2 2-methyl-1,5-diaminopentane having the formula: 10 H 2 N NH 2 10 1,3-diaminopentane, available under the tradename Dytek EP, having the formula:

H

2 N

NH

2 1,3-diaminobutane having the formula: 15

H

2 N NH 2 Jeffamine EDR 148, a diamine having an alkyleneoxy backbone, having the formula:

H

2 ON OO N H 2 20 3-methyl-3-aminoethyl-5-dimethyl-l1-aminocyclohexane (isophorone diamine) having the formula: 34 WO 01/16278 PCT/USUUI/2zi21

NH

2 4NH 2 , and 1,3-bis(methylamino)cyclohexane having the formula:

CH

2

NH

2

CH

2

NH

2 5 ADDITIONAL DETERGENT COMPONENTS The following are non-limiting examples of additional detergent components (adjunct ingredients) useful in the bleach systems, especially laundry detergent compositions, of the present invention, said adjunct ingredients include builders, optical brighteners, soil release polymers, dye transfer agents, dispersants, enzymes, suds suppressers, dyes, perfumes, colorants, 10 filler salts, hydrotropes, photoactivators, fluorescers, fabric conditioners, hydrolyzable surfactants, preservatives, anti-oxidants, chelants, stabilizers, anti-shrinkage agents, anti-wrinkle agents, germicides, fungicides, anti corrosion agents, and mixtures thereof. Builders - The bleach systems of the present invention preferably comprise one or more detergent builders or builder systems. When present, the compositions will typically comprise at 15 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. The level of builder can vary widely depending upon the end use of the composition and its desired physical form. When present, the compositions will typically comprise at least about 1% builder. Formulations typically comprise from about 5% to about 50%, more typically about 20 5% to about 30%, by weight, of detergent builder. Granular formulations typically comprise from about 10% to about 80%, more typically from about 15% to about 50% by weight, of the detergent builder. Lower or higher levels of builder, however, are not meant to be excluded. Inorganic or P-containing detergent builders include, but are not limited to, the alkali metal, ammonium and alkanolammonium salts of polyphosphates (exemplified by the 25 tripolyphosphates, pyrophosphates, and glassy polymeric meta-phosphates), phosphonates, phytic acid, silicates, carbonates (including bicarbonates and sesquicarbonates), sulphates, and aluminosilicates. However, non-phosphate builders are required in some locales. Importantly, the compositions herein function surprisingly well even in the presence of the so-called "weak" 35 VYu U1/I0Z/5 LI~P~sh builders (as compared with phosphates) such as citrate, or in the so-called "underbuilt" situation that may occur with zeolite or layered silicate builders. Examples of silicate builders are the alkali metal silicates, particularly those having a SiO 2 :Na 2 0 ratio in the range 1.6:1 to 3.2:1 and layered silicates, such as the layered sodium 5 silicates described in 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 herein as "SKS-6"). Unlike zeolite builders, the Na SKS-6 silicate builder does not contain aluminum. NaSKS-6 has the delta-Na 2 SiO 5 morphology form of layered silicate. It can be prepared by methods such as those described in German DE-A-3,417,649 and DE-A-3,742,043. SKS-6 is a highly preferred 10 layered silicate for use herein, but other such layered silicates, such as those having the general formula NaMSixO2x+l-yH 2 0 wherein M is sodium or hydrogen, x is a number from 1.9 to 4, preferably 2, and y is a number from 0 to 20, preferably 0 can be used herein. Various 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-Na 2 SiO 5 (NaSKS-6 form) is most preferred for use 15 herein. Other silicates may also be useful such as for example magnesium silicate, which can serve as a crispening agent in granular formulations, as a stabilizing agent for oxygen bleaches, and as a component of suds control systems. Examples of carbonate builders are the alkaline earth and alkali metal carbonates as disclosed in German Patent Application No. 2,321,001 published on November 15, 1973. 20 Aluminosilicate builders are useful in the present invention. Aluminosilicate builders are of great importance in most currently marketed heavy duty granular detergent compositions, and can also be a significant builder ingredient in liquid detergent formulations. Aluminosilicate builders include those having the empirical formula: [Mz(zAIO2)y]-xH 2 0 25 wherein z and y are integers of at least 6, the molar ratio of z to y is in the range from 1.0 to about 0.5, and x is an integer from about 15 to about 264. Useful aluminosilicate ion exchange materials are commercially available. These aluminosilicates can be crystalline or amorphous in structure and can be naturally-occurring aluminosilicates or synthetically derived. A method for producing aluminosilicate ion exchange 30 materials is disclosed in U.S. 3,985,669, Krummel et al, issued October 12, 1976. Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite P (B), Zeolite MAP and Zeolite X. In an especially preferred embodiment, the crystalline aluminosilicate ion exchange material has the formula: Na l2[(A10 2

)

12 (SiO 2

)

12 ]-xH 2 0 36 W' U1/O101I L 1I/U3UU/3J3A 1 wherein x is from about 20 to about 30, especially about 27. This material is known as Zeolite A. Dehydrated zeolites (x = 0 - 10) may also be used herein. Preferably, the aluminosilicate has a particle size of about 0.1-10 microns in diameter. Organic detergent builders suitable for the purposes of the present invention include, but 5 are not restricted to, a wide variety of polycarboxylate compounds. As used herein, "poly carboxylate" refers to compounds having a plurality of carboxylate groups, preferably at least 3 carboxylates. Polycarboxylate builder can generally be added to the composition in acid form, but can also be added in the form of a neutralized salt. When utilized in salt form, alkali metals, such as sodium, potassium, and lithium, or alkanolammonium salts are preferred. 10 Included among the polycarboxylate builders are a variety of categories of useful mate rials. One important category of polycarboxylate builders encompasses the ether polycarboxy lates, including oxydisuccinate, as disclosed in U.S. 3,128,287 Berg, issued April 7, 1964, U.S. 3,635,830 Lamberti et al., issued January 18, 1972, and U.S. 3,936,448 Lamberti, issued February 3, 1976. See also "TMS/TDS" builders of U.S. 4,663,071 Bush et al., issued May 5, 15 1987. Suitable ether polycarboxylates also include cyclic compounds, particularly alicyclic compounds, such as those described in U.S. 3,923,679 Rapko, issued December 2, 1975; U.S. 4,158,635 Crutchfield et al., issued June 19, 1979; U.S. 4,120,874 Crutchfield et al., issued October 17, 1978; and U.S. 4,102,903 Crutchfield et al., issued July 25, 1978. Other useful detergency builders include the ether hydroxypolycarboxylates, copolymers 20 of maleic anhydride with ethylene or vinyl methyl ether, 1, 3, 5-trihydroxy benzene-2, 4, 6 trisulphonic acid, and carboxymethyloxysuccinic acid, the various alkali metal, ammonium and substituted ammonium salts of polyacetic acids such as ethylenediamine tetraacetic acid and nitrilotriacetic acid, as well as polycarboxylates such as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, and 25 soluble salts thereof. Citrate builders, e.g., citric 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 biodegradability. Citrates can also be used in granular compositions, especially in combination with zeolite and/or layered silicate 30 builders. Oxydisuccinates are also especially useful in such compositions and combinations. Also suitable in the bleach systems of the present invention are the 3,3-dicarboxy-4-oxa 1,6-hexanedioates and the related compounds disclosed in U.S. 4,566,984, Bush, issued January 28, 1986. Useful succinic acid builders include the C 5

-C

2 0 alkyl and alkenyl succinic acids and salts thereof. A particularly preferred compound of this type is dodecenylsuccinic acid. Specific 35 examples of succinate builders include: laurylsuccinate, myristylsuccinate, palmitylsuccinate, 2 37 VVU U1 /a rL I/U3UU/L33ZI dodecenylsuccinate (preferred), 2-pentadecenylsuccinate, and the like. Laurylsuccinates are the preferred builders of this group, and are described in European Patent Application 86200690.5/0,200,263, published November 5, 1986. Other suitable polycarboxylates are disclosed in U.S. 4,144,226, Crutchfield et al., issued 5 March 13, 1979 and in U.S. 3,308,067, Diehl, issued March 7, 1967. See also Diehl U.S. Patent 3,723,322. Fatty acids, e.g., C 12

-C

18 monocarboxylic acids, can also be incorporated into the compositions alone, or in combination with the aforesaid builders, especially citrate and/or the succinate builders, to provide additional builder activity. Such use of fatty acids will generally 10 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 for mulation of bars used for hand-laundering operations, the various alkali metal phosphates such as the well-known sodium tripolyphosphates, sodium pyrophosphate and sodium orthophosphate can be used. Phosphonate builders such as ethane- I -hydroxy- 1,1 -diphosphonate and other 15 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. Chelating Agents - The bleach systems herein may also optionally contain one or more iron and/or manganese chelating agents. Such chelating agents can be selected from the group consisting of amino carboxylates, amino phosphonates, polyfunctionally-substituted aromatic 20 chelating agents and mixtures therein, all as hereinafter defined. Without intending to be bound by theory, it is believed that the benefit of these materials is due in part to their exceptional ability to remove iron and manganese ions from washing solutions by formation of soluble chelates. Examples of suitable chelating agents and levels of use are described in U.S. Pat. Nos. 5,576,282 and 5,728,671. 25 A preferred biodegradable chelator for use herein is ethylenediamine disuccinate ("EDDS"), especially the [S,S] isomer as described in U.S. Patent 4,704,233, November 3, 1987, to Hartman and Perkins. The compositions herein may also contain water-soluble methyl glycine diacetic acid (MGDA) salts (or acid form) as a chelant or co-builder useful with, for example, insoluble 30 builders such as zeolites, layered silicates and the like. If utilized, these chelating agents will generally comprise from about 0.1% by weight of the bleach systems herein to about 15%, more preferably 3.0% by weight of the bleach systems herein. Dye Transfer Inhibiting Agents - The bleach systems of the present invention may also 35 include one or more compounds, dye transfer inhibiting agents, for inhibiting dye transfer from 38 WU UI/1Oz /5 'LI/UGUU/AJAI one fabric to another of solubilized and suspended dyes encountered during fabric laundering and conditioning operations involving colored fabrics. Suitable polymeric dye transfer inhibiting agents include, but are not limited to, polyvinylpyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone 5 and N-vinylimidazole, polyvinyloxazolidones and polyvinylimidazoles or mixtures thereof. Examples of such dye transfer inhibiting agents are disclosed in U.S. Pat. Nos. 5,707,950 and 5,707,951. Additional suitable dye transfer inhibiting agents include, but are not limited to, cross linked polymers. Cross-linked polymers are polymers whose backbone are interconnected to a 10 certain degree; these links can be of chemical or physical nature, possibly with active groups on the backbone or on branches. Cross-linked polymers have been described in the Journal of Polymer Science, volume 22, pages 1035-1039. In one embodiment, the cross-linked polymers are made in such a way that they form a three-dimensional rigid structure, which can entrap dyes in the pores formed by the three 15 dimensional structure. In another embodiment, the cross-linked polymers entrap dyes by swelling. Suitable cross-linked polymers are described in the co-pending European patent application 94870213.9. Addition of such polymers also enhances the performance of the enzymes within the 20 bleach systems herein. The dye transfer inhibiting agents have the ability to complex or adsorb fugitive dyes wash out of dyed fabrics before the dyes have the opportunity to become attached to other articles in the wash. When present in the bleach systems herein, the dye transfer inhibiting agents are present at 25 levels from about 0.0001%, more preferably about 0.01%, most preferably about 0.05% by weight of the bleach systems to about 10%, more preferably about 2%, most preferably about 1% by weight of the bleach systems. Dispersants - The bleach systems of the present invention can also contain dispersants. Suitable water-soluble organic salts are the homo- or co-polymeric acids or their salts, in which 30 the polycarboxylic acid comprises at least two carboxyl radicals separated from each other by not more than two carbon atoms. Polymers of this type are disclosed in GB-A-1,596,756. Examples of such salts are polyacrylates of MW 2000-5000 and their copolymers with maleic anhydride, such copolymers having a molecular weight of from 1,000 to 100,000. 39 WU U1/1b27 r L. 1/UUU/zh.3I Especially, copolymer of acrylate and methylacrylate such as the 480N having a molecular weight of 4000, at a level from 0.5-20% by weight of composition can be added in the detergent compositions of the present invention. The compositions of the invention may contain a lime soap peptiser compound, which has 5 a lime soap dispersing power (LSDP), as defined hereinafter of no more than 8, preferably no more than 7, most preferably no more than 6. The lime soap peptiser compound is preferably present at a level from 0% to 20% by weight. A numerical measure of the effectiveness of a lime soap peptiser is given by the lime soap dispersant power (LSDP) which is determined using the lime soap dispersant test as described in 10 an article by H.C. Borghetty and C.A. Bergman, J. Am. Oil. Chem. Soc., volume 27, pages 88-90, (1950). This lime soap dispersion test method is widely used by practitioners in this art field being referred to, for example, in the following review articles; W.N. Linfield, Surfactant science Series, Volume 7, page 3; W.N. Linfield, Tenside surf. det., volume 27, pages 159-163, (1990); and M.K. Nagarajan, W.F. Masler, Cosmetics and Toiletries, volume 104, pages 71-73, (1989). The LSDP 15 is the % weight ratio of dispersing agent to sodium oleate required to disperse the lime soap deposits formed by 0.025g of sodium oleate in 30ml of water of 333ppm CaCo 3 (Ca:Mg=3:2) equivalent hardness. Surfactants having good lime soap peptiser capability will include certain amine oxides, betaines, sulfobetaines, alkyl ethoxysulfates and ethoxylated alcohols. 20 Exemplary surfactants having a LSDP of no more than 8 for use in accord with the present invention include C 1 6

-C

1 8 dimethyl amine oxide, C 1 2 -C 1 8 alkyl ethoxysulfates with an average degree of ethoxylation of from 1-5, particularly C 12

-C

15 alkyl ethoxysulfate surfactant with a degree of ethoxylation of amount 3 (LSDP=4), and the C1 4

-C

1 5 ethoxylated alcohols with an average degree of ethoxylation of either 12 (LSDP=6) or 30, sold under the tradenames 25 Lutensol A012 and Lutensol A030 respectively, by BASF GmbH. Polymeric lime soap peptisers suitable for use herein are described in the article by M.K. Nagarajan, W.F. Masler, to be found in Cosmetics and Toiletries, volume 104, pages 71-73, (1989). Hydrophobic bleaches such as 4-[N-octanoyl-6-aminohexanoyl]benzene sulfonate, 4-[N 30 nonanoyl-6-aminohexanoyl]benzene sulfonate, 4-[N-decanoyl-6-aminohexanoyl]benzene sulfonate and mixtures thereof; and nonanoyloxy benzene sulfonate together with hydrophilic / hydrophobic bleach formulations can also be used as lime soap peptisers compounds. Enzymes - The bleach systems can comprise in addition to the amylase of the present invention one or more detergent enzymes which provide cleaning performance and/or fabric care 35 benefits. Such enzymes can include proteases, amylases, cellulases and lipases. They may be 40 WU U1I1OI/5 rL I U UIZ.30LI incorporated into the non-aqueous liquid bleach systems herein in the form of suspensions, "marumes" or "prills". Another suitable type of enzyme comprises those in the form of slurries of enzymes in nonionic surfactants, e.g., the enzymes marketed by Novo Nordisk under the tradename "SL" or the microencapsulated enzymes marketed by Novo Nordisk under the 5 tradename "LDP." Suitable enzymes and levels of use are described in U.S. Pat. No. 5,576,282. Enzymes added to the compositions herein in the form of conventional enzyme prills are especially preferred for use herein. Such prills will generally range in size from about 100 to 1,000 microns, more preferably from about 200 to 800 microns and will be suspended throughout the non-aqueous liquid phase of the composition. Prills in the compositions of the present 10 invention have been found, in comparison with other enzyme forms, to exhibit especially desirable enzyme stability in terms of retention of enzymatic activity over time. Thus, compositions which utilize enzyme prills need not contain conventional enzyme stabilizing such as must frequently be used when enzymes are incorporated into aqueous liquid detergents. Examples of suitable enzymes include, but are not limited to, hemicellulases, peroxidases, 15 proteases, cellulases, xylanases, lipases, phospholipases, esterases, cutinases, pectinases, keratanases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases, pentosanases, malanases, 1-glucanases, arabinosidases, hyaluronidase, chondroitinase, laccase, known amylases, mannanases, xyloglucanases and mixtures thereof. A preferred combination is a bleach system having a cocktail of conventional applicable enzymes like 20 protease, lipase, cutinase and/or cellulase in conjunction with the amylase of the present invention. Examples of such suitable enzymes are disclosed in U.S. Patent Nos. 5,576,282, 5,728,671 and 5,707,950 Suitable proteases are the subtilisins which are obtained from particular strains of B. 25 subtilis and B. licheniformis (subtilisin BPN and BPN'). One suitable protease is obtained from a strain of Bacillus, having maximum activity throughout the pH range of 8-12, developed and sold as ESPERASE® by Novo Industries A/S of Denmark, hereinafter "Novo". The preparation of this enzyme and analogous enzymes is described in GB 1,243,784 to Novo. Other suitable proteases include ALCALASE®, DURAZYM® and SAVINASE® from Novo and 30 MAXATASE®, 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, published October 29, 1986, which refers 35 to a modified bacterial serine protealytic enzyme which is called "Protease A" herein. More 41 WO 01/16278 rL. iu"/) izL3I preferred is what is called herein "Protease C", which is a variant of an alkaline serine protease from Bacillus in which lysine replaced arginine at position 27, tyrosine replaced valine at position 104, serine replaced asparagine at position 123, and alanine replaced threonine at position 274. Protease C is described in EP 90915958:4, corresponding to WO 91/06637, Published May 16, 5 1991. Genetically modified variants, particularly of Protease C, are also included herein. See also a high pH protease from Bacillus sp. NCIMB 40338 described in WO 93/18140 A to Novo. Enzymatic detergents comprising protease, one or more other enzymes, and a reversible protease inhibitor are described in WO 92/03529 A to Novo. When desired, a protease having decreased adsorption and increased hydrolysis is available as described in WO 95/07791 to Procter & 10 Gamble. A recombinant trypsin-like protease for detergents suitable herein is described in WO 94/25583 to Novo. In more detail, the protease referred to as "Protease D" is a carbonyl hydrolase variant having an amino acid sequence not found in nature, which is derived from a precursor carbonyl hydrolase by substituting a different amino acid for a plurality of amino acid residues at a position 15 in said carbonyl hydrolase equivalent to position +76, preferably also in combination with one or more amino acid residue positions equivalent 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 the numbering of Bacillus amyloliquefaciens subtilisin, as described in WO 95/10615 published April 20, 1995 20 by Genencor International. Also suitable for the present invention are proteases described in patent applications EP 251 446 and WO91/06637 and protease BLAP® described in WO91/02792. The proteolytic enzymes are incorporated in the bleach systems of the present invention a level of from 0.0001% to 2%, preferably from 0.001% to 0.2%, more preferably from 0.005% to 0.1% pure enzyme by weight of the composition. 25 Useful proteases are also described in PCT publications: WO 95/30010 published November 9, 1995 by The Procter & Gamble Company; WO 95/30011 published November 9, 1995 by The Procter & Gamble Company; WO 95/29979 published November 9, 1995 by The Procter & Gamble Company. Other particularly useful proteases are multiply-substituted protease variants comprising a 30 substitution of an amino acid residue with another naturally occurring amino acid residue at an amino acid residue position corresponding to position 103 of Bacillus amyloliquefaciens subtilisin in combination with a substitution of an amino acid residue with another naturally occurring amino acid residue at one or more amino acid residue positions corresponding to positions 1, 3, 4, 8, 9, 10, 12, 13, 16, 17, 18, 19, 20, 21, 22, 24, 27, 33, 37, 38, 42, 43, 48, 55, 57, 58, 61, 62, 68, 72, 35 75, 76, 77, 78, 79, 86, 87, 89, 97, 98, 99, 101, 102, 104, 106, 107, 109, 111, 114, 116, 117, 119, 42 WOU b/16278 Y"I/UNUU/ZJJZI 121, 123, 126, 128, 130, 131, 133, 134, 137, 140, 141, 142, 146, 147, 158, 159, 160, 166, 167, 170, 173, 174, 177, 181, 182, 183, 184, 185, 188, 192, 194, 198, 203, 204, 205,206, 209, 210, 211, 212, 213, 214, 215, 216, 217, 218, 222, 224, 227, 228, 230, 232, 236, 237, 238, 240, 242, 243, 244, 245, 246, 247, 248, 249, 251, 252, 253, 254, 255, 256, 257, 258, 259, 260, 261,262, 5 263, 265, 268, 269, 270, 271, 272, 274 and 275 of Bacillus amyloliquefaciens subtilisin; wherein when said protease variant includes a substitution of amino acid residues at positions corresponding to positions 103 and 76, there is also a substitution of an amino acid residue at one or more amino acid residue positions other than amino acid residue positions corresponding to positions 27, 99, 101, 104, 107, 109, 123, 128, 166, 204, 206, 210, 216, 217, 218, 222, 260, 265 10 or 274 of Bacillus amyloliquefaciens subtilisin and/or multiply-substituted protease variants comprising a substitution of an amino acid residue with another naturally occurring amino acid residue at one or more amino acid residue positions corresponding to positions 62, 212, 230, 232, 252 and 257 of Bacillus amyloliquefaciens subtilisin as described in PCT Published Application Nos. WO 99/20727, WO 99/20726, and WO 99/20723 all owned by The Procter & Gamble 15 Company. More preferably the protease variant includes a substitution set selected from the group consisting of: 12/76/103/104/130/222/245/261; 20 62/103/104/159/232/236/245/248/252; 62/103/104/159/213/232/236/245/248/252; 62/101/103/104/159/212/213/232/236/245/248/252; 68/103/104/159/232/236/245; 68/103/104/159/230/232/236/245; 25 68/103/104/159/209/232/236/245; 68/103/104/159/232/236/245/257; 68/76/103/104/159/213/232/236/245/260; 68/103/104/159/213/232/236/245/248/252; 68/103/104/159/183/232/236/245/248/252; 30 68/103/104/159/185/232/236/245/248/252; 68/103/104/159/185/210/232/236/245/248/252; 68/103/104/159/210/232/236/245/248/252; 68/103/104/159/213/232/236/245; 98/103/104/159/232/236/245/248/252; 35 98/102/103/104/159/212/232/236/245/248/252; 43 V1 U0I1O/15 YI"I.1I5UUZ4J8LI5 101/103/104/159/232/236/245/248/252; 102/103/104/159/232/236/245/248/252; 103/104/159/23/230/236/245; 103/104/159/232/236/245/248/252; 5 103/104/159/217/232/236/245/248/252; 103/104/130/159/232/236/245/248/252; 103/104/131/159/232/236/245/248/252; 103/104/159/213/232/236/245/248/252; and 103/104/159/232/236/245. 10 Still even more preferably the protease variant includes a substitution set selected from the group consisting of: 12R/76D/103A/104T/130T/222S/245R/261D; 15 62D/103A/104I/159D/232V/236H/245R/248D/252K; 62D/103A/1041/159D/213 R/232V/236H/245R/248D/252K; 68A/103A/104I/159D/209W/232V/236H/245R; 68A/76D/103A/104I/159D/213 R/232V/236H/245R/260A; 68A/103A/104I/159D/213E/232V/236H/245R/248D/252K; 20 68A/103A/1041/159D/183D/232V/236H/245R/248D/252K; 68A/103A/1 041/159D/232V/236H/245R; 68A/103A/104I/159D/230V/232V/236H/245R; 68A/103A/104I/159D/232V/236H/245R/257V; 68A/103A/1041/159D/213G/232V/236H/245R/248D/252K; 25 68A/103A/1 041/159D/185D/232V/236H/245R/248D/252K; 68A/103A/104I/159D/185D/210 OL/232V/236H/245R/248D/252K; 68A/103A/104I/159D/210L/232V/236H/245R/248D/252K; 68A/103A/104I/159D/213G/232V/236H/245R; 98L/103A/1041/159D/232V/236H/245R/248D/252K; 30 98L/102A/103A/104I/159D/212G/232V/236H/245R/248D/252K; 101 G/103A/104I/159D/232V/236H/245R/248D/252K; 102A/103A/104I/159D/232V/236H/245R/248D/252K; 103A/1 04I/159D/230V/236H/245R; 103A/1041/159D/232V/236H/245R/248D/252K; 35 103A/104I/159D/217E/232V/236H/245R/248D/252K; 44 WO 01/16278 PCT/US00/23321 103A/1041/130G/159D/232V/236H/245R/248D/252K; 103A/1041/131V/1 59D/232V/236H/245R/248D/252K; 103A/104I/159D/213R/232V/236H/245R/248D/252K; and 103A/104I/159D/232V/236H/245R. 5 Most preferably the protease variant includes the substitution set 101/103/104/159/232/ 236/245/248/252, preferably 101 G/103A/104I/159D/232V/236H/245R/248D/252K. The cellulases usable in the present invention include both bacterial or fungal cellulase. Preferably, they will have a pH optimum of between 5 and 9.5. Suitable cellulases are disclosed in 10 U.S. Patent 4,435,307, Barbesgoard et al, which discloses fungal cellulase produced from Humicola insolens. Suitable cellulases are also disclosed in GB-A-2.075.028; GB-A-2.095.275 and DE-OS-2.247.832. Examples of such cellulases are cellulases produced by a strain of Humicola insolens (Humicola grisea var. thermoidea), particularly the Humicola strain DSM 1800. 15 Other suitable cellulases are cellulases originated from Humicola insolens having a molecular weight of about 50KDa, an isoelectric point of 5.5 and containing 415 amino acids; and a ~43kD endoglucanase derived from Humicola insolens, DSM 1800, exhibiting cellulase activity; a preferred endoglucanase component has the amino acid sequence disclosed in PCT Patent Application No. WO 91/17243. Also suitable cellulases are the EGIII cellulases from 20 Trichoderma longibrachiatum described in WO94/21801, Genencor, published September 29, 1994. Especially suitable cellulases are the cellulases having color care benefits. Examples of such cellulases are cellulases described in European patent application No. 91202879.2, filed November 6, 1991 (Novo). Carezyme and Celluzyme (Novo Nordisk A/S) are especially useful. See also WO91/17243. 25 Peroxidase enzymes are known in the art, and include, for example, horseradish peroxidase, ligninase and haloperoxidase such as chloro- and bromo-peroxidase. Peroxidase containing bleach systems are disclosed, for example, in U.S. Patent Nos. 5,576,282, 5,728,671 and 5,707,950, PCT International Applications WO 89/099813, WO89/09813 and in European Patent application EP No. 91202882.6, filed on November 6, 1991 and EP No. 96870013.8, filed 30 February 20, 1996. Also suitable is the laccase enzyme. Preferred enhancers are substituted phenthiazine and phenoxasine 10 Phenothiazinepropionicacid (PPT), 10-ethylphenothiazine-4-carboxylic acid (EPC), 10 phenoxazinepropionic acid (POP) and 10-methylphenoxazine (described in WO 94/12621) and substituted syringates (C3-C5 substituted alkyl syringates) and phenols. Sodium percarbonate or 35 perborate are preferred sources of hydrogen peroxide. 45 WO 01/16278 Pci/US:UU/izjzi Said peroxidases are normally incorporated in the bleach system at levels from 0.0001% to 2% of active enzyme by weight of the bleach system. Other preferred enzymes that can be included in the bleach systems of the present invention include lipases. Suitable lipase enzymes for detergent usage include those produced by 5 microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as disclosed in British Patent 1,372,034. Suitable lipases include those which show a positive immunological cross-reaction with the antibody of the lipase, produced by the microorganism Pseudomonas fluorescent IAM 1057. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade name Lipase P "Amano," hereinafter referred to as "Amano 10 P". Other suitable commercial lipases include Amano-CES, lipases ex Chromobacter viscosum, e.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. Especially suitable lipases are lipases such as Ml LIPASE® and LIPOMAX® (Gist-Brocades) and LIPOLASE® and LIPOLASE 15 ULTRA®(Novo) which have found to be very effective when used in combination with the compositions of the present invention. Also suitable are cutinases [EC 3.1.1.50] which can be considered as a special kind of lipase, namely lipases which do not require interfacial activation. Addition of cutinases to bleach systems have been described in e.g. WO 88/09367 (Genencor). 20 The lipases and/or cutinases are normally incorporated in the bleach system at levels from 0.0001% to 2% of active enzyme by weight of the bleach system. Known amylases (a and/or B) can be included for removal of carbohydrate-based stains. WO 94/02597, Novo Nordisk A/S published February 03, 1994, describes cleaning compositions which incorporate mutant amylases. See also WO94/1 8314, Genencor, published August 18, 1994 25 and WO95/10603, Novo Nordisk A/S, published April 20, 1995. Other amylases known for use in bleach systems include both a- and p-amylases. ax-Amylases are known in the art and include those disclosed in US Pat. 5,003,257; EP 252,666; WO 91/00353; FR 2,676,456; EP 285,123; EP 525,610; EP 368,341; and British Patent Specification No. 1,296,839 (Novo). Other suitable amylase are stability-enhanced amylases including PURAFACT OX AM® described in WO 30 94/18314, published August 18, 1994 and WO96/05295, Genencor, published February 22, 1996 and amylase variants from Novo Nordisk A/S, disclosed in WO 95/10603, published April 95. Examples of commercial a-amylases products are TERMAMYL®, BAN®, FUNGAMYL® and DURAMYL®, all available from Novo Nordisk A/S Denmark. WO95/26397 describes other suitable amylases : a-amylases characterized by having a specific 35 activity at least 25% higher than the specific activity of TERMAMYL® at a temperature range of 46 WO 01/16278 PI'T/USUU/23I321 25 0 C to 55'C and at a pH value in the range of 8 to 10, measured by the Phadebas® a-amylase activity assay. Other amylolytic enzymes with improved properties with respect to the activity level and the combination of thermostability and a higher activity level are described in WO95/35382. 5 The compositions of the present invention may also comprise a mannanase enzyme. Preferably, the mannanase is selected from the group consisting of: three mannans-degrading enzymes : EC 3.2.1.25 : P3-mannosidase, EC 3.2.1.78 : Endo-l,4-p-mannosidase, referred therein after as "mannanase" and EC 3.2.1.100 : 1,4-p3-mannobiosidase and mixtures thereof (IUPAC Classification- Enzyme nomenclature, 1992 ISBN 0-12-227165-3 Academic Press). 10 More preferably, the treating compositions of the present invention, when a mannanase is present, comprise a 3-1,4-Mannosidase (E.C. 3.2.1.78) referred to as Mannanase. The term "mannanase" or "galactomannanase" denotes a mannanase enzyme defined according to the art as officially being named mannan endo-1,4-beta-mannosidase and having the alternative names beta mannanase and endo-1,4-mannanase and catalysing the reaction: random hydrolysis of 1,4-beta 15 D- mannosidic linkages in mannans, galactomannans, glucomannans, and galactoglucomannans. In particular, Mannanases (EC 3.2.1.78) constitute a group of polysaccharases which degrade mannans and denote enzymes which are capable of cleaving polyose chains containing mannose units, i.e. are capable of cleaving glycosidic bonds in mannans, glucomannans, galactomannans and galactogluco-mannans. Mannans are polysaccharides having a backbone 20 composed of 03-1,4- linked mannose; glucomannans are polysaccharides having a backbone or more or less regularly alternating 3-1,4 linked mannose and glucose; galactomannans and galactoglucomannans are mannans and glucomannans with x-1,6 linked galactose sidebranches. These compounds may be acetylated. The degradation of galactomannans and galactoglucomannans is facilitated by full or 25 partial removal of the galactose sidebranches. Further the degradation of the acetylated mannans, glucomannans, galactomannans and galactogluco-mannans is facilitated by full or partial deacetylation. Acetyl groups can be removed by alkali or by mannan acetylesterases. The oligomers which are released from the mannanases or by a combination of mannanases and a galactosidase and/or mannan acetyl esterases can be further degraded to release free maltose by 3 30 mannosidase and/or 3-glucosidase. Mannanases have been identified in several Bacillus organisms. For example, Talbot et al., Appl. Environ. Microbiol., Vol.56, No. 11, pp. 3505-3510 (1990) describes a beta-mannanase derived from Bacillus stearothermophilus in dimer form having molecular weight of 162 kDa and an optimum pH of 5.5-7.5. Mendoza et al., World J. Microbiol. Biotech., Vol. 10, No. 5, pp. 551 35 555 (1994) describes a beta-mannanase derived from Bacillus subtilis having a molecular weight 47 WO 01/16278 YL.1/UsUU/L.3I of 38 kDa, an optimum activity at pH 5.0 and 55C and a pl of 4.8. JP-03047076 discloses a beta mannanase derived from Bacillus sp., having a molecular weight of 373 kDa measured by gel filtration, an optimum pH of 8-10 and a pI of 5.3-5.4. JP-63056289 describes the production of an alkaline, thermostable beta-mannanase which hydrolyses beta-1,4-D-mannopyranoside bonds of 5 e.g. mannans and produces manno-oligosaccharides. JP-63036774 relates to the Bacillus microorganism FERM P-8856 which produces beta-mannanase and beta-mannosidase at an alkaline pH. JP-08051975 discloses alkaline beta-mannanases from alkalophilic Bacillus sp. AM 001. A purified mannanase from Bacillus amyloliquefaciens useful in the bleaching of pulp and paper and a method of preparation thereof is disclosed in WO 97/11164. WO 91/18974 describes 10 a hemicellulase such as a glucanase, xylanase or mannanase active at an extreme pH and temperature. WO 94/25576 discloses an enzyme from Aspergillus aculeatus, CBS 101.43, exhibiting mannanase activity which may be useful for degradation or modification of plant or algae cell wall material. WO 93/24622 discloses a mannanase isolated from Trichoderma reseei useful for bleaching lignocellulosic pulps. An hemicellulase capable of degrading mannan 15 containing hemicellulose is described in WO91/18974 and a purified mannanase from Bacillus amyloliquefaciens is described in WO97/11164. Preferably, the mannanase enzyme will be an alkaline mannanase as defined below, more preferably, a mannanase originating from a bacterial source. Especially, the laundry detergent composition of the present invention will comprise an alkaline mannanase selected from the 20 mannanase from the strain Bacillus agaradhaerens NICMB 40482; the mannanase from Bacillus subtilis strain 168, gene yght; the mannanase from Bacillus sp. 1633 and/or the mannanase from Bacillus sp. AAI12. Most preferred mannanase for the inclusion in the detergent compositions of the present invention is the mannanase enzyme originating from Bacillus sp. 1633 as described in the co-pending Danish patent application No. PA 1998 01340. 25 The terms "alkaline mannanase enzyme" is meant to encompass an enzyme having an enzymatic activity of at least 10%, preferably at least 25%, more preferably at least 40% of its maximum activity at a given pH ranging from 7 to 12, preferably 7.5 to 10.5. The alkaline mannanase from Bacillus agaradhaerens NICMB 40482 is described in the co-pending U.S. patent application serial No. 09/111,256. More specifically, this mannanase is: 30 i) a polypeptide produced by Bacillus agaradhaerens, NCIMB 40482; or ii) a polypeptide comprising an amino acid sequence as shown in positions 32-343 of SEQ ID NO:2 as shown in U.S. patent application serial No. 09/111,256; or iii) an analogue of the polypeptide defined in i) or ii) which is at least 70% homologous with said polypeptide, or is derived from said polypeptide by 35 substitution, deletion or addition of one or several amino acids, or is 48 WOU l/b278 YL- 1/U5UUIZJJZI immunologically reactive with a polyclonal antibody raised against said polypeptide in purified form. Also encompassed is the corresponding isolated polypeptide having mannanase activity selected from the group consisting of: 5 (a) polynucleotide molecules encoding a polypeptide having mannanase activity and comprising a sequence of nucleotides as shown in SEQ ID NO: 1 from nucleotide 97 to nucleotide 1029 as shown in U.S. patent application serial No. 09/111,256; (b) species homologs of (a); (c) polynucleotide molecules that encode a polypeptide having mannanase 10 activity that is at least 70% identical to the amino acid sequence of SEQ ID NO: 2 from amino acid residue 32 to amino acid residue 343 as shown in U.S. patent application serial No. 09/111,256; (d) molecules complementary to (a), (b) or (c); and (e) degenerate nucleotide sequences of (a), (b), (c) or (d). 15 The plasmid pSJ1678 comprising the polynucleotide molecule (the DNA sequence) encoding said mannanase has been transformed into a strain of the Escherichia coli which was deposited by the inventors according to the Budapest Treaty on the International Recognition of the Deposit of Microorganisms for the Purposes of Patent Procedure at the Deutsche Sammlung von Mikroorganismen und Zellkulturen GmbH, Mascheroder Weg lb, D-38124 Braunschweig, 20 Federal Republic of Germany, on 18 May 1998 under the deposition number DSM 12180. A second more preferred enzyme is the mannanase from the Bacillus subtilis strain 168, which is described in the co-pending U.S. patent application serial No. 09/095,163. More specifically, this mannanase is: i) is encoded by the coding part of the DNA sequence shown in SED ID No. 5 25 shown in the U.S. patent application serial No. 09/095,163 or an analogue of said sequence; and/or ii) a polypeptide comprising an amino acid sequence as shown SEQ ID NO:6 shown in the U.S. patent application serial No. 09/095,163; or iii) an analogue of the polypeptide defined in ii) which is at least 70% homologous 30 with said polypeptide, or is derived from said polypeptide by substitution, deletion or addition of one or several amino acids, or is immunologically reactive with a polyclonal antibody raised against said polypeptide in purified form. Also encompassed in the corresponding isolated polypeptide having mannanase activity selected from the group consisting of: 49 WO 01/16278 PcI/uNuu/iZJzi (a) polynucleotide molecules encoding a polypeptide having mannanase activity and comprising a sequence of nucleotides as shown in SEQ ID NO:5 as shown in the U.S. patent application serial No. 09/095,163 (b) species homologs of (a); 5 (c) polynucleotide molecules that encode a polypeptide having mannanase activity that is at least 70% identical to the amino acid sequence of SEQ ID NO: 6 as shown in the U.S. patent application serial No. 09/095,163; (d) molecules complementary to (a), (b) or (c); and (e) degenerate nucleotide sequences of (a), (b), (c) or (d). 10 A third more preferred mannanase is described in the co-pending Danish patent application No. PA 1998 01340. More specifically, this mannanase is: i) a polypeptide produced by Bacillus sp. 1633; ii) a polypeptide comprising an amino acid sequence as shown in positions 33-340 of SEQ ID NO:2 as shown in the Danish application No. PA 1998 01340; 15 or iii) an analogue of the polypeptide defined in i) or ii) which is at least 65% homologous with said polypeptide, is derived from said polypeptide by substitution, deletion or addition of one or several amino acids, or is immunologically reactive with a polyclonal antibody raised against said 20 polypeptide in purified form. Also encompassed is the corresponding isolated polynucleotide molecule selected from the group consisting of: (a) polynucleotide molecules encoding a polypeptide having mannanase activity and comprising a sequence of nucleotides as shown in SEQ ID NO: 1 from nucleotide 25 317 to nucleotide 1243 the Danish application No. PA 1998 01340; (b) species homologs of (a); (c) polynucleotide molecules that encode a polypeptide having mannanase activity that is at least 65% identical to the amino acid sequence of SEQ ID NO: 2 from amino acid residue 33 to amino acid residue 340 the Danish application No. 30 PA 1998 01340; (d) molecules complementary to (a), (b) or (c); and (e) degenerate nucleotide sequences of (a), (b), (c) or (d). The plasmid pBXM3 comprising the polynucleotide molecule (the DNA sequence) encoding a mannanase of the present invention has been transformed into a strain of the 35 Escherichia coli which was deposited by the inventors according to the Budapest Treaty on the 50 WO 01/16278 FlTU UU/2IJI.521 International Recognition of the Deposit of Microorganisms for the Purposes of Patent Procedure at the Deutsche Sammlung von Mikroorganismen und Zellkulturen GmbH, Mascheroder Weg I b, D-38124 Braunschweig, Federal Republic of Germany, on 29 May 1998 under the deposition number DSM 12197. 5 A fourth more preferred mannanase is described in the Danish co-pending patent application No. PA 1998 01341. More specifically, this mannanase is: i) a polypeptide produced by Bacillus sp. AAI 12; ii) a polypeptide comprising an amino acid sequence as shown in positions 25-362 of SEQ ID NO:2as shown in the Danish application No. PA 1998 01341; 10 or iii) an analogue of the polypeptide defined in i) or ii) which is at least 65% homologous with said polypeptide, is derived from said polypeptide by substitution, deletion or addition of one or several amino acids, or is immunologically reactive with a polyclonal antibody raised against said 15 polypeptide in purified form. Also encompassed is the corresponding isolated polynucleotide molecule selected from the group consisting of (a) polynucleotide molecules encoding a polypeptide having mannanase activity and comprising a sequence of nucleotides as shown in SEQ ID NO: 1 from nucleotide 20 225 to nucleotide 1236 as shown in the Danish application No. PA 1998 01341; (b) species homologs of(a); (c) polynucleotide molecules that encode a polypeptide having mannanase activity that is at least 65% identical to the amino acid sequence of SEQ ID NO: 2 from amino acid residue 25 to amino acid residue 362 as shown in the Danish 25 application No. PA 1998 01341; (d) molecules complementary to (a), (b) or (c); and (e) degenerate nucleotide sequences of (a), (b), (c) or (d). The plasmid pBXMI comprising the polynucleotide molecule (the DNA sequence) encoding a mannanase of the present invention has been transformed into a strain of the 30 Escherichia coli which was deposited by the inventors according to the Budapest Treaty on the International Recognition of the Deposit of Microorganisms for the Purposes of Patent Procedure at the Deutsche Sammlung von Mikroorganismen und Zellkulturen GmbH, Mascheroder Weg lb, D-38124 Braunschweig, Federal Republic of Germany, on 7 October 1998 under the deposition number DSM 12433. 51 WO 01/16278 'C/UUU ou .Ii The mannanase, when present, is incorporated into the treating compositions of the present invention preferably at a level of from 0.0001% to 2%, more preferably from 0.0005% to 0.1%, most preferred from 0.001% to 0.02% pure enzyme by weight of the composition. The compositions of the present invention may also comprise a xyloglucanase enzyme. 5 Suitable xyloglucanases for the purpose of the present invention are enzymes exhibiting endoglucanase activity specific for xyloglucan, preferably at a level of from about 0.001% to about 1%, more preferably from about 0.01% to about 0.5%, by weight of the composition. As used herein, the term "endoglucanase activity" means the capability of the enzyme to hydrolyze 1,4-p3-D-glycosidic linkages present in any cellulosic material, such as cellulose, cellulose 10 derivatives, lichenin, P3-D-glucan, or xyloglucan. The endoglucanase activity may be determined in accordance with methods known in the art, examples of which are described in WO 94/14953 and hereinafter. One unit of endoglucanase activity (e.g. CMCU, AVIU, XGU or BGU) is defined as the production of 1 ptmol reducing sugar/min from a glucan substrate, the glucan substrate being, e.g., CMC (CMCU), acid swollen Avicell (AVIU), xyloglucan (XGU) or cereal 03 15 -glucan (BGU). The reducing sugars are determined as described in WO 94/14953 and hereinafter. The specific activity of an endoglucanase towards a substrate is defined as units/mg of protein. Suitable are enzymes exhibiting as its highest activity XGU endoglucanase activity (hereinafter "specific for xyloglucan"), which enzyme: 20 i) is encoded by a DNA sequence comprising or included in at least one of the following partial sequences (a) ATTCATTTGT GGACAGTGGA C (SEQ ID No: 1) (b) GTTGATCGCA CATTGAACCA (SEQ ID NO: 2) (c) ACCCCAGCCG ACCGATTGTC (SEQ ID NO: 3) 25 (d) CTTCCTTACC TCACCATCAT (SEQ ID NO: 4) (e) TTAACATCTT TTCACCATGA (SEQ ID NO: 5) (f) AGCTTTCCCT TCTCTCCCTT (SEQ ID NO: 6) (g) GCCACCCTGG CTTCCGCTGC CAGCCTCC (SEQ ID NO: 7) (h) GACAGTAGCA ATCCAGCATT (SEQ ID NO: 8) 30 (i) AGCATCAGCC GCTTTGTACA (SEQ ID NO: 9) (j) CCATGAAGTT CACCGTATTG (SEQ ID NO: 10) (k) GCACTGCTTC TCTCCCAGGT (SEQ ID NO: 11) (1) GTGGGCGGCC CCTCAGGCAA (SEQ ID NO: 12) (m) ACGCTCCTCC AATTTTCTCT (SEQ ID NO: 13) 35 (n) GGCTGGTAG TAATGAGTCT (SEQ ID NO: 14) 52 WO 01/16278 Iui uiz.3.ZI (o) GGCGCAGAGT TTGGCCAGGC (SEQ ID NO: 15) (p) CAACATCCCC GGTGTTCTGG G (SEQ ID NO: 16) (q) AAAGATTCAT TTGTGGACAG TGGACGTTGA TCGCACATTG AACCAACCCC AGCCGACCGA 5 TTGTCCTTCC TTACCTCACC ATCATTTAAC ATCTTTTCAC CATGAAGCTT TCCCTTCTCT CCCTTGCCAC CCTGGCTTCC GCTGCCAGCC TCCAGCGCCG CACACTTCTG CGGTCAGTGG GATACCGCCA CCGCCGGTGA CTTCACCCTG TACAACGACC TTTGGGGCGA 10 GACGGCCGGC ACCGGCTCCC AGTGCACTGG AGTCGACTCC TACAGCGGCG ACACCATCGC TTGTCACACC AGCAGGTCCT GGTCGGAGTA GCAGCAGCGT CAAGAGCTAT GCCAACG (SEQ ID NO:17) or 15 (r) CAGCATCTCC ATTGAGTAAT CACGTTGGTG TTCGGTGGCC CGCCGTGTTG CGTGGCGGAG GCTGCCGGGA GACGGGTGGG GATGGTGGTG GGAGAGAATG TAGGGCGCCG TGTTTCAGTC CCTAGGCAGG ATACCGGAAA ACCGTGTGGT AGGAGGTTTA TAGGTTTCCA 20 GGAGACGCTG TATAGGGGAT AAATGAGATT GAATGGTGGC CACACTCAAA CCAACCAGGT CCTGTACATA CAATGCATAT ACCAATTATA CCTACCAAAA AAAAAAAAAA AAAAAAAAAA AAAA (SEQ ID NO:18) 25 or a sequence homologous thereto encoding a polypeptide specific for xyloglucan with endoglucanase activity, ii) is immunologically reactive with an antibody raised against a highly purified endoglucanase encoded by the DNA sequence defined in i) and derived from Aspergillus aculeatus, CBS 101.43, and is specific for xyloglucan. 30 More specifically, as used herein the term "specific for xyloglucan" means that the endoglucanse enzyme exhibits its highest endoglucanase activity on a xyloglucan substrate, and preferably less than 75% activity, more preferably less than 50% activity, most preferably less than about 25% activity, on other cellulose-containing substrates such as carboxymethyl cellulose, cellulose, or other glucans. 53 W VVU01/101 Y- I/ U 3UUIZJJL1Z Preferably, the specificity of an endoglucanase towards xyloglucan is further defined as a relative activity determined as the release of reducing sugars at optimal conditions obtained by incubation of the enzyme with xyloglucan and the other substrate to be tested, respectively. For instance, the specificity may be defined as the xyloglucan to 3-glucan activity (XGU/BGU), 5 xyloglucan to carboxy methyl cellulose activity (XGU/CMCU), or xyloglucan to acid swollen Avicell activity (XGU/AVIU), which is preferably greater than about 50, such as 75, 90 or 100. The term "derived from" as used herein refers not only to an endoglucanase produced by strain CBS 101.43, but also an endoglucanase encoded by a DNA sequence isolated from strain CBS 101.43 and produced in a host organism transformed with said DNA sequence. The term 10 "homologue" as used herein indicates a polypeptide encoded by DNA which hybridizes to the same probe as the DNA coding for an endoglucanase enzyme specific for xyloglucan under certain specified conditions (such as presoaking in 5xSSC and prehybridizing for 1 h at -40 0 C in a solution of 5xSSC, 5xDenhardt's solution, and 50 pg of denatured sonicated calf thymus DNA, followed by hybridization in the same solution supplemented with 50 pCi 32-P-dCTP labeled 15 probe for 18 h at -40 0 C and washing three times in 2xSSC, 0.2% SDS at 40'C for 30 minutes). More specifically, the term is intended to refer to a DNA sequence which is at least 70% homologous to any of the sequences shown above encoding an endoglucanase specific for xyloglucan, including at least 75%, at least 80%, at least 85%, at least 90% or even at least 95% with any of the sequences shown above. The term is intended to include modifications of any of 20 the DNA sequences shown above, such as nucleotide substitutions which do not give rise to another amino acid sequence of the polypeptide encoded by the sequence, but which correspond to the codon usage of the host organism into which a DNA construct comprising any of the DNA sequences is introduced or nucleotide substitutions which do give rise to a different amino acid sequence and therefore, possibly, a different amino acid sequence and therefore, possibly, a 25 different protein structure which might give rise to an endoglucanase mutant with different properties than the native enzyme. Other examples of possible modifications are insertion of one or more nucleotides into the sequence, addition of one or more nucleotides at either end of the sequence, or deletion of one or more nucleotides at either end or within the sequence. Endoglucanase specific for xyloglucan useful in the present invention preferably is one 30 which has a XGU/BGU, XGU/CMU and/or XGU/AVIU ratio (as defined above) of more than 50, such as 75, 90 or 100. Furthermore, the endoglucanase specific for xyloglucan is preferably substantially devoid of activity towards P-glucan and/or exhibits at the most 25% such as at the most 10% or about 5%, activity towards carboxymethyl cellulose and/or Avicell when the activity towards 35 xyloglucan is 100%. In addition, endoglucanase specific for xyloglucan of the invention is 54 WU UI/10£/_ L, 1/UU/IAJJI; preferably substantially devoid of transferase activity, an activity which has been observed for most endoglucanases specific for xyloglucan of plant origin. Endoglucanase specific for xyloglucan may be obtained from the fungal species A. aculeatus, as described in WO 94/14953. Microbial endoglucanases specific for xyloglucan has 5 also been described in WO 94/14953. Endoglucanases specific for xyloglucan from plants have been described, but these enzymes have transferase activity and therefore must be considered inferior to microbial endoglucanses specific for xyloglucan whenever extensive degradation of xyloglucan is desirable. An additional advantage of a microbial enzyme is that it, in general, may be produced in higher amounts in a microbial host, than enzymes of other origins. 10 The xyloglucanase, when present, is incorporated into the treating compositions of the invention preferably at a level of from 0.0001% to 2%, more preferably from 0.0005% to 0.1%, most preferred from 0.001% to 0.02% pure enzyme by weight of the composition. The above-mentioned enzymes may be of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin. Purified or non-purified forms of these enzymes may be used. 15 Also included by definition, are mutants of native enzymes. Mutants can be obtained e.g. by protein and/or genetic engineering, chemical and/or physical modifications of native enzymes. Common practice as well is the expression of the enzyme via host organisms in which the genetic material responsible for the production of the enzyme has been cloned. Said enzymes are normally incorporated in the bleach system at levels from 0.0001% to 20 2% of active enzyme by weight of the bleach system. The enzymes can be added as separate single ingredients (prills, granulates, stabilized liquids, 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 oxidation scavengers. Examples of such enzyme oxidation scavengers are ethoxylated tetraethylene polyamines. 25 A range of enzyme materials and means for their incorporation into synthetic bleach systems is also disclosed in WO 93/07263 and WO 93/07260 to Genencor International, WO 89/08694 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 materials useful for liquid detergent formulations, and their incorporation into such 30 formulations, are disclosed in U.S. 4,261,868, Hora et al, April 14, 1981. Enzyme Stabilizers - Enzymes for use in detergents can be stabilized by various techniques. Enzyme stabilization techniques are disclosed and exemplified in U.S. 3,600,319, August 17, 1971, Gedge et al, EP 199,405 and EP 200,586, October 29, 1986, Venegas. Enzyme stabilization systems are also described, for example, in U.S. 3,519,570. A useful Bacillus, sp. 35 AC13 giving proteases, xylanases and cellulases, is described in WO 9401532 to Novo. The 55 wu U11Oz15 rq_/U3U~u/Zaa J enzymes employed herein can be stabilized by the presence of water-soluble sources of calcium and/or magnesium ions in the finished compositions which provide such ions to the enzymes. Suitable enzyme stabilizers and levels of use are described in U.S. Pat. No. 5,576,282. Other Detergent Ingredients - The bleach systems herein may also 5 optionally contain one or more of the following: polymeric dispersing agents, clay soil removal/anti-redeposition agents, brighteners, suds suppressors, dyes, perfumes, structure elasticizing agents, fabric softeners, carriers, hydrotropes, processing aids and/or pigments. Suitable examples of such other detergent ingredients and levels of use are found in U.S. Patent No. 5,576,282. 10 Methods of Cleaning - In addition to the methods for cleaning fabrics, dishes and other hard surfaces, and body parts by personal cleansing, described herein, the invention herein also encompasses a laundering pretreatment process for fabrics which have been soiled or stained comprising directly contacting said stains and/or soils with a highly concentrated form of the bleach system set forth above prior to washing such fabrics using conventional aqueous washing 15 solutions. Preferably, the bleach system remains in contact with the soil/stain for a period of from about 30 seconds to 24 hours prior to washing the pretreated soiled/stained substrate in conventional manner. More preferably, pretreatment times will range from about 1 to 180 minutes. The following examples are meant to exemplify compositions of the present invention, 20 but are not necessarily meant to limit or otherwise define the scope of the invention. In the following examples some abbreviations known to those of ordinary skill in the art are used, consistent with the disclosure set forth herein. EXAMPLE I 25 Bleaching detergent compositions having the form of granular laundry detergents are exemplified by the following formulations. A B C D E Organic Catalyst * 0.034 0.06 0.03 0.10 0.05 Conventional Activator 2.00 2.80 2.00 1.80 5.30 (NOBS) Conventional Activator 0.00 0.00 0.60 0.00 0.00 (TAED) Sodium Percarbonate 5.30 0.00 0.00 4.00 0.00 Sodium Perborate 0.00 5.30 3.60 0.00 4.30 Monohydrate 56 vv Ui loz i/a PCT/US00/23321 Linear Alkylbenzenesulfonate 12.00 0.00 12.00 0.00 21.00 C45AEO.6S 0.00 15.00 0.00 15.00 0.00 C2 Dimethylamine N-Oxide 0.00 2.00 0.00 2.00 0.00 C12 Coco Amidopropyl 1.50 0.00 1.50 0.00 0.00 Betaine Palm N- Methyl Glucamide 1.70 2.00 1.70 2.00 0.00 C12 Dimethylhydroxyethyl- 1.50 0.00 1.50 0.00 0.00 ammonium Chloride AE23-6.5T 2.50 3.50 2.50 3.50 1.00 C25E3S 4.00 0.00 4.00 0.00 0.00 Sodium Tripolyphosphate 25.00 25.00 15.00 15.00 25.00 Acrylic Acid / Maleic Acid 0.00 0.00 0.00 0.00 1.00 Copolymer Polyacrylic Acid, partially 3.00 3.00 3.00 3.00 0.00 neutralized Soil Release Agent 0.00 0.00 0.50 0.40 0.00 Carboxymethylcellulose 0.40 0.40 0.40 0.40 0.40 Sodium Carbonate 2.00 2.00 2.00 0.00 8.00 Sodium Silicate 3.00 3.00 3.00 3.00 6.00 Sodium Bicarbonate 5.00 5.00 5.00 5.00 5.00 Savinase (4T) 1.00 1.00 1.00 1.00 0.60 Termamyl (60T) 0.40 0.40 0.40 0.40 0.40 Lipolase (100T) 0.12 0.12 0.12 0.12 0.12 Carezyme(5T) 0.15 0.15 0.15 0.15 0.15 Diethylenetriaminepenta 1.60 1.60 1.60 1.60 0.40 (methylenephosphonic Acid) Brightener 0.20 0.20 0.20 0.05 0.20 Sulfonated Zinc 0.50 0.00 0.25 0.00 0.00 Phthalocyanine Photobleach MgSO 4 2.20 2.20 2.20 2.20 0.64 Na 2

SO

4 balance balance balance balance balance Organic catalyst can be any of the zwitterionic organic catalysts described herein, preferably it is an iminium-based organic catalyst, more preferably it is a dihydroisoquinolinium-based organic catalyst. 57 VV IJ UIIO

/

1 rI. 1/UUUI3JJZ.I Any of the above compositions can be used to launder fabrics at a concentration of 3500 ppm in water, 25 0 C, and a 15:1 water:cloth ratio. The typical pH is about 9.5 but can be can be adjusted by altering the proportion of acid to Na- salt form of alkylbenzenesulfonate. 5 EXAMPLE II Bleaching detergent compositions having the form of granular laundry detergents are exemplified by the following formulations. A B C DE Organic Catalyst * 0.009 0.04 0.14 0.14 0.002 Conventional Activator 1.80 0.00 0.00 1.00 1.00 (NOBS) Conventional Activator 0.00 1.00 2.50 3.00 0.00 (TAED) Sodium Percarbonate 5.30 0.00 0.00 0.00 0.00 Sodium Perborate 0.00 9.00 17.60 9.00 9.00 Monohydrate Linear 21.00 12.00 0.00 12.00 12.00 Alkylbenzenesulfonate C45AEO.6S 0.00 0.00 15.00 0.00 0.00 C2 Dimethylamine N-Oxide 0.00 0.00 2.00 0.00 0.00 C12 Coco Amidopropyl 0.00 1.50 0.00 1.50 1.50 Betaine Palm N- Methyl Glucamide 0.00 1.70 2.00 1.70 1.70 C12 1.00 1.50 0.00 1.50 1.50 Dimethylhydroxyethylammo nium Chloride AE23-6.5T 0.00 2.50 3.50 2.50 2.50 C25E3S 0.00 4.00 0.00 4.00 4.00 Sodium Tripolyphosphate 25.00 15.00 25.00 15.00 15.00 Polyacrylic Acid, partially 0.00 3.00 3.00 3.00 3.00 neutralized Soil Release Agent 0.30 0.50 0.00 0.50 0.50 Carboxymethylcellulose 0.00 0.40 0.40 0.40 0.40 Sodium Carbonate 0.00 2.00 2.00 2.00 2.00 Sodium Silicate 6.00 3.00 3.00 3.00 3.00 58 WO 01/16278 FI-UUUU/IZaJ.z1 Sodium Bicarbonate 2.00 5.00 5.00 5.00 5.00 Savinase (4T) 0.60 1.00 1.00 1.00 1.00 Termamyl (60T) 0.40 0.40 0.40 0.40 0.40 Lipolase (100T) 0.12 0.12 0.12 0.12 0.12 Carezyme(5T) 0.15 0.15 0.15 0.15 0.15 Diethylenetriaminepenta(met 0.40 0.00 1.60 0.00 0.00 hylenephosphonic Acid) Brightener 0.20 0.30 0.20 0.30 0.30 Sulfonated Zinc 0.25 0.00 0.00 0.00 0.00 Phthalocyanine Photobleach MgSO 4 0.64 0.00 2.20 0.00 0.00 Na 2

SO

4 balance balance balance balance balance *Organic catalyst can be any of the zwitterionic organic catalysts described herein, preferably it is an iminium-based organic catalyst, more preferably it is a dihydroisoquinolinium-based organic catalyst. 5 Any of the above compositions can be used to launder fabrics at a concentration of 3500 ppm in water, 25 0 C, and a 15:1 water:cloth ratio. The typical pH is about 9.5 but can be can be adjusted by altering the proportion of acid to Na- salt form of alkylbenzenesulfonate. EXAMPLE III 10 A bleaching detergent powder in accordance with the present invention comprises the following ingredients: Component Weight % Organic Catalyst* 0.01 15 NOBS 2.0 Sodium Perborate Tetrahydrate 10

C

12 linear alkyl benzene sulfonate 8 Phosphate (as sodium tripolyphosphate) 9 Sodium carbonate 20 20 Talc 15 Brightener, perfume 0.3 Sodium Chloride 25 Water and Minors Balance to 100% 59 WU UIIIOZ75 rL q /UUUIz. a3Zi *Organic catalyst can be any of the zwitterionic organic catalysts described herein, preferably it is an iminium-based organic catalyst, more preferably it is a dihydroisoquinolinium-based organic catalyst. 5 EXAMPLE IV A laundry bar suitable for hand-washing soiled fabrics is prepared by standard extrusion processes and comprises the following: 10 Component Weight % Organic Catalyst* 0.02 NOBS 1.7 TAED 0.2 Sodium Perborate Tetrahydrate 12 15 C 12 linear alkyl benzene sulfonate 30 Phosphate (as sodium tripolyphosphate) 10 Sodium carbonate 5 Sodium pyrophosphate 7 Coconut monoethanolamide 2 20 Zeolite A (0.1-10 micron) 5 Carboxymethylcellulose 0.2 Polyacrylate (m.w. 1400) 0.2 Brightener, perfume 0.2 Protease 0.3 25 CaSO 4 1 MgSO 4 1 Water 4 Filler 2 Balance to 100% 30 *Organic catalyst can be any of the zwitterionic organic catalysts described herein, preferably it is an iminium-based organic catalyst, more preferably it is a dihydroisoquinolinium-based organic catalyst. 2 Can be selected from convenient materials such as CaCO 3 , talc, clay, silicates, and the like. Acidic fillers can be used to reduce pH. 35 60 WO Ulll6278 /UsUUI.Jazi EXAMPLE V A laundry detergent composition suitable for machine use is prepared by standard methods and comprises the following composition: 5 Component Weight% Organic Catalyst* 0.3 TAED 10.0 Sodium Perborate Tetrahydrate 9.2 Sodium Carbonate 23.74 10 Anionic surfactant 14.80 Alumino Silicate 21.30 Silicate 1.85 Diethylenetriaminepentacetic acid 0.43 Polyacrylic acid 2.72 15 Brightener 0.23 Polyethylene glycol solids 1.05 Sulfate 8.21 Perfume 0.25 Processing aid 0.10 20 Miscellaneous 0.43 Water Balance Organic catalyst can be any of the zwitterionic organic catalysts described herein, preferably it is an iminium-based organic catalyst, more preferably it is a dihydroisoquinolinium-based organic 25 catalyst. The composition can be used to launder fabrics at a concentration in solution of about 1000 ppm at a temperature of 20-40 0 C and a water to fabric ratio of about 20:1. 30 EXAMPLE VI Component Weight% Organic Catalyst* 0.082 NOBS 7.20 Sodium Perborate Tetrahydrate 8.0 35 Sodium Carbonate 21.0 61 WO 01/16278 F'I/UUUA.ZI Anionic surfactant 12.0 Alumino Silicate 18.0 Diethylenetriaminepentacetic acid 0.3 Nonionic surfactant 0.5 5 Polyacrylic acid 2.0 Brightener 0.3 Sulfate 17.0 Perfume 0.25 Miscellaneous 2.95 10 Water Balance *Organic catalyst can be any of the zwitterionic organic catalysts described herein, preferably it is an iminium-based organic catalyst, more preferably it is a dihydroisoquinolinium-based organic 15 catalyst. The composition can be used as a laundry auxiliary for laundering fabrics at a concentration in solution of about 850 ppm at a temperature of 5-50 0 C and a water to fabric ratio of about 20:1. 20 EXAMPLE VII A bleaching composition suitable for use in high suds phosphate geographies has the formula: Component A (%wt) B (%wt) 25 Organic Catalyst* 0.02 0.018 NOBS 1.90 2.00 Sodium Perborate Tetrahydrate 2.25 3.00 Sodium Carbonate 13.00 13.00 Anionic surfactant 19.00 19.00 30 Cationic surfactant 0.60 0.60 Nonionic surfactant - 0.40 Sodium Tripolyphosphate 22.50 22.50 Diethylenetriaminepentacetic acid 0.90 0.90 Acrylic acid/Maleic acid copolymer 0.90 0.90 35 Carboxymethylcellulose 0.40 0.40 62 Wk Ul/10278 PFL/USUUIZJJZI Protease 0.70 0.70 Amylase 0.36 0.36 Cellulase 0.35 0.35 Brightener 0.16 0.18 5 Magnesium sulfate 0.70 0.70 Water 3.0 1.0 Sodium sulfate Balance Balance *Organic catalyst can be any of the zwitterionic organic catalysts described herein, preferably it is 10 an iminium-based organic catalyst, more preferably it is a dihydroisoquinolinium-based organic catalyst. While particular embodiments of the subject invention have been described, it will be obvious to those skilled in the art that various changes and modifications of the subject invention 15 can be made without departing from the spirit and scope of the invention. It is intended to cover, in the appended claims, all such modifications that are within the scope of the invention. The compositions of the present invention can be suitably prepared by any process chosen by the formulator, non-limiting examples of which are described in U.S. Patent Nos. 5,691,297; 5,574,005; 5,569,645; 5,565,422; 5,516,448; 5,489,392; and 5,486,303. 20 In addition to the above examples, the bleach systems of the present invention can be formulated into any suitable laundry detergent composition, non-limiting examples of which are described in U.S. Patent Nos. 5,679,630; 5,565,145; 5,478,489; 5,470,507; 5,466,802; 5,460,752; 5,458,810; 5,458,809; and 5,288,431. Having described the invention in detail with reference to preferred embodiments and the 25 examples, it will be clear to those skilled in the art that various changes and modifications may be made without departing from the scope of the invention and the invention is not to be considered limited to what is described in the specification. 63

Claims

1. A bleach system for laundering fabrics in need of cleaning comprising from about 0.001 ppm to about 5 ppm of a zwitterionic organic catalyst compound selected from the group consisting of: 5 a) aryliminium zwitterions, which have a net charge of from about +3 to about -3, that are represented by the formula [II]: R5 6 To7 R N( [II] 10 where R 5 -R 7 are independently selected from substituted or unsubstituted radicals selected from the group consisting of H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, heterocyclic ring, silyl, nitro, halo, cyano, sulfonato, alkoxy, keto, carboxylic and carboalkoxy radicals; also present in this formula is the radical represented by the formula: e 15 To-Z where Z,- is covalently bonded to To, and Zp,- is selected from the group consisting of -CO2, SO3-, -OSO3-, -SO 2 - and -OSO

2- and p is either 1, 2 or 3; To is selected from the group consisting of substituted or unsubstituted, saturated or unsaturated alkyl, cycloalkyl, aryl, alkaryl, 20 aralkyl and heterocyclic ring; b) oxaziridinium zwitterions, which have a net charge of from about +3 to about -3, that are represented by formula [IV]: R" 6' 1 R NE 0 N [IV] 25 where R 5 '-R 7 ' are independently selected from substituted or unsubstituted radicals selected from the group consisting of H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, heterocyclic ring, silyl, nitro, halo, cyano, sulfonato, alkoxy, keto, carboxylic and carboalkoxy radicals; also present in this formula is the radical represented by the formula: 64 WU 01/10£/ YL.1/U3UUIZJJZI -ro---z~p where Z'p- is covalently bonded to T'o, and Z'P- is selected from the group consisting of -CO2 5 SO3-, -OSO 3 -, -SO 2- and -OSO 2- and p is either 1, 2 or 3; T'o is selected from the group consisting of substituted or unsubstituted, saturated or unsaturated alkyl, cycloalkyl, aryl, alkaryl, aralkyl and heterocyclic ring; and c) mixtures thereof. 10 2. The bleach system according to Claim 1 wherein said bleach system further comprises from about 2.0 ppm to about 1200 ppm of one or more peroxygen source.

3. The bleach system according to Claim 1 wherein said bleach system further comprises from about 0.5 ppm to about 300 ppm of one or more peracids. 15

4. The bleach system according to Claim 1 wherein said bleach system further comprises from about 1.0 ppm to about 600 ppm of one or more peroxygen compounds.

5. The bleach system according to Claim 2 wherein said peroxygen source is selected from 20 the group consisting of: (a) preformed peracid compounds selected from the group consisting of percarboxylic acids and salts, percarbonic acids and salts, perimidic acids and salts, peroxymonosulfuric acids and salts, and mixtures thereof; (b) hydrogen peroxide sources selected from the group consisting of perborate 25 compounds, percarbonate compounds, perphosphate compounds and mixtures thereof; and a bleach activator.

6. The bleach system according to Claim 1 wherein said zwitterionic organic catalyst compound is present at a concentration of from about 0.01 ppm to about 3 ppm. 30

7. The bleach system according to Claim 6 wherein said zwitterionic organic catalyst compound is present at a concentration of from about 0.1 ppm to about 2 ppm.

8. The bleach system according to Claim 7 wherein said zwitterionic organic catalyst 35 compound is present at a concentration of from about 0.2 ppm to about 1 ppm. 65 WO U01/16278 YCI'/U!UUIZJ.5J2zI

9. The bleach system according to Claim 1 wherein said zwitterionic organic catalyst compound is selected from the group consisting of: a) aryliminium zwitterions, which have a net charge of from about +3 to about -3, 5 that are represented by the formula [XII]: 28 G R 26-4 R27 6n ToM L ~ 0 25 R [XII] 10 where m is 1 to 3 when G is present and m is 1 to 4 when G is not present; and n is an integer from 0 to 4; each R 26 is independently selected from a substituted or unsubstituted radical selected from the group consisting of H, alkyl, cycloalkyl, aryl, fused aryl, heterocyclic ring, fused heterocyclic ring, nitro, halo, cyano, sulfonato, alkoxy, keto, carboxylic, and carboalkoxy radicals, and any two vicinal R 2 6 substituents may combine to form a fused aryl, fused 15 carbocyclic or fused heterocyclic ring; R 2 5 may be a substituted or unsubstituted radical selected from the group consisting of H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, heterocyclic ring, silyl, nitro, halo, cyano, sulfonato, alkoxy, keto, carboxylic and carboalkoxy radicals; also present in this formula is the radical represented by the formula: 8 20 - To Z where ZP- is covalently bonded to To, and ZP- is selected from the group consisting of -CO2 SO 3 -, -OSO3-, -SO 2- and -OSO 2- and p is either 1, 2 or 3; To is selected from the group consisting of: 25 R29 I -(C)q 1 29 R wherein q is an integer from 1 to 8; R 29 is independently selected from substituted or unsubstituted radicals selected from the group consisting of linear or branched H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, alkylene, heterocyclic ring, alkoxy, arylcarbonyl, carboxyalkyl 66 WU 01/16278 'L1/USULU/IJJ ZI1 and amide groups; G is selected from the group consisting of: (1) -0- ; (2) -N(R 3 0)-; and (3) N(R 3 0 R 3 1 )-; R 2 7 , R 2 8 , R 3 0 and R 3 1 are substituted or unsubstituted radicals independently selected from the group consisting of H, oxygen, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, alkylenes, heterocyclic ring, alkoxys, arylcarbonyl groups, carboxyalkyl groups and amide 5 groups; any of R 2 5 , R 26 , R 27 , R 28 , R 30 and R 3 1 may be joined together with any other of R 2 5 , R 2 6 , R 2 7 , R 2 8 , R 30 and R 3 1 to form part of a common ring; any geminal R 2 7 - R 28 may combine to form a carbonyl; any vicinal R 2 7 - R 3 1 may join to form unsaturation; and wherein any one group of substituents R 2 7 - R 3 1 may combine to form a substituted or unsubstituted fused unsaturated moiety; 10 b) oxaziridinium zwitterions, which have a net charge of from about +3 to about -3, that are represented by formula [XIV]: 28 ' G R [R] R27' In \o Z ' DQ+ 250 0 R [XIV] wherein m is 1 to 3 when G is present and m is 1 to 4 when G is not present; and n is an integer 15 from 0 to 4; each R 26 ' is independently selected from a substituted or unsubstituted radical selected from the group consisting of H, alkyl, cycloalkyl, aryl, fused aryl, heterocyclic ring, fused heterocyclic ring, nitro, halo, cyano, sulfonato, alkoxy, keto, carboxylic, and carboalkoxy radicals, and any two vicinal R 26 ' substituents may combine to form a fused aryl, fused carbocyclic or fused heterocyclic ring; R 2 5 ' may be a substituted or unsubstituted radical selected 20 from the group consisting of H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, heterocyclic ring, silyl, nitro, halo, cyano, sulfonato, alkoxy, keto, carboxylic and carboalkoxy radicals; the radical represented by the formula: -To-Z'E 25 where Z'p- is covalently bonded to T'o, and Z'P- is selected from the group consisting of -CO2 SO3-, -OSO3-, -SO 2- and -OSO2-, and a is either 1 or 2; T'o is selected from the group consisting of: 67 WVV U1/1010 L.I/U3UU/Z3,3.I R29' 1 -(C)q 129' R wherein q is an integer from 1 to 8; R 2 9 ' is independently selected from substituted or unsubstituted radicals selected from the group consisting of linear or branched H, alkyl, 5 cycloalkyl, alkaryl, aryl, aralkyl, alkylene, heterocyclic ring, alkoxy, arylcarbonyl, carboxyalkyl and amide groups; G is selected from the group consisting of: (1) -0- ; (2) -N(R 30 ')-; and (3) N(R 3 0 'R 3 1')-; R 2 7' , R 28 ' , R 30 ' and R 3 1 ' are substituted or unsubstituted radicals independently selected from the group consisting of H, oxygen, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, alkylenes, heterocyclic ring, alkoxys, arylcarbonyl groups, carboxyalkyl groups and amide 10 groups; any of R 2 5' , R 26 ' , R 2 7 ' , R 2 8' , R 3 0 ' and R 3 1 ' may be joined together with any other of R 2 5' , R 2 6 ' , R 27 ' , R 2 8' , R 3 0 ' and R 3 1 ' to form part of a common ring; any geminal R 27 ' - R 2 8 ' may combine to form a carbonyl; any vicinal R 2 7' - R 3 1 ' may join to form unsaturation; and wherein any one group of substituents R 2 7 ' - R 3 1 ' may combine to form a substituted or unsubstituted fused unsaturated moiety; and 15 c) mixtures thereof.

10. The bleach system according to Claim 9 wherein said zwitterionic organic catalyst compound is an aryliminium zwitterion of the formula [XII] wherein R 2 5 is H or methyl, R 2 6 is independently selected from H, alkyl and alkoxy, and for the radical represented by the formula: 20 e -To - Ge ZP- is -CO 2 -, -SO 3 -or -OSO3-, and p is 1 or 2. 25

11. The bleach system according to Claim 10 wherein said zwitterionic organic catalyst compound is an aryliminium zwitterion of the formula [XII] wherein for the radical represented by the formula: 30 ZP- is -CO 2 , -SO 3 or -OSO3, and p is 1, and To is selected from the group consisting of: 68 WU UI/1/Z75 r L,1/UUU/I..)JLI 29 ' I -(C)q 1 29' R wherein q is an integer from 2 to 4, and each R 2 9 is individually, independently selected from the group consisting of H and linear or branched C 1 -C 18 substituted or unsubstituted alkyl and aryl. 5

12. The bleach system according to Claim 1 wherein said bleach system further comprises a surfactant.

13. The bleach system according to Claim I wherein said bleach system further comprises an 10 enzyme.

14. The bleach system according to Claim 1 wherein said bleach system further comprises a chelating agent.

15 15. The bleach system according to Claim 2 wherein said peroxygen source and said zwitterionic organic catalyst compound are present in said bleach system at a molar ratio of greater than 1:1.

16. The bleach system of Claim 1 made by the process comprising: 20 a) providing a wash solution; and b) adding to said wash solution a bleach composition comprising an amount of zwitterionic organic catalyst compound selected from the group consisting of: i) aryliminium zwitterions, which have a net charge of from about +3 to about -3, that are represented by the formula [II]: R5 6 1 R 7 NG 25 R [II] where R 5 -R 7 are independently selected from substituted or unsubstituted radicals selected from the group consisting of H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, 30 heterocyclic ring, silyl, nitro, halo, cyano, sulfonato, alkoxy, keto, carboxylic and 69 WO 01/16278 rFLT/UUU/2Ji.L carboalkoxy radicals; also present in this formula is the radical represented by the formula: 5 where Z,- is covalently bonded to To, and ZP- is selected from the group consisting of CO2-, -SO3-, -OSO3-, -SO 2 - and -OSO2 - and p is either 1, 2 or 3; To is selected from the group consisting of substituted or unsubstituted, saturated or unsaturated alkyl, cycloalkyl, aryl, alkaryl, aralkyl and heterocyclic ring; 10 ii) oxaziridinium zwitterions, which have a net charge of from about +3 to about -3, that are represented by formula [IV]: R" 6' 1 R N®E To- P [IV] 15 where R 5 '-R 7 ' are independently selected from substituted or unsubstituted radicals selected from the group consisting of H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, heterocyclic ring, silyl, nitro, halo, cyano, sulfonato, alkoxy, keto, carboxylic and carboalkoxy radicals; also present in this formula is the radical represented by the formula: 20 -To p where Z'p- is covalently bonded to T'o, and Z'p- is selected from the group consisting of CO2-, -SO3-, -OSO3-, -SO 2- and -OSO 2- and p is either 1, 2 or 3; T'o is selected from 25 the group consisting of substituted or unsubstituted, saturated or unsaturated alkyl, cycloalkyl, aryl, alkaryl, aralkyl and heterocyclic ring; and iii) mixtures thereof; such that the resulting concentration of the zwitterionic organic catalyst compound in said wash solution is from about 0.001 ppm to about 5 ppm. 30

17. A method for laundering a fabric in need of laundering, said method comprises contacting said fabric with a laundry solution having a bleach system according to Claim 1. 70 WU UI/lOZ/5 L. 1IUUU1.3.,1

18. The method according to Claim 17 wherein said fabric is a colored fabric.

19. The method according to Claim 17 wherein said method is carried out in an automatic 5 washing machine.

20. A bleach system for laundering fabrics in need of cleaning comprising a) a peroxygen source; and b) a zwitterionic organic catalyst compound selected from the group consisting of: 10 i) aryliminium zwitterions, which have a net charge of from about +3 to about -3, that are represented by the formula [II]: R 5 6 1 R N® R 7 [II] 15 where R 5 -R 7 are independently selected from substituted or unsubstituted radicals selected from the group consisting of H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, heterocyclic ring, silyl, nitro, halo, cyano, sulfonato, alkoxy, keto, carboxylic and carboalkoxy radicals; also present in this formula is the radical represented by the formula: 20 - To 4p where ZP- is covalently bonded to To, and ZP,- is selected from the group consisting of CO 2 -, -SO3-, -OSO3-, -SO 2- and -OSO 2- and p is either 1, 2 or 3; To is selected from the 25 group consisting of substituted or unsubstituted, saturated or unsaturated alkyl, cycloalkyl, aryl, alkaryl, aralkyl and heterocyclic ring; ii) oxaziridinium zwitterions, which have a net charge of from about +3 to about -3, that are represented by formula [IV]: R6 5 ' R N& TO- Z R T 71 WO 01U/b0278 't.1/UUU/A3J3 z i [IV] where R 5 '-R 7 ' are independently selected from substituted or unsubstituted radicals selected from the group consisting of H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, 5 heterocyclic ring, silyl, nitro, halo, cyano, sulfonato, alkoxy, keto, carboxylic and carboalkoxy radicals; also present in this formula is the radical represented by the formula: 10 where Z'p- is covalently bonded to T'o, and Z'P- is selected from the group consisting of CO2-, -SO3-, -OSO3-, -SO 2 - and -OSO2 - and p is either 1, 2 or 3; T'o is selected from the group consisting of substituted or unsubstituted, saturated or unsaturated alkyl, cycloalkyl, aryl, alkaryl, aralkyl and heterocyclic ring; and 15 iii) mixtures thereof; wherein said peroxygen source and said zwitterionic organic catalyst compound are present in said bleach system at a molar ratio greater than 1:1.

21. The bleach system according to Claim 20 wherein said peroxygen source and said 20 zwitterionic organic catalyst compound are present in said bleach system at a molar ratio of from about 30,000:1 to about 10:1.

22. The bleach system according to Claim 21 wherein said peroxygen source and said zwitterionic organic catalyst compound are present in said bleach system at a molar ratio of from 25 about 10,000:1 to about 50:1.

23. The bleach system according to Claim 22 wherein said peroxygen source and said zwitterionic organic catalyst compound are present in said bleach system at a molar ratio of from about 5,000:1 to about 100:1. 30

24. The bleach system according to Claim 23 wherein said peroxygen source and said zwitterionic organic catalyst compound are present in said bleach system at a molar ratio of from about 3,500:1 to about 150:1. 35

25. A bleach system for laundering fabrics in need of cleaning comprising 72 WO 01/16278 PCT/US00/23321 a) a peracid; and b) a zwitterionic organic catalyst compound selected from the group consisting of: i) aryliminium zwitterions, which have a net charge of from about +3 to about -3, that are represented by the formula [II]: R 5 R6 To 5 [II] where R 5 -R 7 are independently selected from substituted or unsubstituted radicals selected from the group consisting of H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, 10 heterocyclic ring, silyl, nitro, halo, cyano, sulfonato, alkoxy, keto, carboxylic and carboalkoxy radicals; also present in this formula is the radical represented by the formula: To -Z e 15 where Zp- is covalently bonded to To, and Z,- is selected from the group consisting of CO2-, -SO3-, -OSO3-, -SO 2 - and -OSO 2- and p is either 1, 2 or 3; To is selected from the group consisting of substituted or unsubstituted, saturated or unsaturated alkyl, cycloalkyl, aryl, alkaryl, aralkyl and heterocyclic ring; 20 ii) oxaziridinium zwitterions, which have a net charge of from about +3 to about -3, that are represented by formula [IV]: R, 6' N To-Z R N 0 P [IV] 25 where R 5 '-R 7 ' are independently selected from substituted or unsubstituted radicals selected from the group consisting of H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, heterocyclic ring, silyl, nitro, halo, cyano, sulfonato, alkoxy, keto, carboxylic and carboalkoxy radicals; also present in this formula is the radical represented by the formula: 73 WU UI/101/ YL, I /UUUIAJJA1 -To--p where Z'," is covalently bonded to T'o, and Z'P- is selected from the group consisting of 5 CO2-, -SO3-, -OSO3", -SO 2 - and -OSO 2 - and p is either 1, 2 or 3; T'o is selected from the group consisting of substituted or unsubstituted, saturated or unsaturated alkyl, cycloalkyl, aryl, alkaryl, aralkyl and heterocyclic ring; and iii) mixtures thereof; wherein said peracid and said zwitterionic organic catalyst compound are present in said bleach 10 system at a molar ratio greater than 1:1. 74