MXPA02002126A

MXPA02002126A - Color safe laundry methods employing zwitterionic formulation components.

Info

Publication number: MXPA02002126A
Application number: MXPA02002126A
Authority: MX
Inventors: Robert Richard Dykstra
Original assignee: Procter & Gamble
Priority date: 1999-08-27
Filing date: 2000-08-25
Publication date: 2002-09-18
Also published as: WO2001016278A1; EP1206518A1; TR200200457T2; AU6935700A; AR028165A1; CZ2002687A3; CN1382206A; CA2381924A1; JP2003508589A; MA25544A1; BR0013643A

Abstract

The present invention relates to zwitterionic organic catalyst compound bleach systems and methods for using such bleach systems to increase color safety during laundering of 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.

Description

PE LAVANDERY METHODS THAT KEEP THE COLOR. THAT EMPLOY ZWITTERIONIC FORMULATION COMPONENTS FIELD OF THE INVENTION 5 The present invention describes bleaching systems of zwitterionic organic catalyst compound and methods for using said • bleaching systems to provide increased color security during fabric washing; Especially fabrics of color. More particularly this invention describes bleaching systems comprising zwitterionic ions; Quaternary imine bleach reinforcing compounds; zwitterionic quaternary oxaziridinium bleaching species; and mixtures thereof, and methods employing said bleaching systems in the washing of fabrics, especially colored fabrics. BACKGROUND OF THE INVENTION - Oxygen bleaching agents have become very • popular in recent years in personal and home care products for 20 facilitate the removal of stains or dirt. The bleaches are particularly desirable for their removal of stains, cleaning of dirty cloth, bleaching and hygiene properties. Oxygen bleaching agents have had particular acceptance in laundry products such as as detergents, in products for automatic dishwashing machines and in hard surface cleaners. Oxygen bleaching agents, however, are somewhat limited in their effectiveness. Some commonly encountered disadvantages include color damage on 5 fabrics and damage to laundry appliances, specifically plastic hoses that these appliances may contain. In addition, oxygen bleach agnes tend to be extremely dependent on the scale of • temperature. In this way, the colder the solution where they are used, the less effective the bleaching action will be. Usually, it 10 require temperatures above 60 ° C to obtain an effectiveness of an oxygen bleaching agent in solution. To solve the problem of dependence on the aforementioned temperature scale, 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 group, typically hydrogen peroxide or its anion, to form a more effective peroxy acid oxidant. It is the peroxyacid compound that subsequently • oxidizes the dirty or stained substrate material. However, the activators 20 bleaching depends in some way on the temperature. Bleach activators are most effective at temperate water temperatures of around 40oC to about 60oC. In water temperatures of less than about 40 ° C, the peroxyacid compound loses some of its bleaching effectiveness. The US patent nos. 5,576,282 and 5,817,614 both for Miracle et al. attempts to develop bleaching systems comprising zwitterionic organic catalyst compounds that are effective under lower temperature water conditions and are relatively safe for colors. Although the bleaching systems shown in this patent provide improved color security compared to traditional organic catalyst bleaching systems, such as cationic organic catalyst bleaching systems, examples of which are shown in US Pat. Nos. 5,360,568 , 5,360,569, 5,370,826 and 5,482,515 all to Madison et al., Consumers want bleaching products that provide more color security. A serious disadvantage associated with methods of using conventional organic catalysts, examples of which are described in the US patents no. 5,360,568, 5,360,569 and 5,370,826 all to Madison et al., And in US Pat. Nos. 5,576,282 and 5,817,614, both to Miracle et al., Is that said organic catalysts are employed in a very high concentration in use. 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 scale of about 5 ppm to about 100 ppm per liter of medium. This concentration can result in unacceptable color damage to the fabric dye. In addition, such a high concentration can lead to a lot of available oxygen ("AvO") consumption, leading to an altered performance profile (i.e., changing the balance between peracid bleach and organic catalyst bleach). It may be possible to improve the performance of bleaching of spots with organic catalyst concentration but only at the expense of the dye damage and at a certain moment the damage of the dye becomes unacceptable. Accordingly, there is a need to maximize the stain bleaching performance ratio for dye damage of organic catalyst bleaching systems. Based on the foregoing, it is evident that there remains a need for bleaching systems of organic zwitterionic ion catalyst compound and laundry methods employing such bleaching systems of organic zwitterionic ion catalyst compound that provide effective bleaching under water conditions. of lower temperature and provide superior color tracking properties compared to the laundry methods employing the organic catalyst bleaching systems shown in the prior art, as shown above, and there is a need to maximize the performance ratio of the bleaching of stains for coloring damage of the organic catalyst bleaching systems.

BRIEF DESCRIPTION OF THE INVENTION The present invention meets the need mentioned above. The present invention provides bleaching systems of organic zwitterionic ion catalyst compound and methods for washing fabrics, especially colored fabrics employing said bleaching systems. The zwitterionic organic catalyst compounds of the present invention, and the bleaching systems comprising said organic amphoteric ion catalyst compounds provide better bleaching effectiveness in lower temperature washing applications at the same time that provide improved color security, resulting in a blaze effectiveness and improved color security compared to conventional cationic organic catalyst and zwitterionic bleach systems. The organic zwitterionic ion catalyst compound bleaching systems of the present invention act in conjunction with or without, preferably, conventional peroxygen bleach sources to provide the superior fabric color security and the aforementioned improved bleaching effectiveness. More particularly, this invention discloses organic zwitterionic ion catalyst compounds such as the zwitterionic ion quaternary ion bleach-enhancing compounds, zwitterionic ion quaternary oxaziridinium bleaching species comprising said organic zwitterionic ion catalyst compounds and laundry methods employing said bleaching systems. Non-limiting examples of the benefits provided by the organic zwitterionic ion catalyst compounds and bleaching systems employing them include superior bleaching effectiveness even in water with lower temperature and improved color security. In one aspect of the present invention, a zwitterionic ion catalyst organic bleach system is provided that demonstrates effective bleaching at a lower water temperature and provides a superior color safety profile as compared to conventional organic catalyst bleach systems. According to another aspect of the present invention, a zwitterionic ion catalyst organic bleach system comprising one or more organic zwitterionic ion catalyst compounds, as described successively, in conjunction with or without a peroxygen source is provided. . According to another aspect of the present invention, there is provided a zwitterionic ion organic catalyst bleaching system comprising one or more organic zwitterionic ion catalyst compounds, as described successively, in conjunction with or without a peroxygen source. In accordance with yet another aspect of the present invention, a method is provided for washing a fabric, especially a colored fabric, which It requires washing which comprises contacting the fabric with a washing solution comprising one or more bleaching systems of zwitterionic organic catalyst compound described in the present invention. According to yet another aspect of the present invention, a bleaching system of the present invention is provided as elaborated by the process comprising: a) providing a washing solution; and b) adding to said wash solution a bleaching composition comprising an amount of zwitterionic ion catalyst organic compound of the present invention such that the resulting concentration of the organic zwitterionic ion catalyst compound in said wash solution is about 0.001 ppm to about 5 ppm. Accordingly, one of the objects of the present invention is to provide: organic zwitterionic ion catalyst bleaching systems, which demonstrates improved performance even in lower temperature water solutions and improved color security, and a method for washing a fabric, especially a colored fabric, using one or more of the zwitterionic ion catalyst organic bleach systems described in the present invention. One skilled in the art will recognize these and other objects, features and advantages of the present invention from the following description and the appended claims.

All percentages, ratios and proportions mentioned herein are on a weight basis unless otherwise specified. All documents cited here are incorporated by this act by reference.

DETAILED DESCRIPTION OF THE INVENTION The present invention shows zwitterionic ion organic catalyst compounds, bleaching systems, comprising said organic zwitterionic ion catalyst compounds and methods for washing fabrics, especially colored fabrics employing said bleaching systems. The zwitterionic ion catalyst organic compounds of the present invention and the bleaching systems comprising said organic zwitterionic ion catalyst compounds provide improved bleaching effectiveness in lower temperature washing applications at the same time that provide improved color security resulting in a improved color effectiveness and improved color security compared to organic zwitterionic ion catalyst bleaching systems. The organic zwitterionic ion catalyst compound bleaching systems of the present invention act in conjunction with or without, preferably, conventional peroxygen bleach sources to provide the superior fabric color security and the aforementioned improved bleaching effectiveness.

Definitions "Peroxygen source" as used herein means amoebae that generate peroxygen compounds which may include the peroxygen compounds themselves. Examples include but are not limited to bleach activators, peracids, percarbonate, perborate, hydrogen peroxide, bleach-enhancing compounds and / or bleaching species (eg, oxazyridiniums). "Peroxygen compounds" as used in the present invention include peracids and peroxides (eg, hydrogen peroxide, alkylhydroperoxides, etc. "Peracid" as used herein means a peroxyacid such as peroxycarboxylic acid and / or peroxymonosulfuric acid (trademark OXONE) and its salts.

Zwitterionic ion organic catalyst compounds Organic zwitterionic ion catalyst compounds and bleaching systems comprising said organic zwitterionic ion catalyst compounds of the bleaching system of the present invention are preferably used in methods for washing fabrics, especially colored fabrics that require washing. Such methods typically comprise bleaching a stained substrate, preferably a colored fabric, in an aqueous medium with a peroxygen source and with an organic zwitterionic ion catalyst compound whose structure is as defined below wherein the aqueous medium contains active oxygen of the peroxygen compound from about 0.05 to about 250 ppm per liter of medium, and the organic zwitterionic ion catalyst compound from about 0.001 ppm to about 2 ppm , preferably from about 0.01 ppm to about 2 ppm, more preferably from about 0.1 ppm to about 1.5 ppm, and more 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 the organic zwitterionic ion catalyst compound is preferably greater than 1: 1, more preferably the scale of the molar ratio is from about 30,000: 1 to about 10: 1, even more preferably from about 10,000: 1 to about 50: 1, still more preferably from about 5,000: 1 to about 100: 1, even more preferably from about 3,500: 1 to about 150: 1 The molar ratio of the peroxygen compound to the organic zwitterionic ion catalyst compound influences the color safety properties of a bleaching system. However, the ppm concentration of the organic zwitterionic catalyst compound in the bleaching system is the primary factor in establishing the color safety properties of the bleaching systems.

A product can provide, for example, in an aqueous medium a concentration of I ppm of an organic zwitterionic ion catalyst compound with a molecular weight of 300, and a concentration of 66 ppm of NOBS (pemonanoic acid of 35 ppm which assumes perhydrolysis of the 100%) and a concentration of 66 ppm of percarbonate (21 ppm hydrogen peroxide) to provide a molar ratio of peroxygen compound to the zwitterionic organic catalyst compound of 246: 1. A product that provides 240 ppm of TAED (forming 160 ppm of peracetic acid) and 865 ppm of percarbonate (forming 281 ppm of hydrogen peroxide) provides a molar ratio of peroxygen compound to the organic zwitterionic ion catalyst of 3142: 1. At 0.25 ppm organic zwitterionic ion catalyst compound, the molar ratio would be 12568: 1. In addition to the molar ratios of the peroxygen compound to the organic zwitterionic ion catalyst compound, the bleach systems of the present invention can be characterized by the molar ratio of a peracid to organic zwitterionic ion catalyst compound. Preferably, the molar ratio of the peracid for the organic zwitterionic ion catalyst compound is greater than 1: 1, more preferably from about 5,000: 1 to about 5: 1, even more preferably from about 2,000: 1 to about 10. : 1, still more preferably from about 1, 000: 1 to about 15: 1.

The preferred molar ratios of peracid for organic zwitterionic ion catalyst compound vary with the washing conditions. For example, under European wash conditions (typically from about 4500 ppm to about 5000 ppm of detergent components in the wash water), the preferred molar ratio of peracid to organic zwitterionic ion catalyst compound is about 2,000: 1 to about 150: 1. While, under North American washing conditions (typically from about 850 ppm to about 1000 ppm of detergent components in the wash water), the preferred molar ratio of peracid to organic zwitterionic ion catalyst compound is about 150: 1 at about 5: 1. In addition to the molar ratios of peracid for the organic zwitterionic ion catalyst compound, the bleach system of the present invention can be characterized by the molar ratio of a hydrophobic peracid to organic zwitterionic ion catalyst compound., preferably an organic catalyst compound of zwitterionic ion hydrophobic. Preferably the molar ratio of the hydrophobic peracid to the organic zwitterionic ion catalyst compound is from about 500: 1, to about 15: 1, more preferably from about 350: 1 to about 20: 1, even more preferably still from about 200: 1 to about 25: 1 and even more preferably about 100: 1 to about 35: 1 Preferably, the organic zwitterionic ion catalyst compounds of the present invention, more preferably the compounds zwitterionic ion-based organic catalysts of the present invention, include, but are not limited to, reinforcement compounds of 5 bleaching.

I. Bleaching Replenisher Compounds • Bleach Replenishers, preferably iminium-based bleach-enhancing compounds of the present The invention includes, but is not limited to, zwitterionic aryliminium ions, having a net charge of about +3 to about - Zwitterionic aryliminium ions 15 The zwitterionic aryliminium ions, which have a net charge of about +3 to about -3, are represented by the formula 20 [ll] wherein R5-R7 are independently selected from substituted or unsubstituted radicals that are selected from the group consisting of H, alkyl, chloroalkyl, aryl, alkaryl, aralkyl, heterocyclic ring, silyl, nitrogen, halogen, cyano, sulfonate, alkoxy, keto, carboxylic and carboalkoxy; The radical represented by the formula is also present in this formula: - T o. "2? where Zp is covalently bound to T0- and Zp ~ is selected from the group consisting of -CO2-, -S03-, -OS03-, -S02- and OS02- and p is 1, 2 or 3; T0 # is selected from the group consisting of alkyl, cycloalkyl, aryl, alkaryl, aralkyl and substituted or unsubstituted, saturated or unsaturated heterocyclic ring.

Preferably, the zwitterionic aryliminium ions, which have a net charge of about +3 to about -3, are represented by the formula [XII]: [XlO where m is 1 to 3 when G is present and m is 1 to 4 when m is not present; and n is an integer from 0 to 4; each R26 is independently selected from the substituted or unsubstituted radical which is selected from the group consisting of H, alkyl, cycloalkyl, aryl, fused aryl, heterocyclic ring, fused heterocyclic ring, nitrogen, halogen, cyano, sulfonate, alkoxy, keto, carboxylic, and carboalkoxy, and either of the two adjacent R26 substituent atoms may be combined to form a fused aryl, fused carcocyclic ring or fused heterocyclic ring; R25 may be a substituted or unsubstituted radical which is selected from the group of radicals consisting of H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, heterocyclic ring, silyl, nitrogen, halogen, cyano, sulfonate, alkoxy, keto, carboxylic, and carboalkoxy; The radical represented by the formula is also present in this formula: where Zp- is covalently bound to T0 'and Zp- is selected from the group consisting of -C02, -S03-, -OS03-, -SO2 and -OSO2- and p is 1, 2 or 3; T0 is selected from the group consisting of: - where q is an integer from 1 to 8; R29 is independently selected from substituted or unsubstituted radicals which are selected from the group consisting of H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, alkylene heterocyclic ring, alkoxy, arylcarbonyl, carboxyalkyl and straight or branched amide groups; G is selected from the group consisting of (1) -O-; (2) -N (R30); and (3) -N (R30 R31) -; R27, R28, R30 and R31 are substituted or unsubstituted radicals which are independently selected from the group consisting of H, oxygen, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, alkylene, heterocyclic ring, alkoxys, arylcarbonyl groups, carboxyalkyl groups and amide groups; any of R25, R26, R27, R28, R30 and R31 can be joined with any other of R25, R26, R27, R28, R30 and R31 to form part of a common ring; any pair R27-R28 can be combined to form a carbonyl; any adjacent R27-R31 may join to form unsaturation; and wherein any group of substituent atoms R27-R31 may be combined to form a substituted unsubstituted or substituted unsaturated portion. More preferably aryliminium amphoteric ions, having a net charge of about +3 to about -3 as represented by formula [Xll], include those of formula [Xll] where R25 is H or methyl, and the radical represented by the formula: - OR "" 2? Zp is -C02, -SO3- or -OS03-, and p is 1 or 2. More preferably, zwitterionic aryliminium ions are represented by the formula [XI la] *. * X? 3atÁ4 wherein R 4 '- R 44 can be independently selected from a substituted or unsubstituted radical which is selected from the group consisting of H, linear, branched alkyl, cycloalkyl, alkaryl, aryl, aralkyl, alkylene, aromatic radicals , substituted or unsubstituted as long as any of the R ^ -R44 can be joined with any other of the R41-R44 to form part of a common ring; more preferably, at least one, even more preferably two of R4I-R44 are H. More preferably, R41 and / or R44 is a C1-C16 alkyl, linear or branched or cycloalkyl, even more preferably the sum of the carbon atoms within R41 and R44 is 5-15, more preferably 6-13.

II. Bleaching species Bleaching species (oxaziridiniums) can also be used directly according to the present invention. The bleaching species of the present invention include, but are not limited to, zwitterionic oxaziridinium ions, having a net charge of about +3 to about -3. The amphoteric aryliminium ions of the present invention act in conjunction with a source of peroxygen, when present, to increase the effectiveness of bleaching. Without being limited by theory, it is believed that the zwitterionic aryliminium ions react with the peroxygen source to form a more active bleaching species, a zwitterionic zwitterionic quaternary oxazididium compound, as depicted in the following reaction by means of example: Zwitterionic ion oxaziridinium compounds may have an improved or preferred activity at lower temperatures relative to the peroxygen compound.

Zwitterionic oxaziridinium ions Zwitterionic oxaziridinium ions, which have a net charge of about +3 to about -3, are represented by the formula [IV]: [IV] wherein R5'-R7 are independently selected from the substituted or unsubstituted radicals of the group consisting of radicals of H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, heterocyclic ring, silyl, nitrogen, halogen, cyano, sulfonate, alkoxy, keto , carboxylic, and carboalkoxy, in this formula is also present the radical represented by the formula: "-Item l -? _ L? iá? * i. * i. *;. á * ^ f? - * ^ - - * ^ * ^? **? iA * yes ******** **. *. * * *? *? i? * M *** éh * **** t * éi * **. * ^ t *? *. t t where Z'p is covalently linked to T'0, and Z'p- is selected from the group consisting of -C02, -SO3-, -OSO3-, -S02- and -OS02- and p is 1.2. or 3; T0 is selected from the group consisting of alkyl, cycloalkyl, aryl, alkaryl, aralkyl and substituted or unsubstituted, saturated or unsaturated heterocyclic ring. Preferably, the zwitterionic oxaziridinium ions, which have a net charge of about +3 to about -3, are represented by the formula [XIV]: [XIV] where m is 1 to 3 when G is present and m is 1 to 4 when m is not present; and n is an integer from 0 to 4; each R26 is selected so 15 independent of the substituted or unsubstituted radical which is selected from the group consisting of radicals of H, alkyl, cycloalkyl, aryl, fused aryl, heterocyclic ring, fused heterocyclic ring, nitrogen, halogen, cyano, sulfonate, alkoxy, keto, carboxylic, and carboalkoxy, and any of the two adjacent R26 substituent atoms can be combined to Forming a fused aryl, fused carcocyclic ring or fused heterocyclic ring; R25 can be a substituted or unsubstituted radical selected from the group of radicals consisting of H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, heterocyclic ring, silyl, nitrogen, halogen, cyano, sulfonate, aikoxi, keto, carboxylic, and carboalkoxy; The radical represented by the formula is also present in this formula: or * -p Where Z'p- is covalently bound to T'0 'and Z'p- is selected from the group consisting of -CO2, -S03-, -OS03-, -S02 and -OSO2- is already 1 or 2; T'0 is selected from the group consisting of: # where q is an integer from 1 to 8; R29 is independently selected from substituted or unsubstituted radicals which are selected from the group consisting of H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, alkylene, ring Heterocyclic, aikoxy, arylcarbonyl, carboxyalkyl and linear or branched amide groups; as long as all the R29 groups are not independently selected to be H; G is selected from the group consisting of (1) -O-; (2) -N (R30); and (3) -N (R30 'R31') -; R27 ', R28', R30 'and R31' are radicals • Substituted or unsubstituted that are selected independently of the group Which consists of H, oxygen, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, alkylene, heterocyclic ring, alkoxys, arylcarbonyl groups, carboxyalkyl groups and amide groups; any of R25 ', R26', R27 ', R28', R30 'and R3 can be linked with any other of R25', R26 ', R27', R28 ', R30' and R3 for . *. ***? ^ * ^^? ** é? í? * ^ - * ^? xf ** A ^ h ^ ¿^,? ^. ^ a «s ^» s »^^ .-. ^^ be part of a common ring; any pair R27-R28 can be combined to form a carbonyl; any adjacent R27-R31 may join to form unsaturation; and wherein any group of substituent atoms R27 '- R31 may be combined to form a substituted unsubstituted or unsubstituted fused part. More preferably oxaziridinium amphoteric ions, having a net charge of about +3 to about -3 as represented by formula [XIV], include those of formula [XIV] where R25 is H or methyl, and the radical represented by the formula: - T- Z? GT Zp is -C02, -SO3- or -OS03-, and p is 1 or 2. More preferably, the zwitterionic oxaziridinium ions are represented by the formula [XlVa] [XlVa] wherein R41-R44 may be independently selected from a substituted or unsubstituted radical which is selected from the group consisting of H, linear or branched alkyl, cycloalkyl, alkaryl, aryl, aralkyl, alkylene, alkoxy radicals, substituted or not replaced as long as any of the R41-R44 may be joined with any other of the R41-R44 to form part of a common ring; more preferably, at least one, even more preferably two of R ^ -R44 are H. More preferably, R41 and / or R44 is a C1-C16 alkyl, linear or branched or cycloalkyl, even more preferably the sum of the carbon atoms within R41 and R44 is 5-15, more preferably 6-13.

Concentrations of organic catalyst compounds Organic zwitterionic ion catalyst compounds (bleach-enhancing compounds and bleaching species) of the present invention can be added and preferably added to a wash solution, typically aqueous wash solution, at levels of 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). More preferably from about 0.01% (0.01 ppm) to about 0.1% (1 ppm) The conversion values (in ppm) are provided for exemplification purposes, based on a product use concentration of 1000 ppm. A washing solution of 1000 ppm of a product that containing 0.2% organic catalyst compound by weight results in a concentration of organic catalyst compound of 2 ppm. Similarly, a 3500 ppm wash solution of a product containing 0.2% organic catalyst compound by weight results in an organic catalyst compound concentration of 6.5 ppm.

Decomposition of organic catalysts • Organic catalysts, specifically compounds * Bleach boosters of the present invention are susceptible to 10 decomposition by means of several decomposition routes including, but not limited to, the route of aromatization. The reaction of the aromatization (decomposition) of 6-membered ring-bleach reinforcing compounds is well known in the art, as exemplified, without being limited by theory, in Hanquet et al., Tetrahedron 1993, 49, pp. . 15 423-438. Other means of decomposition include, but are not limited to, attacking the bleach-enhancing compound and / or in the bleaching species by nucleophiles, including but not limited to attacking by means of hydroxide anion, perhydroxide anion, carboxylate anion, percarboxylate anion and other nucleophiles present under washing conditions. 20 Methods for delayed (controlled) addition of organic catalyst compounds Surprisingly, it has been found with organic catalyst compounds of limited duration, that the sum of organic catalyst compounds by way of administration forms to a washing solution after a fabric has been added to a washing solution, especially a solution of Washing containing a source of peroxygen, provides improved bleaching compared to the sum of said organic catalyst compounds to the washing solution before a fabric has been added to the washing solution. It is believed, without being limited by theory, that the organic catalyst compound undergoes a decomposition in the washing solution before the introduction of the fabric charge. One method for improving the performance of the organic catalyst compounds is to delay the addition of the organic catalyst compound of the present invention to the washing solution. Another method for improving the performance of organic catalyst compounds is to use an organic catalyst compound with improved stability for washing conditions. Methods for the delayed (controlled) addition of organic catalyst compounds are described in greater detail in the co-pending and co-owned provisional EUA patent application entitled "Controlled Availability of Formulation Components, Compositions and Laundry Methods Employing Same" registered on August 27 of 1999 (P &G Attorney Docket Number 7749P) sf *** "ilntltirfilTi lT Blanket systems comprising organic zwitterionic ion catalyst compounds In addition to the aforementioned use of organic zwitterionic ion catalyst compounds, the organic zwitterionic ion catalyst compounds of the present invention can be used in conjunction with or without , preferably with a peroxygen source in other bleaching systems, regardless of their form. For example, organic zwitterionic ion catalyst compounds can be employed in a laundry additive product. In the bleaching systems of the present invention, the peroxygen source may be present at levels of from about 0.1% to about 60% by weight of the system, and preferably from about 0.0001% to about 1% by weight of the system, with greater preference of about 0.001% to about 0.5%, even more preferably about 0.004% to about 0.25%. More preferably from about 0.01% to about 0.1%. The bleaching systems of the present invention can be used advantageously in laundry applications, cleaning of hard surfaces, automatic washing machine applications as well as in cosmetic applications such as dentures, teeth, hair and skin. However, because of the unique advantages of improved color security and improved effectiveness in cold and possibly lukewarm water solutions due to possible improved stability, the organic catalyst compounds of the present invention are ideally suited for applications of . ,, ¿. ~ ~ *: * ÚMÍ. ** - laundry and laundry bleaching such as bleaching containers or laundry bleach additives. In addition, the bleach-reinforcing compounds of the present invention can be used in granular and liquid compositions. The organic zwitterionic ion catalyst compounds and bleaching systems comprising the organic catalyst compounds can be used as antimicrobial agents and disinfectants. Accordingly, the bleaching systems of the present invention may include several additional ingredients that are desirable in laundry applications. Such ingredients include detersive surfactants, bleach catalysts, detergency builders, chelating agents, enzymes, polymeric soil release agents, brighteners and other ingredients. Compositions including any of these additional 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 bleaching system. The bleaching systems preferably include at least one detersive surfactant, at least one chelating agent, at least one detersive enzyme and preferably has a pH of from about 6 to about 12, preferably from 8 to about 10.5 in a solution of 1% of the bleaching system. t m. &A.- M? t. & .a *** *:. ***** ^, ... a ^ ", ^^ - ^^^ -. * ^ **** ** In another embodiment of the present invention, a method is provided for washing a fabric, especially a colored fabric, that requires washing. The preferred method comprises contacting the fabric with a washing solution. The fabric can comprise mostly any fabric capable of being washed under normal consumer use conditions. The washing solution comprises a bleaching system comprising one or more organic zwitterionic ion catalyst compounds of the present invention, as described in the present invention. The water temperatures preferably on a scale of about 0 ° C to about 50 ° C or higher. The water for the fabric radius is preferably from about 1: 1 to about 15: 1. The laundry solution may further include at least one additional ingredient which is selected from the group consisting of detersive surfactants, chelating agents, detersive enzymes and mixtures thereof. Preferably, the laundry solution has a pH of from about 6 to about 12, preferably from about 8 to about 10.5 in a 1% solution in bleaching systems. The bleaching systems of the present invention typically and preferably comprise a source of peroxygen. Peroxygen sources are well known in the art and the peroxygen source employed in the present invention can comprise any of these well-known sources, including the peroxygen compounds as well as compounds that under conditions of consumer use provide a ^ - -tii Atf- * 4 ^ ^^ - - ** ~ ¡¡¡¡¡¡¡¡¡^ ^ ^ ^ ^ ^ ^ ^^^ ¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡^^^^ Effective amount of peroxygen in situ . The source of peroxygen may include a source of hydrogen peroxide, the in situ formation of a peracid anion through the reaction of a source of hydrogen peroxide and a bleach activator, preformed peracid compounds or mixtures of the sources of peroxygen appropriate. Of course, a person skilled in the art will recognize that other sources of peroxygen can be employed without having to take the scope of the invention as a reference point. Preferably, the peroxygen source is selected from the group consisting of: (i) preformed peracid compounds which are 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) sources of hydrogen peroxide which are selected from the group consisting of perborate compounds, percarbonate compounds, perphosphate compounds and mixtures thereof, and a bleach activator. When present, the peroxygen sources (sources of hydrogen peroxide and / or peracids) will typically be at levels of 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 be about 0.1%, preferably about 0.5% to about 60%, preferably about 40%, by weight of the bleach system comprising the agent bleach activator. of bleaching plus. to. Preformed Peracids The preformed peracid compound as used in the present invention is any convenient compound that is stable and that under conditions of consumer use provides an effective amount of peracid anion. The organic catalysts of the present invention can be used in conjunction with a preformed peracid compound which is 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. same, examples of which are described in the US patent no. 5,576,282 to Miracle et al. A class of suitable organic peroxycarboxylic acids have the general formula: O II YRCO-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 may contain one or two peroxy groups and may be aliphatic or aromatics When the organic peroxycarboxylic acid is aliphatic, the unsubstituted peracid has the general formula: Where Y may be, for example, H, CH 3, CH 2 Cl, C (O) OH, or C (0) OOH; and n is an integer from 0 to 20. When the peroxycarboxylic acid is aromatic, the unsubstituted peracid has the general formula: fc where Y can be, for example, hydrogen, alkyl, alkylagen, halogen, C (0) OH or C (O) OOH. Typical monoperoxic acids useful in the present invention include aryl and alkyl peroxyacids such as: (i) peroxybenzoic acid and substituted ring peroxybenzoic acid, for example, peroxy-a-naphthoic acid, monoperoxyphthalic acid (magnesium salt hexahydrate) , and o-carboxybenzamidoperoxyhexanoic acid (sodium salt); (Ii) aliphatic, substituted aliphatic and monoperoxy arylalkyl acids, for example, peroxylauric acid, peroxistearic acid, N-nonanoylaminoperoxycaproic acid (NAPCA), N, N- (3-) acid ** i * * á _iá, _ octilsuccinoyl) aminoperoxycaproic (SAPA) and N, N-phthaloylaminoperoxycaproic acid (PAP); (iii) amidoperoxyacids, for example, monononylamide peroxisuccinic acid (NAPSA) or peroxyadipic acid (NAPAA). Typical diperoxy acids useful in the present invention include alkyldiperoxy acids and aryldiperoxy acids, such as: (iv) 1,12-diperoxydecanedioic acid; (v) 1,9-diperoxyazelaic acid; (vi) diperoxy fibersic acid; diperoxysebacic acid and diperoxyisophthalic acid; (vii) 2-decyliperoxybutane-1,4-dionic acid; (viii) 4,4'-sulfonylbisperoxybenzoic acid. Such bleaching agents are shown in U.S. Patent 4,483,781, Hartman, issued November 20, 1984, U.S. Patent 4,634,551 to Burns et al., European Patent Application 0,133,354, Banks et al. published on February 20, 1985, and US Patent 4,412,934, Chung et al. Issued November 1, 1983. Sourees also includes 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.l. DuPont de Nemours of Wilmington, DE can also be employed as an appropriate source of peroxymonosulfuric acid. , afe ^ .- &Ag > «R ... Í« .. r¡i ^ | b. Sources of Hydrogen Peroxide The source of hydrogen peroxide can be any suitable source of hydrogen peroxide and be presented at levels such as those described in full in U.S. Patent No. 5,576,282. For example, the source of hydrogen peroxide can be selected from the group consisting of perborate compounds, percarbonate compounds, perphosphate compounds, and mixtures thereof. The sources of hydrogen peroxide are described in more detail in the Kirk Othmer's Encyclopedia of Chemical Technology, 4th Ed (1992, John Wiley &Sons), Vol. 271-300"Bleaching Agents (Survey) ", and include the various forms of sodium perborate and sodium percarbonate, including various modified and coated forms. The preferred source of hydrogen peroxide used herein can be any convenient source, including hydrogen peroxide itself. For example , perborate, for example, sodium perborate (any hydrate but preferably the mono or tetrahydrate), sodium carbonate peroxyhydrate or equivalent percarbonate salts, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate or sodium peroxide can be used. useful sources of available oxygen such as persulfate bleach (eg, OXONE, manufactured by DuPont). Particularly preferred are sodium perborate monohydrate and sodium percarbonate. it is also possible to use mixtures of any peroxide source sule hydrogen.

A preferred percarbonate bleach comprises dry particles with an average particle size in the range of about 500 microns to about 1,000 microns, no more than about 10% by weight of said particles that are smaller than about 200 microns. and no more than about 10% by weight of said particles larger than about 1.250 microns. Optionally, the percarbonate can be coated with a silicate, borate or water-soluble surfactant. Percarbonate is available from various commercial sources such as FMC, Solvay and Tokai Denka. The compositions of the present invention may also comprise as the bleaching agent a 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 comprising enzymes. b. BLENDING ACTIVATORS Preferably, the peroxygen source in the composition is formulated with an activator (peracid precursor). The activator is present at levels of about 0.01%, preferably about 0.5%, more preferably about 1% at about 15%, preferably about 10%, more preferably about 8%, in weight of the composition. A bleach activator as used herein is any compound which when used in conjunction with a source of hydrogen peroxide leads to the in situ production of the peracid corresponding to the bleach activator. Unlimited examples of activators are shown in full in U.S. Patent No. 5,576,282, U.S. Patent 4,915,854 and U.S. Patent 4,412,934. See also US 4,634,551 for other activators and bleaches typical here useful. Preferred activators are selected from the group consisting of tetraacetylethyl amine (TAED), benzoylcaprolactam (BzCL), 4-nitrogen benzoylcaprolactam, 3-chlorobenzoylcaprolactam, benzoyloxybenzenesulfonate (BOBS), nonanoyloxybenzenesulfonate (NOBS), phenylbenzoate (PhBz), decanoyloxybenzenesulfonate (C10-OBS) ), benzoylvalerolactam (BZVL), Octanoyloxybenzenesulfonate (C8-OBS), perhydrolyzable esters and mixtures thereof, more preferably benzoylcaprolactam and benzoylvalerolactam. Particularly preferred bleach activators in the pH range of from about 8 to about 9.5 are those that are selected with a leaving group OBS or VL. Preferred hydrophobic activators bleaching include but are not limited to, nonanoiloxibencensulfonato (NOBS), sodium salt of 4- [N- (nonanoyl) amino hexanoyloxy] -bencensulfonato (HACA-OBS) an example of which is described in patent US No. 5,523,434, lauroyloxybenzenesulfonate (LOBS or C12-OBS), 10- undecenoyloxybenzenesulfonate (UDOBS or C11-OBS with unsaturation at position 10), and decanoyloxybenzoic acid (DOBA). Preferred bleach activators are those described in U.S. Patent No. 5,698,504 Christie et al., Issued December 16, 1997; USA 5,695,679 Christie et al. issued on December 9, 1997; US 5,686,401 Willey et al., Issued November 11, 1997; US 5,686,014 Hartshorn et al., Issued November 11, 1997; US 5,405,412 Willey et al., Issued April 11, 1995; US 5,405,413 Willey et al., Issued April 11, 1995; US 5,130,045 Mitchel et al., Issued 10 July 14, 1992; and US 4,412,934 Chung et al., issued November 1, 1983, and co-pending US patent applications, Nos. Mk 08 / 709,072, 08 / 064,564, which are incorporated by reference herein. The molar ratio of the peroxygen bleaching compound 15 (as AvO) for the bleach activator in the present invention is generally in the scale of at least 1: 1, preferably of about 20: 1, more preferably of about 10: 1 to about 1: 1, preferably at approximately 3: 1. • Bleach activators can also be included 20 substituted quaternaries. The bleaching systems present preferably comprise a quaternary substituted bleach activator (QSBA) or a substituted quaternary peracid (QSP); more preferably, the first. The preferred QSBA structures are described more detailed in U.S. Patent 5,686,015 Willey et al., issued November 11, 1997; US 5,654,421 Taylor et al., Issued August 5, 1997; US 5,460,747 Gosselink et al., Issued October 24, 1995; US 5,584,888 Miracle et al., Issued December 17, 1996; and US 5,578,136 Taylor et al., issued November 26, 1996; which are incorporated in the present invention by reference. The highly preferred bleach activators useful herein are # substituted amides as described in US patent 5,698,504, US 5,695,679, and US 5,686,014 previously cited in the present invention. Preferred examples of said bleach activators include: (6-octanamidocaproyl) oxybenzenesulfonate, (6-nonanamidocaproyl) My oxybenzenesulfonate, (6-decanamidocaproyl) oxybenzenesulfonate and mixtures thereof. Other useful activators, shown in the US patents 15 5,698,504, US 5,695,679, US 5,686,014 previously cited in the present invention and US 4,966,723Hodge et al., Issued October 30, 1990, include activators of the benzoxazin type, such as a C6H4 ring to which they are fused to 1, 2-positions one part --C (O) OC (R1) = N-. Depending on the activator and the precise application, 20 obtain good bleaching results from bleaching systems having pH in use of from about 6 to about 13, preferably from about 9.0 to about 10.5. Typically, for example, activators with electron replacement parts are used for scales of b » ,? * - * * ** £ > j? jhJ¡ Mfcf..i ,,. ^ -liLaaAcS. pH almost neutral or subneutral. Alkalis and buffering agents can be used to ensure said pH. Acylactam activators as described in US patents 5,698,504, US 5,695,679 and US 5,686,014, previously 5 cited, are very useful here, especially acylcaprolactams (see for example WO 94-28102 A) and acylvalerolactams (see EUA 5,503,639 Willey et al. al., issued April 2, 1996 incorporated in the present invention by reference). 10 d. Organic peroxides, especially diacyl peroxides In addition to the bleaching agents described above, the bleaching systems of the present invention may optionally include organic peroxides. Organic peroxides are illustrated extensively in Kirk Othmer, Encyclopedia of Chemical Technology, Vol. 17, John Wiley 15 and Sons, 1982 on pages 27-90 and especially on pages 63-72, all incorporated in the present invention by reference. If a diacyl peroxide is used, it will preferably be one that exerts minimal adverse impact on placement / filming 20 e. Metal-containing bleach catalysts Bleaching systems can also optionally include metal-containing bleach catalysts, preferably cobalt and manganese container bleach catalysts.

One type of metal container bleach catalyst is a catalyst system comprising a transition metal cation of defined bleach catalytic activity, such as copper, iron, titanium, ruthenium tungsten, molybdenum, or manganese cations, an auxiliary metal cation with little or no catalytic bleaching activity, such as zinc or aluminum cations, and an inhibitor with defined stability constants for the auxiliary and catalytic metal cations, particularly ethylenediaminetetraacetic acid, ethylenediaminetetra (methylenephosphonic acid) and water soluble salts of the same. Said catalysts are shown in U.S. Patent 4,430,243 Bragg, issued February 2, 1982. i. Metal manganese complexes If desired, the compositions mentioned 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 shown in U.S. Patent 5,576,282 Miracie et al., Issued November 19, 1996; US 5,246,621 Favre et al., Issued September 21, 1993; US 5,244,594 Favre et al., Issued September 14, 1993; US 5,194,416 Jureller et al., Issued March 16, 1993; US 5,114,606 van Vliet et al., Issued May 19, 1992; and European patent publications At the same time, there was no change in the number of rooms, the number of rooms was 549.271 A1, 549.272 Al, 544.440 A2, and 544.490 A1; Preferred examples of these catalysts include MnlV2 (u-0) 3 (1, 4,7-trimethyl-1, 4,7-triazacyclononane) 2 (PF6) 2, Mnlll2 (u-0)? (U-OAc) 2 (1, 4,7- trimethyl-1, 4,7-triazacyclononane) 2 (C10) 2, MnlV4 (u-0) 6 (1, 4,7-triazacyclononane) 4 (CIO4) 4, MnlllMnlV4 (u-0)? (u-OAc) 2- (1, 4,7-trimethyl-1, 4,7-triazaclclononane) 2 (CIO 4) 3, MnlV (1, 4,7-trimethyl-1, 4,7-triazacyclononane) - (OCH 3) 3 (PF6 ), and mixtures thereof. Other metal-based bleach catalysts include those shown in US Patent 4,430,243 included by reference above and EUA 5,114,611 van Kralingen, issued May 19, 1992. The use of manganese with several complex ligands to enhance bleaching in the following: US 4,728,455 Rerek, issued March 1, 1988; US 5,284,944 Madison, issued February 8, 1994; US 5,246,612 van Dijk et al., Issued September 21, 1993; US 5,256,779 Kerschner et al., Issued October 26, 2993; US 5,280,117 Kerschner et al., Issued January 18, 1994; US 5,274,147 Kerschner et al., Issued December 28, 1993; USA 5,153,161 Kerschner et al., Issued October 6, 1992; and US 5,227,084 Martens et al., issued July 13, 1993.

I. Cobalt metal complexes The cobalt bleach catalysts useful herein are known and described, for example, in US Patent 5,597,936 Perkins et al., lÜflVU lilf * • *** ** - *, * **? * »? * - M? I? *** J **** I ***. íiásßet ******** - *.

Issued on January 28, 1997; US 5,595,967 Míracle et al., Issued January 21, 1997; US 5,703,030 Perkins et al., Issued December 30, 1997; and M. L. Tobe, "Base Hydrolysis of Transition-Metal Complexes", Adv. Inorg. Bioinorg. Meeh., (1983), 2, pages 1-94. The most preferred cobalt catalyst here useful are the cobalt pentaaminacetate salts having the formula [Co (NH3) 5OAc] Ty, wherein "OAc" represents an acetate medium and "Ty" is an anion, and • especially cobalt pentaaminacetate chloride, [Co (NH3) sOAc] CI2; as [Co (NH3) 5OAc] (OAc) 2; [Co (NH3) 5OAc] (PF6) 2; [Co (NH3) 5OAc] (S04); 10 [Co (NH3) 5OAc] (BF4) 2; and [Co (NH3) 5OAc] (N03) 2 (in the present invention "PAC"). These cobalt catalysts are prepared by means of • known methods, such as that shown for example in US 5,597,936, US 5,595,967, US 5,703,030, previously cited, the article 15 Tobe and 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 (Prentiee-Hall, 1970), pp. 461-3; Inorg. Chem., 18, 1497-1502 (1979); Inorg.

• Chem., 21, 2881-2885 (1982); Inorg. Chem., 18, 2023-2025 (1979); Inorg. 20 Synthesis, 173-176 (1960); and journal of Physical Chemistry, 56, 22-25 (1952). i ± AÁLá *. * "- ^ * -J * *****, - *.-xJ &. * iii Metallic transition complexes of cyclic macropol rigid ligands The compositions mentioned herein may also include as bleach catalysts a transition metal complex of a rigid macropolycyclic ligand The phrase "cyclic macropol rigid ligand" is sometimes abbreviated as "MRL" thereafter The amount used is a catalytically effective amount, appropriate of about 1 ppb or more, for example up to about 99.9%, more typically about 0.001 ppm or more, preferably from about 0.05 ppm to about 500 ppm (where "ppb" denotes parts per billion in weight and "ppm" denotes parts per million by weight). Appropriate transition metals, for example, Mn are illustrated below. "Macropolycyclic" means that an MRL is a macrocycle and is polycyclic. "Polycyclic" means at least bicyclic. The term "rigid" as used in the present invention includes "having a superstructure" and "cross bridge". "Rigid" has been defined as forced converse of flexibility: see DH Busch., Chemical Reviews, (1993), 93, 847-860, incorporated by reference, more particularly, "rigid" as used in the present invention means that the MRL must be decidedly stiffer than a macrocycle ("macrocycle base") that is otherwise identical (with the same ring size and type and number of atoms in the main ring) but lacks a superstructure (especially parts of union or preferably bridging parts) found in the MRLs In determining the comparative stiffness of macrocycles with or without superstructures, the practitioner will use the free form (not the metal bonding form) of the macrocycles.The stiffness is well known to be useful when comparing macrocycles; Appropriate tools for determining, measuring or comparing rigidity include 5 methods of computation (see, for example, Zimmer, Chemical Reviews. (1995), 95 (38), 2629-2648 or Hancock et al., Inorganic Chimica Acta, (1989), 164, 73-84. The preferred MRLs here are a special type of ultrarigid ligand that bridges. A "cross bridge" is illustrated in an unlimited way in 1.11 later. In 1.11, the cross bridge is a part of -CH2CH2-. Link N1 and N8 in the illustrative structure. For comparison, an E bridge of the "same side", for example if you were to enter one through N1 and N12 in 1.11, it would not be enough to constitute a "cross bridge" and therefore it would not be preferred. Suitable metals in the rigid ligand complexes include Mn (il), Mn (III), Mn (IV); Mn (V), Fe (ll), Fe (lll), Fe (IV), Co (l), Co (ll), Co (lll), Ni (l), Ni (ll), Ni (IH), Cu (l), Cu (ll), CU (III), Cr (ll), Cr (lll), Cr (IV), Cr (V), Cr (VI), V (lll), V (IV), V (V), Mo (1V), Mo (V), Mo (VI), W (IV), W (V), W (VI), Pd (ll), Ru (ll), Ru (lll), and Ru (IV). Preferred transition metals in the instant metal transition bleach catalyst 20 include manganese, iron and chromium. More generally, the MRLs (and the corresponding metal transition catalysts) mentioned herein comprise: (a) at least one macrocycle main ring comprising four or more heteroatoms; and (b) a covalently connected non-metallic superstructure capable of increasing the stiffness of the macrocycle, preferably selected from (i) a link superstructure, such as a junction part (i) a cross-bridge superstructure, such as a part cross bridge connection; and (iii) combinations thereof. The term "superstructure" is used in the present invention as defined in the literature of Busch et al., See, for example, articles written by Busch in "Chemical Reviews". The preferred superstructures mentioned herein not only improve the stiffness of the base macrocycle, but also favor the bending ability of the macrocycle in such a way that it coordinates with a metal in a groove. The superstructures can be remarkably simple, for example, a joining part such as any of those illustrated in formula A and formula B can be used. • \ 20 (CH2) n Formula A where n is an integer, eg 2 to 8, preferably less than 6, typically 2 to 4, or Formula B wherein m and n are integers of about 1 to 8, more preferably 1 to 3; Z is N or CH; and T is a compatible substituent atom, for example, H, alkyl, trialkylammonium, halogen, nitrogen, sulfonate, or the like. The aromatic ring at 1.10 can be replaced by means of a saturated ring, wherein the Z-atom connected to the ring can contain N, O, S or C. Suitable MRLs are illustrated without limit by the following compound: Formula C This is an MRL that according to the invention is a highly preferred, cross-linked, methyl-substituted cyclam derivative (all tertiary nitrogen atoms). Formally, this ligand is called 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 Panic, W. H. Powell and J-C Richer (Eds.), Blackwell Scientific Publications, Boston, 1993; see especially section R 2.4.2.1. The metal transition bleach catalysts of Macrocyclic Rigid Ligands which are suitable for use in the compositions of the invention can generally include known compounds where they conform to the definition given herein, as well as, more preferably any of a large number of new compounds expressly designated for the cleaning or laundry uses present, and unlimitedly illustrated by any of the following: Dichloro-5,12-dimethyl-1, 5,8,12-tetraazabicyclo [6.6.2] hexadecane Manganese (ll) Diacuo-5,12-dimethyl-1, 5,8,12-tetraazablciclo [6.6.2] hexadecane Manganese (ll) Hexafluorophosphate Acuo-hydroxy-5,12-dimethyl-1, 5,8,12-tetraazabicyclo [6.6.2] hexadecane Manganese (lll) Hexafluorophosphate Diacuo-5,12-dimet-1, 5,8,12-tetraazabicyclo [6.6 .2] Manganese hexadecane (ll) Tetrafluoroborate Dichloro-5,12-dimethyl-1, 5,8,12-tetraazabicyclo [6.6.2] hexadecane Manganese (lll) Hexafluorophosphate Dichloro-5,12-di-n-butyl-1, 5,8,12-tetraazabicyclo [6.6.2] hexadecane Manganese (II) * * • f •• * • ü-? Fi & tmtM- * * '**? *. * t¿ *, **. *? Jt? Jt *.

Dichloro-5,12-dibenzyl-1, 5,8,12-tetraazabicyclo [6.6.2] hexadecane Manganese (II) Dichloro-5-n-butyl-12-methyl-1, 5,8,12-tetraaza-bicyclo [6.6.2] hexadecane Manganese (ll) 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 (ll). (f) Other blanching catalysts The compositions mentioned herein may comprise one or more bleach catalysts. Preferred bleach catalysts are the zwitterionic ion bleach catalysts, which are described in U.S. Patent No. 5,576,282 (especially, 3- (3,4-dihydroisoquinoline) propanesulfonate Other bleach catalysts include cationic bleach catalysts such as US Pat. 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 are described, and as a practical matter, and not by way of limiting, the compositions and The aforementioned cleaning processes can be adjusted to provide in the order of at least one part per hundred of a million active bleach catalyst species in the aqueous washing medium, and preferably will provide from about 0.01 ppm to about 25 ppm, with greater preference of about 0.05 ppm to about 10 ppm, and more preferably from about 0.1 ppm to about 5 ppm, of the catalyst bleaching species in solution n washing. In order to obtain said levels in the washing solution of an automatic washing process, the typical compositions mentioned in the present invention will comprise from about 0.0005% to about 0.2%, more preferably from about 0.004% to about 0.08% , of bleaching catalyst, especially cobalt catalysts or # manganese, by weight of the cleaning composition. Preferably, the peroxygen source is selected from the sources of hydrogen peroxide that are selected from the group consisting of perborate compounds, percarbonate compounds, A-perfosphate compounds and mixtures thereof, and a bleach activator. Preferably, the bleach activator is selected from the group consisting of hydrophobic bleach activators as shown in the present invention. The purpose of said bleaching system is to mitigate the undesired decomposition of the organic catalyst, and to allow the peracid to achieve the bleaching performance in a fabric that so requires, such as a stained fabric, in a washing solution prior to the availability of the bleach. 20 organic catalyst. The time that elapses between the peracid becoming active in a wash solution and that the organic catalyst compounds become active can be on the scale of about 1 second to approximately 24 hours. Alternatively, because the organic catalyst compounds are relatively stable in the wash solution, the peracid becomes active in the wash solution after the organic catalyst compound becomes active or available. The purpose of a delayed addition bleaching system (which may or may not be used in conjunction with this invention) is to allow the peracid to achieve a maximum bleaching performance in a fabric that requires cleaning, such as a soiled cloth, in a wash solution prior to the introduction of the organic catalyst compound. In other words, a bleaching system comprising an organic catalyst compound that becomes active in a wash solution after a cloth requiring cleaning has been added to the wash solution. Alternatively, because the organic catalyst compounds may have improved stability, a bleaching system comprising an organic catalyst compound which becomes active in a washing solution can be used before a fabric requiring cleaning is added to the washing solution. A preferred bleaching system according to the present invention is a bleaching system comprising: (a) a peroxygen source, and (b) an organic zwitterionic ion catalyst compound.; wherein the organic zwitterionic ion catalyst compound becomes active in a wash solution containing said bleaching system some time after said peroxygen source becomes active. The peroxygen source, as previously mentioned, is preferably selected from the group consisting of: (i) preformed peracid compounds which are selected from the group consisting of percarboxylic acids and salts, percarbon acids and salts, perimidic acids and salts, peroxymonosulfuric acids and salts, and mixtures thereof, and (ii) hydrogen peroxide sources which are selected from the group consisting of perborate compounds, percarbonate compounds, perphosphate compounds and mixtures thereof, and an activator of bleach. The bleaching systems of the present invention also preferably comprise, in addition to one or more organic catalysts, described below, one or more auxiliary cleaning materials, preferably compatible with the organic catalysts and / or any enzyme present in the bleaching system. The term "compatible", as used in the present invention, means that the materials of the bleaching system do not reduce the bleaching activity of the organic catalyst and / or any enzymatic activity of any enzyme present in the bleaching system to such an extent. that the organic catalyst and / or enzyme is not effective as desired during situations of normal use. The term "auxiliary cleaning materials", as used in the present invention, means any liquid, solid or gaseous material chosen for the particular type of desired bleaching system and the form of the product (for example, granular, powder, stick, paste, aerosol, tablet, gel, foam) whose materials are preferably also compatible with the protease enzymes and agents of the invention. bleaching used in the composition. The granulated compositions can also be presented in "compact" form and the liquid compositions in "concentrated" form. The specific selection of auxiliary cleaning materials is carried out considering the surface, article or fabric to be cleaned, and the desired form of the composition for the cleaning conditions during use (for example, by means of the use of washing detergent) . Examples of auxiliary cleaning materials include, but are not limited to, surfactants, detergency builders, bleaches, bleach activators, bleach catalysts, other enzymes, enzyme stabilization systems, chelators, optical brighteners, soil release polymers. dye transfer agents, dispersants, suds suppressors, dyes, perfumes, dyes, filler salts, hydrotropes, photoactivators, fluorescent agents, fabric conditioners, hydrolyzable surfactants, preservatives, antioxidants, anti-shrinking agents, anti-wrinkle agents, germicides, fungicides , color spots, antioxidant and / or anti-corrosion agents, alkalinity sources, solubilization agents, carriers, processing aids, pigments and pH control agents as described in US Patent Nos. 5,705,464, 5,710,115, 5,698,504, 5,695,679 , 5,686,014 and 5,646,101. The iil LáJL? *: * -i¡mi * .. í * ,. uüt, ^ ** specific bleaching system materials are exemplified in detail later. If the auxiliary cleaning materials are not compatible with the protease variants in the bleaching systems, appropriate methods can be used to keep the auxiliary cleaning materials and the protease variants separate (not in contact with one another) until appropriate the combination of the two components. Appropriate methods can be any method known in the art, such as capsules, encapsulation, tablets, physical separation, etc. Such bleaching systems include detergent compositions for cleaning hard surfaces, unlimited in shape (eg, liquid, granulated, paste, foam, aerosol, etc.); fabric cleaning detergent compositions, unlimited in shape (for example, granular, liquid, bar, etc.) formulations of washing compositions (unlimited in shape and including automatic granulated and liquid washing); oral bleaching systems, unlimited in shape (for example, tooth formulations, in toothpaste and mouth rinses); and teeth whitening systems, unlimited in shape (for example, liquids, tablets). The fabric bleaching systems of the present invention are basically intended to be used in the washing cycle of a washing machine; however, other uses may be contemplated, such as pretreatment product for very dirty fabrics, or soaking product; the use is not necessarily limited to the context of the washing machine, and the compositions of the present invention may be used alone or in combination with compatible hand washing compositions. The bleach systems may include from about 1% to about 99.9% by weight of the composition of the cleaning auxiliary materials. As used in the present invention, "systems of # bleaching which is not for fabrics "includes hard surface bleaching systems, dishwashing compositions, oral bleaching systems, denture bleaching systems and personal cleansing compositions.When the bleaching systems of the present invention are formulated as compositions Suitable for use in a washing machine washing method, the compositions of the present invention preferably contain a compound both surfactant and builder 15 and additionally one or more auxiliary cleaning materials which are preferably selected from organic polymeric compounds, bleaching, additional enzymes, suds suppressants, dispersants, lime soap dispersants, dirt suspending agents and ^ Antiredeposition and corrosion inhibitors. The laundry compositions 20 may also contain softening agents, as additional cleaning auxiliary materials. The compositions of the present invention can also be used as detergent additive products in solid and liquid form.

Said additive products are intended to supplement or reinforce 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 compositions of the invention preferably contain a surface active agent and preferably other auxiliary cleaning materials which are selected from organic polymeric compounds, foam improvers, group II metal ions. , solvents, hydrotropes and additional enzymes. If required, the density of laundry detergent compositions mentioned herein ranges from about 400 to about 1200 g / liter, preferably 500 to 950 g / liter of composition measured at 20 ° C. The "compact" form of the bleaching systems here The above mentioned is best reflected by density and, in terms of composition, by the amount of inorganic filling salts; the inorganic filling salts are conventional ingredients of detergent compositions in powder form; in conventional detergent compositions, the filling salts are present in substantial amounts, typically 17-35% 20 by weight of the total composition in the compact compositions. In compact compositions, the filling salt is present in amounts not exceeding 15% of the total composition, preferably not exceeding 10%, more preferably not exceeding 5% by weight of the composition.

The inorganic filler salts, according to the meaning in the present compositions, are selected from the group of alkali metal salts and alkali chlorides and sulfates. A preferred salt is sodium sulfate. The liquid bleaching systems according to the present invention can also be presented in a "concentrated" form, in which case, the liquid bleaching systems, according to the present invention, will contain a lower amount of water, as compared to liquid detergents. conventional Typically, the water content of the concentrated liquid bleaching system is preferably less than 40%, more preferably less than 30%, more preferably less than 20% by weight of the bleaching system.

Auxiliary cleaning materials. Although not essential for the purposes of the present invention, several conventional auxiliaries illustrated hereinafter are suitable for use in instant bleaching systems and can be incorporated in preferred embodiments of the invention, for example to assist or improve the cleaning performance, for treating the substrate to be cleaned, or for modifying the aesthetics of the bleaching system as in the case with perfumes, colorants, dyes or the like. The 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 operation of cleaning for which it will be used. Unless otherwise specified, the bleaching systems of the invention may for example be formulated as "heavy duty" or all-purpose washing agents in the form of powder or granules, especially laundry detergents, washing agents for all purpose in the form of paste, gel or liquids, especially the so-called heavy duty liquid types; liquid detergents for fine fabrics; handwashing agents by hand or light workwashing agents, especially those of the high foaming type; washing machine agents, including the various types of rinse aid, tablet, granulate and liquid for domestic and institutional use; liquid cleaning and disinfecting agents, including antibacterial hand washing types, laundry bars, mouth rinses, denture cleaners, shampoos for trolleys or mats, bath cleaners, hair shampoos and hair rinses; bath gels and foam baths and metal cleaners; as well as cleaning aids such as bleach additives and pretreatment types or "sticky stain".

Surfactants The compositions of the present invention preferably contain a detersive surfactant. The detersive surfactant is typically selected from the group consisting of anionic, non-ionic, cationic, ampholytic, zwitterionic ions, and mixtures thereof. By selecting the type and amount of detersive surfactant, along with others ttfci l »-» Aí_ & * * *? Í? .. JL ** * .- i k * .íí l _ t *. ., »,,. to *? auxiliary materials shown in the present invention, the present detergent compositions can be formulated for use in the context of laundry cleaning or in other different cleaning applications, particularly including washing of dishes. The particular surfactants used can vary widely depending on the specific last use programmed. Subsequently, suitable surfactants are described. Examples of non-ionic, anionic, cationic, zwitterionic and zwitterionic surfactants are provided in "Surface Active Agents and Detergents" (Vol. I and II by Schwartz, Perry and Berch).

A variety of such surfactants are also shown in US Patent 3,929,678, issued December 30, 1975 to Laughiin, et al. in column 23, line 58 to column 29, line 23. Typically, the surfactant is present at a level of about 0.1%, preferably about 1%, with higher Preferably, about 5% by weight of the bleaching systems will be about 99.9%, preferably about 80%, more preferably about 35%, more preferably about 30% by weight of the bleaching systems. 20 Anionic Surfactants The anionic surfactants useful in the present invention are preferably selected from the group consisting of linear alkylbenzenesulfonate, alphaolefin sulphonate, paraffinsulfonates, íd.j,? jtÍ?, - £ kl? t ** t. ** 1 . i * ii. *? . ^ Tfah, ^ .... faith, .. alkylethersulphonate, alkyl sulfates, alkylalkoxysulfate, alkylsulfonates, alkylalkoxycarboxylate, alkoxylated alkylsulfates, sarcosinates, taurinates, and mixtures thereof. An effective amount may be used, typically from about 0.5% to about 90%, preferably from about 5% to about 60%, more preferably from about 10 to about 30%, by weight of anionic detersive surfactant. Alkyl sulfate surfactants are another type of anionic surfactant of importance for use in the present invention. In addition to providing excellent general cleaning ability when 10 used in combination with polydroxylic fatty acid amides (see below), including good oil / grease cleaning on a wide range of temperatures, water concentrations and wash times, • the dissolution of alkyl sulphates can be obtained, as well as improved formulability in liquid detergents, the formulations are soluble salts in Water or acids of the formula ROS03M wherein R is preferably a C- or C-24 hydrocarbyl, preferably an alkyl or hydroxyalkyl with a C- or C-2 alkyl component, more preferably a C 12 C-is alkyl or hydroxyalkyl , and M is H or a cation, for example, an alkali metal cation • (Group IA) (for example, sodium, potassium, lithium), substituted ammonium cations or Unsubstituted such as methyl-, dimethyl-, and trimethyl ammonium and quaternary ammonium cations, for example tetramethylammonium and dimethyl piperdinium, and cations derived from alkanolamines such as ethanolamine, diethanolamine, triethanolamine and mixtures thereof and the like. Typically, they are preferred C? 2-? 6 alkyl chains due to lower wash temperatures (e.g., below about 50 ° C) and C16-1 alkyl chains are preferred 8 due to higher wash temperatures (e.g., per enzyme) around 50 ° C). The alkoxylated alkyl sulfate surfactants are another category of useful anionic surfactants. These surfactants are water-soluble salts or acids typically of the formula • RO (A) mS03M wherein R is a hydroxyalkyl group or C ?0-C24 alkyl not substituted with a C? Or C24 alquilo alkyl component, preferably a Hydroxyalkyl or C 12 -C 20 alkyl, more preferably hydroxyalkyl or C 2 -C 8 alkyl, A is an ethoxy or propoxy unit, m is greater than zero, typically between about 0.5 and about 6, with greater • preference between about 0.5 and about 3, and M is H or a cation which can be, for example, a metal cation (eg, sodium, potassium, 15 lithium, etc.), substituted ammonium cation or ammonium. The ethoxylated alkyl sulfates as well as the propoxylated alkyl sulphates are contemplated in this document. Specific examples of substituted ammonium cations include quaternary ammonium cations and methyl-, dimethyl-, trimethyl-ammonium cations, such as tetramethylammonium, dimethylpiperidinium and cations derived from alkanolamines, For example, monoethanolamine, diethanolamine and triethanolamine and mixtures thereof. Exemplary surfactants are polyethoxylated alkyl sulfate Ci2-C | 8 (1.0), polyethoxylated alkyl sulfate C12-C18 (2.25), polyethoxylated alkyl sulfate C12-C18 (3.0), and polyethoxylated alkyl sulfate C? 2-C? ß (4.0), where M ar *? ás * í? á? É *** Í -..- í * i (jtiá * 1 • > - fo *! ** ** .. ** *. ****. ***. *** £ **. ** & , *,. **** *** i * it * a * ***** ** & m ********* ** t, *? *? ***** t * *? *** a * ^ *** i? I * - ~ ***** &- «. - conveniently selects sodium and potassium. The surfactants for use in the present invention can be obtained from synthetic or natural alcohol feedbacks.The chain lengths represent average hydrocarbon distributions, including branching.Additionally and preferably, the surfactant can be a medium chain, alkylalkoxylated branched alkyl sulfate. branched medium chain or medium chain branched alkoxylated alkyl sulfate.

• Surfactants are described in No. 60/061, 971, Case No. 6881 P October 14, 1997, No. 60/061, 975, Case No. 6882P October 14, 1997, No. 10 601062,086, case No. 6883P October 14, 1997, No. 601061, 916, case No. 6884P October 14, 1997, No. 60/061, 970, case No. 6885P October 14, 1997, No. 601062,407 , Case No. 6886P October 14, 1997. Other appropriate medium chain branched surfactants can be found in the US patent applications with series no. 60 / 032,035 (case 15 No. 6401 P), 60/031, 845 (case No. 6402P), 601031, 916 (case No. 6403P), 60/031, 917 (case No. 6404P), 60/031, 761 (case No. 6405P), 60/031, 762 (case No. 6406P) and 601031,844 (case No. 6409P). Mixtures of these branched surfactants with agents are also suitable • conventional linear surfactants for use in the present 20 compositions. Another preferred anionic surfactant is the so-called alkyl benzene sulphonate or MLAS surfactants. Some suitable MLAS surfactants, methods for making them and compositions IJ,? **? * K..a .- * - * - * .., ... .a, J ^ "..., .... a ^ ft jfc, ^ of exemplification are described in the US patent applications co-pending with serial numbers 601053,319 (case No. 6766P), 601053,318 (case No. 6767P), 601053,321 (case No. 6768P), 60 / 053,209 (case No. 6769P), 60 / 053,328 (case No. 6770P), case 601053,186 (case No. 6771 P), case number 601055,437 (case No. 6796P), case number 60 / 105,017 (Case No. 7303P), and case No. 601104,962 (Case No. 7304P) . Examples of anionic surfactants are provided • appropriate in "Surface Active Agents and Detergents" (Vol. I and II by Schwartz, Perry and Berch). 10 Non-ionic detergent surfactants Generally non-ionic detergent surfactants • are shown in US Patent 3,929,678, Laughiin et al., Issued December 30, 1975, column 13, line 14 through column 16, line 6, 15 incorporated in the present invention by reference. For exemplification, unlimited classes of useful non-ionic surfactants include: amine oxides, alkyl ethoxylated, alkanoyl glucosamide, alkylbetaines, sulfobetaine and mixtures thereof. Amine oxides are non-ionic surfactants 20 semipolar and include water-soluble amine oxides containing an alkyl part of from about 10 to about 18 carbon atoms and 2 parts which are selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from about 1 to about 3 carbon atoms; water-soluble phosphine oxides containing an alkyl part of from about 10 to about 18 carbon atoms and 2 parts which are selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from about 1 to about 3 5 carbon atoms; and water soluble sulfoxides containing an alkyl part of from about 10 to about 18 carbon atoms and 2 parts which are selected from the group consisting of alkyl parts and parts #hydroxyalkyl containing from about 1 to about 3 carbon atoms. The semipolar non-ionic detergent surfactants include amine oxide surfactants having the formula O • R3 (OR4) NN (R5) 2 wherein R3 is an alkyl, hydroxyalkyl or alkylphenyl group or mixtures thereof containing from about 8 to about 22 carbon atoms; R4 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 R5 groups can be linked to one another, for example, through an oxygen or nitrogen atom, to form a ring structure.

These amine oxide surfactants in particular include amine oxides alkyl dimethyl C-io-Ciß and amine oxides alkoxy ethyl dihydroxy ethyl C8-C? 2. 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 from about 0.1% to about 15%, even more preferably still around from 0.5% to about 10%, by weight. The condensates of polyethylene oxide, polypropylene and prolibutylene of alkylphenols. In general, polyethylene oxide condensates are preferred. These compounds include the condensation products of alkylphenols having an alkyl group containing from about 6 to about 12 carbon atoms either in straight chain or branched chain configuration with the alkylene oxide. In a preferred embodiment, the ethylene oxide is present in an amount equal to about 5 to about 25 moles of ethylene oxide per mole of alkylphenol. 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 Rohm & Haas Company. These compounds are commonly referred to as alkylphenol alkoxylate, (eg, alkylphenol ethoxylate). The condensation products of aliphatic alcohols with from about 1 to about 25 moles of ethylene oxide. Chain Alkyl alcohol alkyl may 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 alcohol. Examples of commercially available nonionic surfactants of this type include Tergitol® 15-S-9 (the condensation product of linear secondary alcohol of C 1 -C 5 with 9 ethylene oxide), Tergitol® 24-L-6 NMW (the primary alcohol condensation product of C12-C with 6 moles of ethylene oxide with a low molecular weight distribution), both marketed by Union Carbide Corporation; Neodol® 45-9 (the linear alcohol condensation product C? -C-? 5 with 9 moles of ethylene oxide), Neodol® 23-6.5 (the linear alcohol condensation product of C-? 2-C- ? 3 with 6.5 moles of ethylene oxide), Neodol® 45-7 (the linear condensation product of C-C-15 with 7 moles of ethylene oxide), Neodol® 45-4 (the condensation product of linear alcohol C? 4.-C-? 5 with 4 moles of ethylene oxide), marketed by Shell Chemical Company, and Kyro® EOB (the condensation product of C-? 3-C-i5 alcohol with 9 moles of ethylene oxide), marketed by The Procter & Gamble Company. Other commercially available non-ionic surfactants include Dobanol 91-8® marketed by Shell Chemical Co. and Genapol UD-080® marketed kás & i¡á¡i & si «... s uz **. _ by Hoechst. This category of non-ionic surfactant is known usually as "alkyl ethoxylates." Preferred alkyl polyglycosides have the formula R20 (CnH2nO) t (glucosyl)? wherein R2 is selected from the group consisting of alkyl, aliphenyl, hydroxyalkyl, hydroxyalkylphenyl and mixtures thereof wherein the alkyl groups contain from about 10 to about 18, preferably from about 12 to about 14, carbon; n is 2 or 3, preferably 2; t is from 0 to about 10, preferably 0; and x is from about 1.3 to about 10, preferably from about 1.3 to about 3, with greater preference of about 1.3 to about 2.7. Glycosyl is a derivative preferably of glucose. To prepare these compounds, the alcohol or alkylpolyethoxy alcohol is first formed and subsequently reacted with glucose, or a source of glucose, to form the glucosite (bound to the positionl). The additional glycosyl units can be linked between their position 1 and the preceding glycosyl units of position 2, 3, 4 and / or 6, position 2 preferably predominates.

The fatty acid amide surfactants have the formula Or R6CN (R7)? iá * £ ÁA. ? ? t? *? Mt, í? * St * ¿** ..., * Where R6 is an alkyl group containing from about 7 to about 21 (preferably from about 9 to about 17) carbon atoms and each R7 is selected from the group consisting of hydrogen, C -? - C4 alkyl, C? -C4 hydroxyalkyl, and - (C2H O) xH where x ranges from about 1 to about 3. Preferred amides are C8-C2o ammonium amides, monoethanolamides, diethanolamides and isopropanolamides. 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 from about 0.1% to about 215%, even more preferably still from about 0.5% to about 10%, by weight.

Fatty Acid Polydroxylic Amide Surfactant The detergent compositions mentioned herein may also contain an effective amount of a polydroxy fatty acid amide surfactant. By "effective amount" is meant that the formulator of the composition may select an amount of the fatty acid polydroxylic acid to be incorporated into compositions that will improve the cleaning performance of the detergent composition. In general, for conventional levels, the incorporation of around 1%, by weight, the polydroxylic fatty acid amide will improve the cleaning performance. The detergent compositions mentioned herein will typically comprise a weight basis of about 1%, fatty acid polyhydroxy amide surfactant, preferably from about 3% to about 30%, of the fatty acid polydroxy acid amide. The polydroxylic acid amide surfactant component of fatty acid comprises compounds of the structural formula: wherein: R1 is H, hydrocarbyl of C -? - C4, 2-hydroxyethyl, 2-hydroxypropyl, or mixtures thereof, preferably C-? -C4 alkyl, more preferably C2 alkyl, more preferably alkyl Ci (ie methyl), and R2 is a Cs-C3 hydrocarbyl, preferably straight chain alkylene or C7-C19 alkyl, more preferably straight chain alkylene or Cg-C17 alkyl, more preferably alkylene or C 11 -C 15 alkyl, straight chain or mixtures thereof; and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof. Z will preferably derive from a reduced sugar in a reductive tuning reaction; more preferably Z will be a glycityl. Appropriate reduced sugars include glucose, fructose, maltose, lactose, galactose, mannose and xylose. As raw materials, you can use corn syrup with high concentrations of dextrose, corn syrup with high concentrations of fructose and corn syrup with high concentrations of maltose as well as individual sugars mentioned previously. These corn syrups may have a mixture of sugar components for Z. It should be understood that it is not intended to exclude other appropriate raw materials. Z will preferably be selected from the group consisting of -CH2- (CHOH) n-CH2OH, -CH (CH2OH) - (CHOH) n -? - CH2? H, -CH2- (CHOH) 2 (CHOR ') (CHOH) CH2OH, and alkoxylated derivatives thereof, wherein n is an integer from 3 to 5, inclusive, and R 'is H or a cyclic or aliphatic monosaccharide. Most preferred are the glycytyls wherein n is 4, particularly -CH2- (CHOH) 4-CH2OH. R 'can be, for example, N-methyl, N-ethyl, N-propyl, N-isopropyl, N-butyl, N-2-hydroxyethyl, or N-2-hydroxypropyl. R2-CO-N < it 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 -deoxytrotothiathityl, etc. Methods for the preparation of polydroxylic fatty acid amides are known in the art. In general, they can be made by reacting an alkylamine with a reduced sugar in a reductive amination reaction to form an N-alkyl polyhydroxyamine, and subsequently reacting the N-alkyl polyhydroxyamine with a fatty aliphatic ester or triglyceride in a condensation / amination step to form the N-alkyl amide product, N-polyhydroxy fatty acid. Processes for the preparation of compositions containing polydroxylic fatty acid amides are shown, for example, in the patent specification GB 809,060, published on February 18, 1959, by Thomas Hedley & Co., Ltd., US patent 2,965,576, issued December 20, 1960 to ER Wilson, and US patent 2,703,798, Anthony M. Schwartz, issued March 8, 1955, and US patent 1, 985,424, issued on May 25, December 1934 to Piggott, each of which is incorporated in the present invention by reference.

Diamines 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 for the diamine it is around 40: 1 to about 2: 1. Said diamines help to obtain an improved removal of fat and fatty food material while maintaining appropriate foam levels. The diamines suitable for use in the compositions of the present invention have the formula: wherein each R20 is independently selected from the group consisting of hydrogen, straight or branched CrC4 alkyl, alkyleneoxy having the formula: :-( R21 O) and R22-5 where R21 is straight or branched C2-C4 alkylene and mixtures thereof; R 22 is hydrogen, C 1 -C 4 alkyl, and mixtures thereof; and is from 1 to about 10; X is a unit selected from: i) linear C3-C? Alkylene, C3-C-? Alkylene or branched, cyclic C3-C10 alkylene, C3-C? Or branched cyclic alkylene, an alkylenoxyalkylene having the formula: :-( R21 O) and R21- wherein R21 and y are the same as previously defined; Ii) linear alkylene of C3-C-? O, C3-C? 0 branched linear, C3-C-? 0 cyclic, C3-C? Or branched cyclic, amylene of C-C-io, wherein said The unit comprises one or more donor electrons or replacement electron parts that provide said diamine with a pKa greater than about 8; and iii) mixtures of (i) and (i) as long as said diamine has • a pKg of at least 8. The preferred diamines of the present invention have a pK-t and pK2 which are on the scale of about 8 to about 11.5, preferably on the scale of about 8.4 to about 11, with greater preference of around 8.6 to about 10.75. For the ÍAÚ-líÁ * * Í Íi í í í * í í, ¡? *** ?? &? Í ** í * t *, ^ * ^., I., * *. *. *. purposes of the present invention the term "pKa" means exactly the same as for the terms "pKi" and "pK2" either separately or collectively. The term pKa as used in the present invention through the present specification in the same manner as those skilled in the art employ them. The pKa values are obtained from standard literature sources for example, "Critical Stability Constants: Volume 2, Amines" by Smith and Martel, Plenum Press, N.Y. and London, (1975). # As a definition applied in the present invention, the pKa values of the diamines are specified as measured in a solution 10 aqueous at 25 ° C having an ionic strength of about 0.1 to about 0.5 M. As used in the present invention, the pKa is an equilibrium constant that depends on the temperature and ionic strength, • therefore, the value reported by literature references, not measured in the manner described above, should not be in complete agreement with the values 15 and scales comprising the present invention. To eliminate ambiguity, the relevant conditions and / or references employed for pka of this invention are as defined in the present invention or in "Critical Stability Constants: Volume 2, Amines". A typical method of measurement is the potentiometric titration of the acid with sodium hydroxide and Determination of the pKa by means of appropriate methods as described and referenced in "The Chemist's Ready Reference Handbook" by Shugar and Dean, McGraw Hill, NY, 1990.

Preferred diamines for yield and supply considerations are 1, 3-bis (methylamino) cyclohexane, 1,3-diaminopropane (pK -? = 10.5, pK2 = 8.8), 1,6-diaminohexane (pK? = 11; pK2 = 10) ), 1,3-diaminopentane (Dytek EP) (pK ^ IO.5, pK2 = 8.9), 2-methyl-1,5- diaminopentane (Dytek A) (pK -? = 11.2, pK2 = 10.0). Other preferred materials are the primary / secondary diamines with alkylene spacers that are on the C -Cß scale. In general, primary 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: 1,6-diaminohexane having the formula: 1,3-diaminopropane having the formula: 2-methyl-1, 5-diaminopentane having the formula: 1, 3-diaminopentane, available under the trademark Dytek EP, which has the formula: 1,3-diaminobutane having the formula: Jefamina EDR 148, a diamine having an alkyleneoxy base structure, having the formula: H2N or NH, 3-methyl-3-aminoethyl-5-dimethyl-1-aminocyclohexane (isophorone diamine) having the formula 1, 3-bis (methylamino) cyclohexane which has the formula: Additional detergent components The following are unlimited examples of unlimited detergent components (auxiliary ingredients) useful in bleaching systems, especially laundry detergent compositions, of the present invention, said auxiliary ingredients include detergency builders, optical brighteners, soil release polymers dye transfer agents, dispersants, enzymes, suds suppressors, dyes, perfumes, dyes, filler salts, hydrotropes, photoactivators, fluorescent agents, fabric conditioners, hydrolyzable surfactants, preservatives, antioxidants, chelators, stabilizers, anti-shrinking agents, anti-wrinkle agents, germicides, fungicides, anticorrosion agents and mixtures thereof.

Detergency builders The bleaching systems of the present invention preferably comprise one or more detergency builders or builders. When present, the compositions will typically comprise at least about 1% builder, preferably about 5%, more preferably about 10% to about 80%, preferably about 50%, more preferably about 30% by weight of detergency builder.

I fÍ? fí '- * -'- J -' a¿afe »^ - ** - ^ ja- - ~ * A-¿* - The level of builder can vary widely depending on the final use of the composition and its desired physical form. When present, the compositions will typically comprise at least 1% builder. The formulations will typically comprise from about 5% to about 50%, more typically from about 5% to about 30%, by weight, builder. Granulated formulations typically comprise from about 10% to about 80%, more typically from about 15% to about 50% by weight, of the builder. However, this does not mean that upper or lower levels of builder are excluded. P- or inorganic-containing detergency builders include, but are not limited to, alkali metals, ammonium and alkanolammonium salts of polyphosphates (exemplified by tryphosphates, pyrophosphates, and vitreous polymeric metaphosphates), phosphonates, phytic acid, silicates, carbonates (including bicarbonates and sesquicarbonates), sulfates and aluminosilicates. However, non-phosphate builders are required in some places. Very important, the compositions mentioned herein work surprisingly well even in the presence of the so-called "diluted" detergency builder (as compared to phosphates) such as a citrate, or in the so-called "lower detergency improvement" situation. which can be presented with zeolite or stratified silicate builders.

Examples of silicate builders are alkali metal silicates, particularly those having a radius of S02: Na2O in the range of 1.6: 1 to 3.2: 1 and layered silicates, such as the sodium layered silicates described in US Pat. US Patent 4,664,839 5 Rieck, issued May 12, 1987. NaSKS-6 is the registered trademark for a crystalline layered silicate marketed by Hoechst (commonly abbreviated in the present invention as "SKS-6"). Unlike the # zeolite builders, the NaSKS-6 builder does not contain aluminum. NaSKS-6 has the form of delta-Na2S05 morphology of 10 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 layered silicate for use in this invention, but other layered silicates can be used, such as those having the general formula NaMSixO 2? +? 'And H 2 O wherein M is sodium 15 or hydrogen, x is a number from 1.9 to 4, preferably 2, and y is a number from 0 to 20, preferably 0. Other stratified silicates from Hoechst include NaSKS-5, NaSKS-7 and NaSKS-11, as the alpha forms , beta and gamma. As noted above, the delta-Na2SiO5 (NaSKS-6) form is the • most preferred for use in the present invention. Other silicates can Also useful are such as, for example, magnesium silicate, which can serve as a contrast enhancing agent in granular formulations, as a stabilizing agent for oxygen bleach, and as a component of foam control systems.

Examples of the carbonate builders are the alkali metal and alkaline earth carbonates such as those shown in German Patent Application No. 2,321,001 published November 15, 1973. 5 The aluminosilicate builders are useful in the present invention. The aluminosilicate builders are of great importance in most detergent compositions # Heavy duty granulate currently marketed, and can also be an important detergency ingredient in formulations 10 liquid detergents. The detergency builders include those that have the empirical formula: [Mz (zA102) and] -xH2O • where z and y are integers of at least 6, the molar ratio of z for y is on the scale of 1.0 to about 0.5, and x it is an integer of around 15 15 to about 264. Useful aluminosilicate ion exchange materials are commercially available. These aluminosilicates can be crystalline or amorphous in structure and can be aluminosilicates that occur naturally or synthetically derived. A method for 20 producing aluminosilicate ion exchange materials is shown in US Patent 3,985,669, Krummel et al, issued October 12, 1976. Preferred synthetic crystalline aluminosilicate ion exchange materials useful in this invention are available under the designation 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? 2 [(AI02)? 2 (Si02) 12] -? H20 wherein x is from about 20 to about 30, especially about 27. This material is known as Zeolite A. Dehydrated zeolites (x = 0-10) can also be used. Preferably, the aluminosilicate has a particle size of about 0.1-10 microns in diameter. Organic builders suitable for the purposes of the present invention include, but are not limited to, a wide variety of polycarboxylate compounds. As used in the present invention, "carboxylate" refers to compounds having a plurality of carboxylate groups, preferably at least 3 carboxylates. The polycarboxylate builder generally can be added to the composition in acid form, but can also be added in the form of a neutralized salt. When used in the form of a salt, alkali metals, such as sodium, potassium and lithium or alkanolammonium salts, are preferred. Polycarboxylate builders include a variety of categories of useful materials. An important category of polycarboxylate builders comprises ether polycarboxylates, including oxydisuccinate, as shown in the US patent 3,128,287 Berg, issued April 7, 1964. 3,635,830 Lamberti et al., Issued January 18, 1972, and US 3,936,448 Lamberti, issued February 3, 1976. See also "TMS TDS" detergency builders of U.S. Patent 4,663,071 Bush et al., issued May 5, 1987. Suitable polycarboxylate ethers also include cyclic compounds, particularly alicyclic compounds, such as those described in US Patent 3,923,679 Rapko, issued December 2, 1975; US 4,158,635 Crutchfield et al., Issued June 19, 1979; USA 4,120,874 # Crutchfield et al., Issued October 17, 1978; and USA. No. 4,102,903 Crutchfield et al., Issued July 25, 1978. Other useful builders include hydroxypolycarboxylate ethers, maleic anhydride copolymers with ethylene or vinyl methyl ether, 1,3,5-trihydroxy benzene-2,4,6 acid. - trisulphonic and carboxymethyloxysuccinic acid, the various alkali metals, ammonium and substituted ammonium salts of polyacetic acid such as the acid Ethylenediaminetetraacetic acid and nitrilotriacetic acid, as well as polycarboxylates such as melific acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene 1, 3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, and soluble salts thereof.

• Citrate builders, for example acid The citric acid and soluble salts thereof (particularly sodium salts), are polycarboxylate builders of particular importance for heavy-duty liquid detergent formulations due to their availability of renewable sources and their biodegradable capacity. The ^ ¡^ **** t * í ***** **. *. ..... j »! . * ^ t,. * ,. * j **? t ********. ** citrates can also be used in granular compositions, especially in combination with layered silicate and / or zeolite builders. Oxydisuccinates are also especially useful in said compositions and combinations. Also suitable in the bleaching systems of the present invention are the 3,3-dicarboxy-4-oxa-1,6-hexanedioates and the related compounds shown in US Pat. No. 4,566,984, Bush, issued 28 January 1, 1986. Useful succinic acid builder enhancers include succinic alkenyl and C5-C2o alkyl acids and salts of the 10 same. A particularly preferred compound of this type is dodecenylsuccinic acid. Specific examples of succinate detergency builders include: lauryl succinate, myristylsuccinate, palmityl succinate, 2-dodecenylsuccinate (preferred), 2-pentadecenylsuccinate and the like. Preferred detergency builders of this type are lauryl succinates and 15 are described in European patent application 86200690.5 / 0,200,263, published on November 5, 1986. Other suitable polycarboxylates are shown in US Patent No. 4,144,226, Crutchfield et al .. issued March 13, 1979 and in the US. • 3,308,067, Diehl, issued on March 7, 1967. See also Diehl 20 US patent 3,723,322. Fatty acids, for example, C12-C18 monocarboxylic acids, can also be incorporated into the compositions alone, or in combination with the aforementioned builders, tAtJET, * i'ta * - »'* -» -. t ^ *. «h- ^ .t? t ** *? *? * - ** **. *** ** ** -} - ***** i ^ *.,? go ^? ^ *** ii * á **** ^ * M ***? *? ** A ******* k especially citrate and / or the succinate builders to provide additional builder activity. Such use of fatty acids will generally result in a decrease in foam formation, which should be taken into account by the formulator. In situations where phosphorus-based builders, and especially in the formulation of bars used for manual laundry operations, can be used, the various alkali metal phosphates such as the well-known sodium tripolyphosphates, sodium pyrophosphate and orthophosphate can be used. of sodium. Phosphonate builders such as ethane-1-hydroxy-1, 1-diphosphonate and other known phosphonates can also be used (see, for example, US patents 3,159,581, 3,213,030, 3,422,021, 3,400,148 and 3,422,137).

Guelatary Agents The bleaching systems mentioned herein may also optionally contain one or more iron and / or manganese chelating agents. Said chelating agents can be selected from the group consisting of aminocarboxylates, aminophosphonates, polyfunctionally substituted aromatic chelating agents and mixtures thereof, as defined below. Without being limited by theory, it is believed that the benefit of these materials is due in part to their exceptional ability fetL-AAá i J ... afea, to remove iron and manganese ions from washing solutions by forming soluble chelating agents. Examples of suitable chelating agents and levels of use are described in U.S. Patent Nos. 5,576,282 and 5,728,671. A preferred biodegradable chelator for use in this invention is ethylene diamine disuccinate ("EDDS"), especially the [S, S] isomer as described in US Pat. No. 4,704,233, November 3, 1987, to Hartman and Perkins. The compositions mentioned herein may also contain water-soluble methylglycine diabetic acid (MODA) salts (or acid form) as a useful collateral chelator or builder with, for example, insoluble builders such as zeolites, silicates stratified and similar. If used, these chelating agents will generally comprise from about 0.1% by weight of the bleaching systems mentioned herein to about 15%, most preferably 3.0% by weight of the bleaching systems mentioned herein.

Dye transfer inhibiting agents The bleaching systems of the present invention may also include one or more compounds, dye transfer inhibiting agents, to inhibit the transfer of dye from one fabric to another.

YE . ... ... ^ iH ^^ > ai riteg.¿ ^ fcja?. '. At. ^ j * -Aa «soluble and suspended dyes found during laundry operations and conditioning of fabrics 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 and N-vinylimidazole, polyvinyloxazolidones and polyvinylimidazoles or mixtures thereof. Examples of said dye transfer inhibiting agents are shown in U.S. Patent Nos. 5,707,950 and 5,707,951. Additional suitable dye transfer inhibiting agents include, but are not limited to, entangled polymers. Interlaced polymers are polymers whose base structures are interconnected to a certain degree; these unions can be of a chemical or physical nature, possibly with active groups in the base structure or in branches. The Journal of Polymer Science, volume 22, pages 1035-1039 describes the interlaced polymers. In one embodiment, the entangled polymers are made in such a way that they form a rigid three-dimensional structure, which can trap dyes in the pores formed by the three-dimensional structure. In another embodiment, the interlaced polymers trap dyes by absorption. Suitable crosslinked polymers are described in co-pending European patent application 94870213.9.

In addition, said polymers also improve the performance of the enzymes within the bleaching systems mentioned herein. The dye transfer inhibiting agents have the ability to reduce or absorb fugitive dyes during the washing of the painted fabrics before the dyes have the opportunity to stick to other articles in the wash. When they are present in the bleaching systems here # mentioned, the dye transfer inhibiting agents are present at levels of about 0.0001%, more preferably around 10 of 0.01%, more preferably about 0.05% by weight of the bleaching systems to about 10%, with greater preference 2%, more preferably 1% by weight of the bleaching systems.

Dispersants 15 The bleach systems of the present invention may also contain dispersants. Suitable organic water-soluble salts are homopolymeric or copolymeric acids or their salts, wherein the polycarboxylic acid comprises at least two carboxyl radicals • separated from each other by no more than two carbon atoms. Polymers of this type are s in GB-A-1, 596,756. Examples of such salts are the polyacrylates of MW 2000-5000 and their copolymers with maleic anhydride, said copolymers have a molecular weight of 1,000 to 100,000.

Especially, an acrylate-methylacrylate copolymer such as 480N having a molecular weight of 4000, at a level of 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 peptizer compound, which has a lime soap dispersant powder (LSDP), as defined hereinafter as not more than 8. # preferably not more than 7, more preferably not more than 6. The lime soap peptizer compound is preferably present at 10 a level of 0% to 20% by weight. The lime soap dispersant powder (LSDP) provides a numerical effectiveness measure of lime soap peptizer which is determined using the lime soap dispersant test as described in the article written by H.C. Borghetty and C.A. Bergman, J. Am. Oil. 15 Chem. Soc, volume 27, pages 88-90, (1950). Practitioners of this technique widely use the lime soap dispersion test method which is referred to, for example, in the following articles; W.N. Linfield, Surfactant science Series, Volume 7, pages 3; W.N. Linfield, • Tenside surfing. det., volume 27, pages 159-163, (1990); and M.K. Nagarajan, 20 W.F. Masler, Cosmetics and Toiletries, volume 104, pages 71-73, (1989). The LSDP is the weight ratio in% dispersing agent for sodium oleate required to disperse the lime soap deposits formed by 0. 025g of sodium oleate in 30ml of water of equivalent hardness of 333ppm CaCo3 (Ca: Mg = 3: 2). Surfactants having good capacity for lime soap peptizer will include certain amine oxides, botaines, sulfobetaines, alkyl ethoxy sulfates and ethoxylated alcohols. Exemplary surfactants with an LSDP of not more than 8 for use in accordance with the present invention include dimethylamine oxide of C-iß-Ciß, C 2 -C-β-β-alkyl ether sulfates with an average degree of ethoxylation of 1-5. , particularly C? 2-C? 5 alkylcytoxy sulfate surfactant with a degree of ethoxylation of quantity 3 (LSDP = 4), and ethoxylated alcohols of CH-C-IS with an average degree of ethoxylation of 12 (LSDP = 6) or 30, sold under the trademarks Lutensol A012 and Lutensol A030 respectively, by BASF GmbH. In the article written by M.K. Nagarajan, W.F. Masler, to 15 found in Cosmetics and Toiletries, volume 104, pages 71-73, (1989) describes the polymeric lime soap peptizers suitable for use in the present invention. Hydrophobic whiteners such as 4- [N-octanoyl-6-aminohexanoyl] benzenesulfonate, 4- [N-nonanoyl-6-aminohexanoyl] benzenesulfonate, 4- [N-decanoyl] can also be used as lime soap peptiser compounds. -6-aminohexanoyl] benzenesulfonate and mixtures thereof íá * á *? * ?, kMiá ^, A *. same; and nonanoyloxybenzenesulfonate together with hydrophilic / hydrophobic bleach formulations.

Enzymes Bleaching systems may comprise in addition to the amylase of the present invention one or more detergent enzymes that provide cleaning performance and / or fabric care benefits. Said enzymes may include proteases, amylases, cellulases and lipases. They may be incorporated into the non-aqueous liquid bleaching systems mentioned herein in the form of suspensions, "granules" or "small globules". Another suitable type of enzyme comprises those in the form of enzyme pastes in non-ionic surfactants, for example, the enzymes marketed by Novo Nordisk under the trademark "SL" or the microencapsulated enzymes marketed by Novo Nordisk under the trademark " LDP. " Suitable enzymes and levels of use are described in U.S. Patent No. 5,576,282. Enzymes that are added to the compositions that are mentioned herein in the form of conventional small enzyme globules for use in this invention are preferred. Said small globules will generally have a size of about 100 to 1,000 microns, more preferably around 200 to 800 microns and will be suspended throughout the non-aqueous liquid phase of the composition. The small globules in the compositions of the present invention have been found, compared to other forms of enzyme, to especially exhibit the desired enzyme stability in terms of extra time enzyme activity retention. In this way, compositions using small globules of enzymes require no conventional enzyme stabilizer as is normally used when the enzymes are incorporated in aqueous liquid detergents. Examples of suitable enzymes include, but are not limited to, hemicellulases, peroxidases, proteases, cellulases, xylanases, lipases, phospholipases, esterases, cutinases, pectinases, keratanases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tanases, pentosanases, malanases, β-glucanases, arabinosidases, hyaluronidase, chondroitinase, laccase, known amylases, mannanases, xyloglucanases and mixtures thereof. A preferred combination is a bleaching system having a mixture of conventional applicable enzymes such as protease, lipase, cutinase and / or cellulase in conjunction with the amylase of the present invention. Examples of such suitable enzymes are shown in U.S. Patent Nos. 5,576,282, 5,728,671 and 5,707,950. Suitable proteases are the subtilisins that are obtained from particular strains of B. subtilis and B. licheniformis (subtilisin BPN and BPN). An appropriate protease is obtained from a strain of Bacillus, having maximum activity through the pH scale of 8-12, developed and sold as ESPERASE® by Novo Industries A S of Dinarmarca, hereinafter "Novo." The preparation of this enzyme and analogous enzymes are described in GB 1, 243,784 to Novo. Other suitable proteases include ALCALASE®, DURAZYM® and SAVINASE® from Novo and MAXATASE®, MAXACAL®, PROPERASE® and MAXAPEM® (Protein Maxacal undergoing technical study) from Gist-Brocades. Proteolytic enzymes also comprise modified bacterial serine proteases, such as those described in the European patent application serial number 87 303761, 8, registered on April 28, 1987 (particularly pages 17, 24 and 98), and that successively is called "Protease B", and in the European patent application 10 199,404, Venegas, published on October 29, 1986, describing a bacterial serine protellítica enzyme modified hereafter "Protease A" is more preferred the so-called "Protease C", which is a variant of a • Bacillus alkaline serine protease where lysine replaced arginine in position 27, tyrosine replaced valine in position 104, serine replaced 15 asparagine in position 123, and alanine replaced threonine in position 274. Protease C is described in EP 90915958: 4, corresponding to WO 91/06637, published on May 16, 1991. Also included in the present invention are genetically modified variants, particularly of ^ Protease C. See also a protease with high pH of Bacillus sp. NCIMB 20 40338 described in WO 93/18140 A to Novo. WO 92/03529 A to Novo describes enzymatic detergents comprising protease, one or more other enzymes, and a reversible protease inhibitor. When desired, a protease with reduced absorption and hydrolysis is available I * áA.í .-. * M¿ iJ.i_ * i., TÁ * k *, * .. increased as described in WO 95/07791 to Procter & Gamble. A similar recombination trypsin protease for detergents suitable in the present invention is described in WO 94/25583 to Novo. In more detail, the protease known as "Protease 5 D" is a variant of carbonyl hydrolase with a non-naturally occurring amino acid sequence, which is derived from a precursor carbonyl hydrolase by substituting a different amino acid for a plurality of amino acids. amino acid residues at a position in said carbonyl hydrolase equivalent to the +76 position, preferably also in 10 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 Bacillus amyloliquefaciene subtilisin numbering, such 15 as described in WO 95/10615 published on April 20, 1995 by Genencor International. For the present invention, the proteases described in the patent applications EP 251 446 and W091 / 06637 and BLAP® protease described in W091 / 02792. The enzymes ^ p proteolytics are incorporated into the bleaching systems of this 20 invention at the level of 0.0001% to 2%, preferably from 0.001% to 0.2%, more preferably 0.005% to 0.1% pure enzyme by weight of the composition.

Useful proteases are 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 5 The Procter & Gamble Company. Other particularly useful proteases are the multiply substituted protease variants comprising a substitution of a # amino acid residue with another amino acid residue naturally occurring at an amino acid residue position corresponding to position 103 of 10 subtilisin of Bacillus amiloliquefacienes in combination with a substitution of an amino acid residue with another naturally occurring amino acid residue at one or more corresponding amino acid residue positions • 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, 75, 76, 77, 78, 79, 86, 87, 89, 97, 15 98, 99, 101, 102, 104, 106, 107, 109, 111, 114, 116, 117, 119, 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, 20 246, 247, 248, 249, 251, 252, 253, 254, 255, 256, 257, 258, 259, 260, 261, 262, 263, 265, 268, 269, 270, 271, 272, 274 and 275 of subtilisin from Bacillus amiloliquefaciens; wherein said protease variant includes a substitution of amino acid residues at positions corresponding to the positions 103 and 76, there is also a substitution of an amino acid residue at one or more amino acid residue positions other than the 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 or 274 of 5 subtilisin of Bacillus amiloliquefaciens and / or multiply substituted protease variants comprising a substitution of one amino acid residue with another amino acid residue naturally recurrent to one or # more amino acid residue positions corresponding to positions 62, 212, 230, 232, 252 and 257 of Bacillus amiloliquefaciens subtilisin as described in published PCT applications Nos. WO 99/20727, WO 99120726, and WO 99120723 all owned by The Procter & Gamble Company. • Most preferably the protease variant includes a substitution group that is selected from the group consisting of: 15 12/76/103/104/130/222/245/261; 62/1031104/159123212361245/248/252; 62/103/104/1591213/2321236/245/248/252; 62/101/103/104/159/212/213/232/236/245/248/252; • 68/103/104/159/232/236/245; 20 68/103/104/159/230/232/236/245; 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; 68/103/104/159/185/232/236/245/248/252; 68/103/104/159/185/210/232/236/245/248/252; 68/103/104/159/210/232/2361245/248/252; 68/103/104/159/2113/232/236/245; 98/103/104/159/232/236/245/248/252; 98/102/103/104/159/212/232/236/245/248/252; 101/103/104/159/232/236/245/248/252; 102/103/104/159/232/236/245/248/252; 103 / 104/159/230/236/245; 103/104/159/232/236/245/248/252; 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. Even more preferably, the protease variant includes a substitution group that is selected from the group consisting of: 12R / 76D / 103A 104T / 130T / 222S / 245R 261 D; 62D / 103A / 1041 / 159D / 232V / 236H / 245R / 248D / 252K; 62D / 103A / 1041 / 159D / 213R / 232V / 236H / 245R / 248D / 252K; 68A / 103A / 1041 / 159D / 209W / 232V / 236H / 245R; 68A / 76D / 103A / 1041 / 159D / 213R / 232V / 236H / 245R / 260A; 68A / 103A / 1041 / 159D / 213E / 232V / 236H / 245R / 248D / 252K; 68A 103A / 1041 / 159D / 183D / 232V / 236H / 245R / 248D / 252K; 5 68A / 103A / 1041 / 159D / 232V / 236H / 245R; 68A / 103A / 1041 / 159D / 230V / 232V / 236H / 245R; 68A / 103A / 1041 / 159D / 232V / 236H / 245R / 257V; # 68A 103A / 1041 / 159D / 213G / 232V / 236H / 245R / 248D / 252K; 68A / 103A / 1041 / 159D / 185D / 232V / 236H / 245R / 248D / 252K; 10 68A / 103A / 1041 / 159D / 185D / 210L / 232V / 236H / 245R / 248D / 252K; 68A 103A / 1041 / 159D / 210L / 232V / 236H / 245R / 248D / 252K; 68A 103A / 1041 / 159D / 213G / 232V / 236H / 245R; 98L / 103A / 1041 / 159D / 232V / 236H / 245R / 248D / 252K; 98L / 102A / 103A / 1041 / 159D / 212G / 232V / 236H / 245R / 248D / 252K; 15 101 G / 103A / 1041 / 159D / 232V / 236H / 245R / 248D / 252K; 102A / 103A / 1041 / 159D / 232V / 236H / 245R / 248D / 252K; 103A / 1041 / 159D / 230V / 236H / 245R; 103A / 1041 / 159D / 232V / 236H / 245R / 248D / 252K; f 103A / 1041 / 159D / 217E / 232V / 236H / 245R / 248D / 252K; 20 103A / 1041 / 130G / 159D / 232V / 236H / 245R / 248D / 252K; 103A / 1041 / 13IV / 159D / 232V / 236H / 245R / 248D / 252K; 103A / 1041 / 159D / 213R / 232V / 236H / 245R / 248D / 252K; and 103A / 1041 / 159D / 232V / 236H / 245R More preferably, the protease variant includes the substitution group 101/103/104/159/232/236/245/248/252, preferably 101 G / 103A / 1041 / 159D / 232V / 236H / 245R / 248D / 252K. The cellulases usable in the present invention include bacterial or fungal cellulases. Preferably, they will have an optimum pH between 5 and 9.5. Appropriate cellulases are shown in U.S. Patent 4,435,307, Barbesgoard et al, which shows fangal cellulase produced from Humicola insolens. Suitable cellulases are shown in GB-A-2,075,028; GB-A-2,095,275 and DE-OS-2,247,832. Examples of said cellulases are the cellulases produced by insolens strain (Humicola grísea var. Termoidea), particularly the strain of Humicola DSM 1800. • Other suitable cellulases are the cellulases that are derived from Humicola isolens having a molecular weight of about 15 50KDa, an isoelectric point of 5.5 and containing amino acids 415; and an endoglucanase -43kD which is derived from Humicola isolens, DSM 1800, and which shows cellulase activity; A preferred component of endoglucanase has an amino acid sequence which is shown in patent application PCT No. WO 91117243. Suitable cellulases are the EGIII cellulases of 20 Trichoderma longibrachiatum described in W094121801, Genencor, published September 29, 1994. Particularly suitable cellulases are cellulases that show color care benefits. Examples of said cellulases are the cellulases described in the European patent application No. 91202879. 2, registered on November 6, 1991 (Novo). Especially useful are Carezyme and Celluzyme (Novo Nordisk A / S). See also W091 / 17243. Peroxidase enzymes are known in the art, and include, for example, horseradish peroxidase, ligninase, and haloperoxidase such as chlorine and bromo-peroxidase. The peroxidase contained in the bleaching systems are shown, for example, in U.S. Patent Nos. 5,576,282, • 5,728,671 and 5,707,950, international applications of PCT WO 89/099813, W089 / 09813 and in the European patent application EP No. 91202882.6, 10 registered on November 6, 1991 and EP No. 96870013.8, registered on February 20, 1996 The laccase enzyme is also appropriate. Preferred builders are the fentiazine and • substituted phenoxasine 10-phenothiazinepropionic acid (PPT), 10-ethylphenothiazine-4-carboxylic acid (EPC), 10-phenoxyacinpropionic acid (POP) and 15-methylphenoxacin (described in WO 94/12621) and substituted serinate (seringatos de C3-C5 alkyl, substituted) and phenols. Preferred sources of hydrogen peroxide are perborate or sodium percarbonate. Said peroxidases are normally incorporated in the bleaching system at levels of 0.0001% to 2% of active enzyme by weight of the 20 bleaching. Other preferred enzymes that may be included in the bleaching systems of the present invention include lipases. Suitable lipase enzymes for detergent use include those produced by microorganisms from the group of Pseudomonas, such as Pseudomonas stutzeri ATCC 19,154, as shown in British Patent 1, 372,034. Suitable lipases include those that show a positive immunological cross-reaction with the lipase antibody, produced by the fluorescent Pseudomonas microorganisms lAM 1057. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trademark Lipase P "Ameno," hereafter "Amano-P". Other lipases Suitable commercial carriers include Ameno-CES lipases, ex Chromobacter viscosum, for example, Chromobacter viscosum ver. lipolyticum NRRLB 3673 10 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. Particularly suitable lipases are lipases such as Ml LIPASE® and LIPOMAX® (Gist-Brocades) and LIPOLASE® and LIPOLASE ULTRA® (Novo) which are considered to be very effective when 15 used in combination with the compositions of the present invention. Also suitable are cutinases [EC 3.1.1.50] that can be considered as a special type of lipase, merely lipases that require n interfacial activation. Other cutinases for bleaching systems t are described in, for example, WO 88/09367 (Genencor). The lipases and / or cutinases are normally incorporated in the bleaching system at levels of 0.0001% to 2% of active enzyme by weight of the bleaching system.

Known amylases (a and / or β) can be included for removal of carbohydrate-based stains. WO 94/02597, Novo Nordisk A / S published on February 3, 1994, describes cleaning compositions incorporating mutant amylases. See also W094 / 18314, Genencor, published August 18, 1994 and W095110603, Novo Nordisk A / S, published April 20, 1995. Other amylases known to be used in bleaching systems include both amylase a and amllasa ß. In the art, amylases a and include those shown in the US patent 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 amylases are amylases of improved stability including PURAFACT OX AMO described in WO 94118314, published August 18, 1994 and W096 / 05295, Genencor, published on February 22, 1996 and amylase variants of Novo Nordisk A / S, shown in WO 95110603, published in April 1995. Examples of commercial α-amylase products are TERMAMYL®, BAN®, FUNGAMYL® and DURAMYL®, all available from Novo Nordisk A / S Denmark. W095126397 describes other suitable amylases: α-amylases are characterized by having a specific activity at least 25% higher than the specific activity of TERMAMYL® at a temperature range of 25 ° C to 55 ° C and a pH value on the scale from 8 to 10, measured by the α-amylase Phadebas® activity assay. Other amylolytic enzymes with properties are described in W095 / 35382 improved with respect to the activity level and the combination of thermostability and a higher activity level. The compositions of the present invention may also comprise a mannanase enzyme. Preferably, the mannanase is selected from the group consisting of: three enzymes of degrading mannan: EC 3.2.1.25: ß-mannosidase, EC 3.2.1.78: Endo-1, 4-ß-mannosidase, hereinafter "mannanase" and EC 3.2.1.100: 1, 4-ß-manobiosidase and mixtures thereof. (IUPAC Enzyme Classification Nomenclature, 1992 ISBN 0-12-227165-3 Academic Press). More preferably, the treatment compositions of the present invention, when a mannanase is present, comprises a β-1,4-mannosidase (E.C. 3.2.1.78) known as Mananase. The term "mannanase" or "galactomannanase" denotes a mannanase enzyme defined according to the technique as officially named mannan endo-1, 4-beta-mannosidase and with the optional names beta-mannanase and endo-1,4-mannan and catalyzing the reaction: random hydrolysis of 1, 4-beta-D-mannosidic bonds, mannones, galactomannans, glucomannans, and galactoglucomannans. In particular, mannanases (EC 3.2.1.78) constitute a group of polysaccharides that degrade mannans and denote enzymes that are capable of splitting polyose chains containing mannose units, that is, they are capable of splitting glycosidic bonds into mannans, glucomannans, galactomannans and galactogluco-manans. The mannans are polysaccharides ^ fltlliJllillÉBrí irtilililNli 'iilMf \ X- Dn? -rf - ni - ^^^^^^^ htfr ^ - * »- c - ~ * > - < * 'having a base structure composed of ß-1, 4-linked mañosa; glucomannans are polysaccharides that have a base structure or more or less alternating regularly glucose and ß-1, 4-linked mañosa; the galactomannans and galactoglucomannans are mannans and glucomannans with 5 branches of α-1,6-galactose. These compounds can be acetylated. The degradation of galactomannans and galactoglucomannans is facilitated by the total or partial removal of the galactose branches. In addition, the degradation of mannans, glucomannans, Acetylated galactomannans and galactogluctans are facilitated by total or partial deacetylation. The acetyl groups can be removed by means of alkali or by means of mannitol acetylesterases. The oligomers released by the mannanases or by a combination of mannanases and acetylesterases of a-galactosidase and / or mannan can furthermore be degraded 15 to release free maltose by means of β-mannosidase and / or β-glucosidase. Mannanases have been identified in several Bacillus organisms. for example, Talbot et al., Appl. Environ. Microbiol., Vo1.56, No. 11, pp. 3505-3510 (1990) describes a beta-mannanase derived from Bacillus stearothermophilus in the form of a dimer with a molecular weight of 162 kDa and pH 20 optimum of 5.5-7.5. Mendoza et al., World J. Microbiol. Biotech., Vol. 10, No. 5, pp. 551555 (1994) describes a beta-mannanase derived from Bacillus subtilis with a molecular weight of 38 kDa, an optimal activity at pH 5.0 and 55C and a pl of 4.8. JP-03047076 shows a beta-mananase derived from Bacillus sp., with a molecular weight of 373 kDa measured by gel filtration, an optimum pH of 8-10 and a pl of 5.3-5.4. JP-63056289 discloses the production of a thermostable alkaline beta-mannanase which hydrolyzes beta-1,4-D-mannopyranoside linkages from, for example, mannans and which produces hand-5 oligosaccharides. JP-63036774 describes the microorganism of Bacillus FERM P-8856 which produces beta-mannanase and beta-mannosidase at an alkaline pH. JP-08051975 shows alkaline beta-mannanases from Bacillus alcalofilicos sp. AM001 A purified mannase from Bacillus amiloliquefacienos useful in the bleaching of pulp and paper and a method of preparation thereof 10 show in WO 97111164. WO 91/18974 describes a hemicellulase such as an active of glucanase, xylanase or mannanase at an extreme pH and temperature. WO 94125576 shows an enzyme of Aspergillus aculeatus, CBS 101.43, which exhibits mannase activity which may be useful for the degradation or modification of cell wall material of plant or algae. WO 15 93/24622 shows an isolated mannanase from Trichoderma reseei useful for bleaching lignocellulosic pulps. In W091118974 a hemicellulase capable of degrading hemicellulase containing mannan and in W097111164 describes a purified mannanase from .Bacillus ^ amiloliquefacienos. Preferably, the mannanase enzyme will be an alkaline mannanase as defined below, more preferably, a mannanase whose origin is in a bacterial source. Especially, the laundry detergent composition of the present invention will comprise an alkaline mannanase which is selected from the mannanase of the strain Bacillus agaradhaerens NICMB 40482; Mannase from Bacillus subtilis strain 168, gene yght; the mannase from Bacillus sp. 1633 and / or the mannase of Bacillus sp. AAI12. More preferably, the mannanase for inclusion in the detergent compositions of the present invention is the mannanase enzyme whose origin is in Bacillus sp. 1633 as described in the co-pending Dutch patent application No. PA 1998 01340. The terms "alkanal mannanase enzyme" encompass an enzyme with an enzymatic activity of at least 10%, preferably at least 25%, more preferably at least 40% of its maximum activity at a certain pH that is located on the scale of 7 to 12, preferably 7.5 to 10.5. The alkaline mannanase from Bacillus agaradhaerens NICMB 40482 is described in the co-pending EUA patent application serial number 091111, 256. More specifically, this mannanase is: 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 the EUA patent application serial number 091111, 256; or iii) an analogue of the polypeptide defined in i) or ii) that is at least 70% homologous with said polypeptide, or is a derivative of said polypeptide by substitution, deletion, or addition of one or more amino acids, c A »* & £? i. -tü ^ feSa ^ rfl ^ i. or is immunologically reactive with a polyclonal antibody that is against said polypeptide in purified form.

It also comprises the corresponding isolated polypeptide with a mannanase activity which is selected from the group consisting of: (a) polynucleotide molecules which encode a polypeptide with mannanase activity and which comprise a sequence of nucletides such • as shown in SEQ ID NO: 1 of nucleotide 97 to nucleotide 1029 as shown in the EUA patent application with serial number. 09/111, 256; 10 (b) homologous species of (a); (c) polynucleotide molecules that encode a polypeptide with mannanase activity of at least 70% identical to the sequence of • amino acid of SEQ ID NO: 2 from amino acid residue 32 to amino acid residue 343 as shown in the US patent application with 15 serial number 09/111, 256; (d) complementary molecules for (a), (b) or (c); and (e) nucleotide sequences of (a), (b), (c) or (d). Plasmid pSJ1678 comprising the polynucleotide molecule (the DNA sequence) encoding said mannanase, has been transformed into a strain of Escherichia coli that the inventors deposited 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 Ib, D-38124 Braunschweig, Federal Republic of Germany, on May 18, 1998 with deposition number DSM 12180. A second preferred enzyme is mannanase of Bacillus subtilis strain 168, which is described in the co-pending EUA patent application serial number 09 / 095,163. More specifically, this mannanase: i) is encoded by the code portion of the DNA sequence shown in SED ID No. 5 shown in patent application serial number 09 / 095,163 or an analogue of said sequence; and / or ii) a polypeptide comprising an amino acid sequence as shown in SEQ ID N0: 6 shown in the EUA patent application serial number 09 / 095,163; or iii) an analogue of the polypeptide defined in ii) which is at least 70% homologous to said polypeptide, or which is a derivative of said polypeptide by substitution, deletion or addition of one or more amino acids, or is immunologically reactive with a polyclonal antibody that is against said polypeptide in purified form. It also comprises the corresponding isolated polypeptide with a mannanase activity that is selected from the group consisting of: (a) polynucleide molecules encoding a polyeptide with mannanase activity and comprising a sequence of nucleolides as shown in SEQ ID NO: 5 as shown in the EUA patent application with serial number. 09 / 095,163; (b) homologous species of (a); (c) polynucleotide molecules encoding a polypeptide with mannanase activity of at least 70% identical to the amino acid sequence of SEQ ID NO: 6 as shown in the EUA patent application serial number 09 / 095,163; (d) complementary molecules for (a), (b) or (c); and (e) nucleotide sequences of (a), (b), (c) or (d). A third most preferred enzyme is described in co-pending Danish patent application No. PA 1998 01340. More specifically, this mannanase is: i) a polypeptide produced by Bacillus sp. 1633; I) a polypeptide comprising an amino acid sequence as shown in positions 33-340 of SEQ ID NO: 2 shown in the Danish application No. PA 1998 01340; or iii) an analogue of the polypeptide defined in i) or ii) which is at least 65% homologous to said polypeptide, or which is a derivative of said polypeptide by substitution, deletion or addition of one or more amino acids, or is immunologically reactive with a polyclonal antibody that is against said polypeptide in purified form. It also comprises the isolated polynucleotide molecule which is selected from the group consisting of: (a) polynucleotide molecules which encode a polypeptide with mannanase activity and which comprise a sequence of nucletides such * ¿, A. * Á.ii - * í ± i * ¿¿¿¿&¿ * i * - *** - ** > * as shown in SEQ ID NO: 1 of nucleotide 317 to nucleotide 1243 as shown in the Danish application No. PA 1998 01340; (b) homologous species of (a); (c) polynucleotide molecules that encode a polypeptide with mannanase activity of at least 65% identical to the amino acid sequence of SEQ ID NO: 2 from amino acid residue 33 to amino acid residue 340 as shown in the patent application Danish No. • 1998 01340; (d) complementary molecules for (a), (b) or (c); and 10 (e) nucleotide sequences degraded from (a), (b), (c) or (d). Plasmid pBXM3 comprising the polynucleotide molecule (the DNA sequence) encoding said mannanase, has been transformed into a strain of Escherichia coli that the inventors deposited in accordance with the Budapest International Treaty for the Deposit of Microorganisms for Purposes 15 of Patent Procedures in the Deutsche Sammiung von Mikroorganismen und Zellkulturen GmbH, Mascheroder Weg Ib, D-38124 Braunschweig, Federal Republic Republic of Germany, on May 29, 1998 under deposit number DSM 12197. kina fourth preferred mannanase is described in the application of 20 Danish co-pending patent No. PA 1998 01341, this mannanase is: i) a polypeptide produced by Bacillus sp. AAI 12; I) a polypeptide comprising an amino acid sequence as shown in positions 25-362 of SEQ ID. N0: 2 as shown in the Danish patent application Serial No. PA 1998 01341; or iii) an analogue of the polypeptide defined in i) or ii) that is at least 65% homologous with said polypeptide, is derived from said polypeptide by substitution, removal or addition of one or more amino acids, or is immunologically reactive with an antibody polyclonal raised against said polypeptide in purified form. Also encompassed is the corresponding isolated polynucleotide molecule selected from the group consisting of: (a) polynucleotide molecules that encode a polypeptide having mannanase activity and comprising a nucleotide sequence as shown in SEQ ID NO. NO: 1 from nucleotide 225 to nucleotide 1236 as shown in Danish patent application No. PA 1998 01341; (b) homologous species 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. NO: 2 from amino acid residue 25 to amino acid residue 362 as shown in Danish patent application Serial No. PA 1998 01340; (d) molecules complementary to (a), (b) or (c); and (e) degraded nucleotide sequences of (a), (b), (c) or (d).

Plasmid pBXM1 comprising the polynucleotide molecule (the DNA sequence) encoding a mannanase of the present invention has been transformed into a strain of Escherichia coli which was deposited by the inventors in accordance with the Budapest Treaty in the International Deposit Recognition of Microorganisms for the Purposes of Patent Procedures in the Deutsche Sammiung von Mikroorganismen und Zellkulturen GmbH, Mascheroder Weg Ib, D-38124 Braunschweig, Federal Republic of Germany, on October 7, 1998 under deposit number DSM 12433. Mannanase, when present, it is incorporated into the treatment compositions of the present invention preferably at a level of from 0.0001% to 2%, more preferably from 0.0005% to 0.1%, with even greater preference 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. Xyloglucanases suitable for the purpose of the present invention are enzymes that exhibit endoglucanase activity specific for xyloglucan, preferably at a level of 0.001% to about 1%, more preferably 0.01% to about 0.5%, by weight of the composition. As used herein, the term "endoglucanase activity" means the ability of the enzyme to hydrolyse 1, 4-β-D-glycosidic bonds present in any cellulosic material, such as cellulose, cellulose derivatives, lichenine, β-D - iit t * X *** ^ ** ^., ^ if *, jtiiaa glucan, or xyloglucan. The endoglucanase activity can be determined according to methods known in the art, examples of which are described in WO 94/14953 and below. One unit of endoglucanase activity (eg, CMCU, AVIU, XGU or BGU) is defined as the production of 1 μmol of sugar reduction / minute from a glucan substrate, the glucan substrate is for example, CMC (CMCU), of expanded acid Avicell (AVIU), xyloglucan (XGU) or ß-glucan (BGU) of cereal. The reducing sugars are determined as described in WO 94/14953 and below. The specific activity of an endoglucanase towards a substrate is defined as units / milligrams of protein. Enzymes exhibiting higher activity in their activity XGU endoglucanase (hereinafter "specific for xyloglucan), whose enzyme: i) is encoded by a DNA sequence comprising or included in at least one of the following sequences are suitable. partial (a) ATTCATTTGT GGACAGTGGA C (SEQ ID NO: 1) (b) GTTGATCGCA CATTGAACCA (SEC ID NO: 2) (c) ACCCCAGCCG ACCGATTGTC (SEC ID NO: 3) (d) CTTCCTTACC TCACCATCAT ( SEQ 1D 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) (i) AGCATCAGCC GCTTTGTACA (SEQ ID NO: 9) Ü) CCATGAAGTT CACCGTATTG (SEQ ID NO: 10) (k) GCACTGCTTC TCTCCCAGGT (SEQ ID NO. NO: 11) (I) GTGGGCGGCC CCTCAGGCAA (SEQ ID NO: 12) (m) ACGCTCCTCC AATTTTCTCT (SEQ ID NO: 13) (n) GGCTGGTAG TAATGAGTCT (SEC ID NO: 14) (or) GGCGCAGAGT TTGGCCAGGC (SEQ 1 D NO: 15) (p) CAACAT CCCC GGTGTTCTGG G (SEC ID. NO: 16) (q) AAAGATTCAT TTGTGGACAG TGGACGTTGA TCGCACATTG AACCAACCCC AGCCGACCGA TTGTCCTTCC TTACCTCACC ATCATTTAAC ATCTTTTCAC CATGAAGCTT TCCCTTCTCT CCCTTGCCAC CCTGGCTTCC GCTGCCAGCC TCCAGCGCCG CACACTTCTG CGGTCAGTGG GATACCGCCA CCGCCGGTGA CTTCACCCTG TACAACGACC TTTGGGGCGA GACGGCCGGC ACCGGCTCCC AGTGCACTGG AGTCGACTCC TACAGCGGCG ACACCATCGC TTGTCACACC AGCAGGTCCT GGTCGGAGTA GCAGCAGCGT CAAGAGCTAT GCCAACG (SEC ID N0: 17) or ******?. ***:?: á, A * Í'-Íi¡Í * H '- * »' 's. ^^ * ^ *** ^ ******** ** - **** ^ ********* t ,, .a > ai .a ..i > ttiJ, J.fc ^ Jl ^ Aafa ^! taLlA? a (r) CAGCATCTCC ATTGAGTAAT CACGTTGGTG TTCGGTGGCC CGCCGTGTTG CGTGGCGGAG GCTGCCGGGA GACGGGTGGG GATGGTGGTG GGAGAGAATG TAGGGCGCCG TGTTTCAGTC 5 CCTAGGCAGG ATACCGGAAA ACCGTGTGGT AGGAGGTTTA TAGGTTTCCA GGAGACGCTG TATAGGGGAT AAATGAGATT GAATGGTGGC CACACTCAAA CCAACCAGGT CCTGTACATA CAATGCATAT ACCAATTATA CCTACCAAAA AAAAAAAAAA AAAAAAAAAA AAAA (SEQ ID NO: 18) or a sequence analogous thereto which encodes a polypeptide specific for xyloglucan with endoglucanase activity. Ii) is immunologically reactive with an elevated antibody against a highly purified endoglucanase encoded by the DNA sequence defined in i) and which is derived from Aspergillus aculeatus, CBS 101.43, and is specific for xyloglucan. Very specifically, as used in the present invention, the term "specific for xyloglucan" means that the enzyme endoglucanase • exhibits its highest endoglucanase activity on a xyloglucan substrate, and 20 preferably with a percentage less than 75%, more preferably less than 50% activity, more preferably even less than 25% activity, or other substrates that they contain cellulose such as carboxymethylcellulose, cellulose, or other glucans.

Preferably, the specificity of an endoglucanase makes xyloglucan is further defined as a relative activity determined as the release of reducing sugars at optimum conditions obtained by incubation of the enzyme with xyloglucan and other substrates that are tested, respectively. For example, the specific character can be defined as xyloglucan to β-glucan activity (XGU / BGU), xyloglucan to carboxymethylcellulose activity (XGU / CMCU), or xyloglucan to Avicell expandable acid activity (XGU / AVIU), which is preferably higher from 50, to about 75, 90 or 100. The term "derived from" is used in the present invention to refer not only to an endoglucanase produced by the CBS 101.43 strain, but also to 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 "homologous" is used in the present invention to indicate a polypeptide encoded by DNA that hybridizes to the same probe as the DNA encodes a endoglucanase enzyme specific for xyloglucan under certain specified conditions (such as pre-soaking in 5xSSC and prohibited for 1 hour at -40 ° C in a 5xSSC solution, dxDenhardt solution, and 50 μg of denatured sonified calf fimo DNA, followed by hybridization in the same solution supplemented with probe labeled with 50 μCi 32-P-dCTP for 18 hours at -40 ° C and washing three times in 2xSSC, 0.2% SDS at 40 ° C for 30 minutes). Very specifically, the term is intended to refer to a DNA sequence that is at least 70% homologous to any of the sequences shown above coding for a endoglucanase specific for xyloglucan, including at least 75%, at least 80%, at least 85%, at least 90 % or even at least 95% with any 5 of the sequences shown above. The term is intended to include modifications of any of the DNA sequences shown above, such as nucleotide substitutions that do not give rise to another amino acid sequence of the polypeptide encoded by the sequence, but which correspond to the codon use of the host organism in which A DNA structure comprising any of the DNA sequences is introduced into or are substitutions of nucleotides that give rise to a different amino acid sequence and therefore, it is possible, a sequence of • amino acid and therefore it is also possible a different structure of proteins that can give rise to a mutant endoglucanase with different 15 properties that the enzyme origin. Other examples of possible modifications are the insertion of one or more nucleotides in the sequence, the vision of one or more nucleotides, either at the end of the sequence, or the deletion of one or more nucleotides at either end or within the sequence . w The endoglucanase specific for xyloglucan useful in the present The preferred invention is one having a ratio of XGUBGU, XGU / CMU and / or XGU / AVIU (as defined above) greater than 50, such as 75, 90 or 100.

Moreover, the xyloglucan specific endoglucanase is preferably substantially devoid of activity towards β-glucan and / or exhibits a maximum of 25% such that at most 10% or about 5% activity towards carboxylmethylcellulose and / or Avicell when the activity towards xyloglucan It is 100%. In addition, the endoglucanase specific for the xyloglucan of the invention is preferably substantially devoid of transferase activity, an activity that has been observed for plant-specific xyloglucan endoglucanases. The endoglucanase specific for xyloglucan can be obtained from the fungal species of A. aculeatus, as described in WO 94/14953. Microbial endoglucanases specific for xyloglucan have also been described in WO 94/14953. The endogiucanases specific for xyloglucan from plants have been described above, but these enzymes have transferase activity and therefore should be considered inferior to the microbial endoglucanases specific for xyloglucan as long as extensive xyloglucan degradation is desirable. An additional advantage of a microbial enzyme is that, in general, it can be produced in larger quantities in a microbial host, than enzymes of other origins. Xyloglucanase, when present, is incorporated into the treatment compositions of the invention preferably at a level of from 0.0001% to 2%, more preferably from 0.0005% to 0.1%, with greater still preferred from 0.001% to 0.02% pure enzyme by weight of the composition. The enzymes mentioned above may be of any suitable origin, such as plant, animal, bacterial, fungal and yeast origin. Also the purified or non-purified forms of these enzymes can be used. Mutants of source enzymes are also included by definition. Mutants can be obtained for example • by genetic manipulation and / or proteins, chemical and / or physical modifications of source enzymes. The common practice as well as the expression of the enzyme by host organisms in which the genetic material is responsible for the production of the enzyme that has been cloned said enzymes are normally incorporated into the bleaching system at levels of 0.0001% to 2% of the active enzyme by weight of the bleaching system. The enzymes can be added as separate single ingredients (granules, granules, stabilized liquids, etc. containing an enzyme) or as mixtures of two or more enzymes (for example cogranulates). Other suitable detergent ingredients that can be • add, they are enzymatic oxidation purifiers. Examples of said enzyme oxidation scavengers are ethoxylated tetraethylenepolyamines A scale of enzyme materials and means for their incorporation into synthetic bleaching systems are also described in WO 93/07263 and WO 93/07260 to Genencor International, WO 89/08694 a Novo, and US 3,553,139, January 5, 1971 to McCarty et al. Enzymes are also described further in US 4,101,457, Place et al, July 18, 1978, and in US 4,507,219, Hughes, March 26, 1985. Useful enzyme materials for liquid detergent formulations, and their incorporation into said formulations are described in US 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 described and exemplified in US 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 US 3,519,570. A Bacillus species, sp. AC13 which gives proteases, xylanases and cellulases, is described in WO 9401532 to Novo. The enzymes that are employed in the present invention can be stabilized by the presence of water-soluble sources of calcium and / or magnesium ions in the finished compositions that provide said ions to the enzymes. Stabilizers and levels of use of suitable enzymes are described in U.S. Patent No. 5,576,282.

Other Detergent Ingredients Bleach compositions herein may also optionally contain one or more of the following: dispersing agents polymeric, clay soil removal / anti-redeposition agents, brighteners, foam suppressors, colorants, perfumes, structure-elasticizing agents, fabric softeners, vehicles, hydrothores, processing aids and / or pigments. Suitable examples of said different detergent ingredients and levels of use can be found in U.S. Patent No. 5,576,282 Cleaning methods In addition to the methods for cleaning fabrics, dishes and other 10 difficult surfaces, and personal cleansing body parts described herein, the invention also encompasses a laundry pre-treatment procedure for soiled or stained fabrics which directly comprises contacting said stains and / or dirt with a highly concentrated form of a money laundering system established previously for the 15 washing said fabrics using conventional aqueous wash solutions. Preferably, the bleaching system remains in contact with the dirt / stain for a period of about 30 seconds to 24 hours before washing the pre-treated dirt / stain substrate from ^ conventional way. More preferably, the pre-treatment times 20 are around 1 to 180 minutes. The following examples are for exemplifying compositions of the present invention, but do not necessarily mean that they are limited or in any way define the scope of the invention.

In the following examples some known abbreviations are used for the technique exspertos, consistent with the description set forth herein.

EXAMPLE I Bleaching detergent compositions in the form of granular laundry detergents are exemplified by the following formulations: ABCDE Organic catalyst * 0.034 0.06 0.03 0.10 0.05 Conventional activator (NOBS) 2.00 2.80 2.00 1.80 5.30 5.30 Conventional activator (TAED) 0.00 0.00 0.60 0.00 0.00 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 Linear alkylbenzene sulfonate 12.00 0.00 12.00 0.00 21.00 C45AE0.6S 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 Glucamide span N-methyl 1.70 2.00 1.70 2.00 0.00 C12 dimethylhydroxyethylammonium 1.50 0.00 1.50 0.00 0.00 chlorine 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 0.00 Copolymer Acid polyacrylic, partially 3.00 3.00 3.00 3.00 0.00 neutralized Dust-releasing agent 0.00 0.00 0.50 0.40 0.00 10 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 Savinasa (4T) 1.00 1.00 1.00 1.00 0.60 Termamilo (60T) 0.40 0.40 0.40 0.40 0.40 15 Lipolase (100T) 0.12 0.12 0.12 0.12 0.12 0.12 Carezime (5T) 0.15 0.15 0.15 0.15 0.15 0.15 Diethylenetriaminpenta (acid 1.60 1.60 1.60 1.60 0.40 methylene phosphonic) Brightener 0.20 0.20 0.20 0.05 0.20 Sulfonated zinc 0.50 0.00 0.25 0.00 0.00 • Phthalocyanine photoblank 20 MgS04 2.20 2.20 2.20 2.20 0.64 Na2S0 Rest Rest Rest Rest * The organic catalyst can be any of the zwitterionic organic catalysts described herein, preferably is an organic iminium-based catalyst, more preferably is an organic catalyst based on dihydroisoquinolinio Any of the above compositions can be used to wash fabrics in a consultation of 3500 ppm in water, 25 ° C, and a ratio of 15: 1 water: clothes. The typical pH is around 9.5 but it # can adjust altering the proportion of acid to the salt form of Na of alkylbenzenesulfonate. EXAMPLE II * Bleaching detergent compositions having the form of granular laundry detergents are exemplified by the following formulations: 15 ABCDE Organic catalyst * 0.009 0.04 0.14 0.14 0.002 Conventional activator (NOBS) 1.80 0.00 0.00 1.00 1.00 Conventional activator (TAED) 0.00 1.00 2.50 3.00 0.00 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 20 Linear Alkylbenzenesulfonate 21.00 12.00 0.00 12.00 12.00 C45AE0.6S 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 Glucamide span N-methyl 0.00 1.70 2.00 1.70 1.70 C12 dimethylhydroxyethylammonium 1.00 1.50 0.00 1.5O 1.50 chlorine 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 Dirt release agent 0.30 0.50 0.00 0.5 O 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 Sodium bicarbonate 2.00 5.00 5.00 5.00 5.00 10 Savinase (4T) 0.60 1.00 1.00 1.00 1.00 Termamilo (60T) 0.40 0.40 0.40 0.40 0.40 Lipolase (100T) 0.12 0.12 0.12 0.12 0.12 Carezime (5T) 0.15 0.15 0.15 0.15 0.15 • acid 0.40 0.00 1.60 0.00 0.00 Diethylenetriaminpentamethylenephosphine) 15 Brightener 0.20 0.30 0.20 0.30 0.30 Sulfonated zinc 0.25 0.00 0.00 0.00 0.00 Phthalocyanine bleacher MgS04 0.64 0.00 2.20 0.00 0.00 Na2S04 rest rest rest rest • 20 * The organic catalyst can be any of the zwitterionic organic catalysts described herein, preferably it is a catalyst iminium-based organic, more preferably it is an organic catalyst based on dihydroisoquinolinium taji jliiÜirtliÉÉri'lt 1¿ AtMiiÜMiti "- ahti ^ a" i --- * "-i - ..» S¿i ^ A. »lbJ ^^^. fc ^ .- ^ Any of the previous compositions you can use to wash fabrics in a concentration of 3500 ppm in water, 25 ° C, and a ratio of 15: 1 water: clothes. The typical pH is around 9.5 but it can adjust by altering the proportion of acid to the Na salt form of alkylbenzenesulfonate.

EXAMPLE III A bleaching detergent powder according to the present invention comprises the following ingredients: Compound% weight Organic catalyst * 0.01 NOBS 2.0 Perborate sodium tetrahydrate 10 C12 linear alkyl benzene sulfonate 8 Phosphate (as sodium tripolyphosphate) 9 Sodium carbonate 20 Talcum 15 Rinse aid, perfume 0.3 Sodium chloride 25 Water and minors Rest at 100% * The organic catalyst can be any of the zwitterionic organic catalysts described herein, preferably it is an organic catalyst based on iminium, more preferably it is an organic catalyst based on dihydroisoquinolinium EXAMPLE IV A laundry bar suitable for manual washing of Dirty fabrics are prepared by standard extrusion procedures and It includes the following: Compound% weight 10 Organic catalyst * 0.02 NOBS 1.7 TAED 0.2 Perborate sodium tetrahydrate 12 • C12 30 linear phosphate (as sodium tripolyphosphate) 10 Sodium carbonate 5 15 Sodium pyrophosphate 7 Coconut monoethanolamide 2 Zeolite A (0.1-10 microns) 5 Carboxymethylcellulose 0.2 Polyacrylate (m.w. 1400) 0.2 F Rinse aid, perfume 0.2 Protease 0.3 20 CaS04 1 MgS04 1 Water 4 Filler2 Rest at 100% * The organic catalyst can be any of the zwitterionic organic catalysts described herein, preferably it is an organic catalyst based on minium, more preferably it is an organic catalyst based on dihydroisoquinolinium 2 It can be selected from suitable materials such as CaCO3, talc, clay , silicates, and the like. Acidic fillers can be used to reduce the pH.

EXAMPLE V A laundry detergent composition suitable for machine use is prepared by standard extrusion methods and comprises the following: * The organic catalyst can be any of the zwitterionic organic catalysts described herein, preferably it is an organic iminium-based catalyst, more preferably it is an organic catalyst based on dihydroisoquinolinio. The fabric washing composition can be used at a solution concentration of about 1000 ppm at a temperature of 20-40 ° C and a water to fabric ratio of about 20: 1.

EXAMPLE VI Composition% weight Organic catalyst * 0.082 NOBS 7.20 Perborate sodium tetrahydrate 8.0 Sodium carbonate 21.0 Anionic surfactant 12.0 Aluminum silicate 18.0 Diethylenetriaminpentaacetic acid 0.3 Nonionic surfactant 0.5 Polyacrylic acid 2.0 Brightener 0.3 Sulphate 17.0 Perfume 0.25 Miscellaneous 2.95 Water Rest * The organic catalyst can be any of the organic catalysts zwitterionics described herein, preferably is a catalyst iminium-based organic, more preferably is an organic catalyst based on dihydroisoquinolinio The composition can be used as a laundry aid to wash fabrics at a concentration in solution of around 850 ppm at a temperature of 5-50 ° C and a proportion of water to fabrics around 20: 1.

EXAMPLE VII A bleaching composition suitable for use in geographies of high foam phosphate has the formula: Compound A (% weight) B (% weight) Organic catalyst * 0.02 0.018 NOBS 1.90 2.00 Perborate sodium tetrahydrate 2.25 3.00 Sodium carbonate 13.00 13.00 Anionic surfactant 19.00 19.00 Cationic surfactant 0.60 0.60 Nonionic surfactant - 0.40 Sodium tripolyphosphate 22.50 22.50 Diethylenetriaminpentaacetic acid 0.90 0.90 Acrylic acid / maleic acid copolymer 0.90 0.90 Carboxylmethylcellulose 0.40 0.40 Protease 0.70 0.70 Amylase 0.36 0.36 Cellulase 0.35 0.35 Brightener 0.16 0.18 Magnesium sulphate 0.70 0.70 Water 3.0 1.0 Sodium sulfate Rest Rest * The organic catalyst can be any of the zwitterionic organic catalysts described herein, preferably it is an organic catalyst based on iminium, more preferably it is an organic catalyst based on dihydroisoquinolinium. While particular embodiments of the present invention have been described, it will be obvious to those skilled in the art that various changes and modifications may be made to the present invention without departing from the spirit and scope of the invention. It is intended to cover, in the appended claims, all those modifications that are within the scope of the invention. The compositions of the present invention can be prepared in a suitable manner by any method chosen by the formulator, the non-limiting examples of which are described in the US patents Nos. 5,691, 297; 5,574,005; 5,569,645; 5,565,422; 5,516,448; 5,489,392; Y 5,486,303. In addition to the foregoing examples, the bleaching systems of the present invention can be formulated in any suitable laundry detergent composition, the 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 examples, it will be apparent 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 considered to be limited in scope. Regarding what is described in the specification.

LIST OF SEQUENCES < 110 > The Procter & Gamble Company Dykstra, Robert < 120 > Color-retaining laundry methods employing zwitterionic formulation components < 130 > 7758M < 150 > 60 / 151,174 < 151 > 1999-08-27 < 160 > 18 < 170 > Patentln version 3.0 < 210 > 1 < 211 > 21 < 212 > DNA < 213 > Aspergillus aculeatus < 400 > 1 attcatttgt ggacagtgga c 21 < 210 > 2 < 211 > 20 < 212 > DNA < 213 > Aspergillus aculeatus < 400 > gttgatcgca cattgaacca 20 < 210 > 3 < 211 > 20 < 212 > DNA < 213 > Aspergillus aculeatus < 400 > 3 accccagccg accgattgtc 20 F < 210 > 4 < 211 > 20 < 212 > DNA 10 < 213 > Aspergillus aculeatus < 400 > 4 cttccttacc tcaccatcat 20 • < 210 > 5 < 211 > 20 15 < 212 > DNA < 213 > Aspergillus aculeatus < 400 > 5 ttaacatctt ttcaccatga 20 < 210 > 6 < 211 > 20 20 < 212 > DNA < 213 > Aspergillus aculeatus < 400 > 6 agctttccct tctctccctt 20 IJUjáü, ^ ** ^^ - t? iiÉÍfl ^^ á¡m * - ~ < 210 > 7 < 211 > 28 < 212 > DNA < 213 > Aspergillus aculeatus < 400 > 7 gccaccctgg cttccgctgc cagcctcc 28 < 210 > 8 < 211 > 20 < 212 > DNA < 213 > Aspergillus aculeatus < 400 > 8 gacagtagca atccagcatt 20 < 210 > 9 < 211 > 20 < 212 > DNA < 213 > Aspergillus aculeatus < 400 > 9 agcatcagcc gctttgtaca 20 < 210 > 10 < 211 > 20 < 212 > DNA < 213 > Aspergillus aculeatus < 400 > 10 ccatgaagtt caccgtattg 20 < 210 > 11 < 211 > 20 < 212 > DNA < 213 > Aspergillus aculeatus < 400 > 11 gcactgcttc tctcccaggt 20 F < 210 > 12 < 211 > 20 10 < 212 > DNA < 213 > Aspergillus aculeatus < 400 > 12 gtgggcggcc cctcaggcaa 20 < 210 > 13 15 < 211 > 20 < 212 > .ADN < 213 > Aspergillus aculeatus < 400 > 13 F acgctcctcc aattttctct 20 twenty «TAÍ it ^ JMlJAtjtmiaMa ^.« JaJ? aa «*« M .. ^ > ... ~ »^»? * »- > * ^. *? ~ * -% ^ \ & tk * ¡tJk * ^ eía * ^, '? - t n'lfea & a. < 210 > 14 < 211 > 19 < 212 > DNA < 213 > Aspergillus aculeatus < 400 > 14 ggctggtagt aatgagtct 19 < 210 > 15 < 211 > 20 • < 212 > DNA < 213 > Aspergillus aculeatus 10 < 400 > 15 ggcgcagagt ttggccaggc 20 F < 210 > 16 < 211 > 21 < 212 > DNA 15 < 213 > Aspergillus aculeatus < 400 > 16 caacatcccc ggtgttctgg g 21 < 210 > 17 < 211 > 347 20 < 212 > DNA < 213 > Aspergillus aculeatus < 400 > 17 aaagattcat ttgtggacag tggacgttga tcgcacattg aaccaacccc agccgaccga 60 ttgtccttcc ttacctcacc atcatttaac atcttttcac catgaagctt tcccttctct 120 cccttgccac cctggcttcc gctgccagcc tccagcgccg cacacttctg cggtcagtgg 180 gataccgcca ccgccggtga cttcaccctg tacaacgacc tttggggcga gacggccggc 240 accggctccc agtgcactgg agtcgactcc tacagcggcg acaccatcgc ttgtcacacc 300 agcaggtcct ggtcggagta gcagcagcgt caagagctat gccaacg 347 < 210 > 18 < 211 > 294 < 212 > DNA < 213 > Aspergillus aculeatus < 400 > 18 cagcatctcc attgagtaat cacgttggtg ttcggtggcc cgccgtgttg cgtggcggag 60 gctgccggga gacgggtggg gatggtggtg ggagagaatg tagggcgccg tgtttcagtc 120 cctaggcagg ataccggaaa accgtgtggt aggaggttta taggtttcca ggagacgctg 180 tataggggat aaatgagatt gaatggtggc cacactcaaa ccaaccaggt cctgtacata 240 aaaaaaaaaa aaaa accaattata caatgcatat cctaccaaaa aaaaaaaaaa 294

Claims

NOVELTY OF THE INVENTION CLAIMS 1. A bleaching system for washing fabrics requiring cleaning comprises from about 0.001 ppm to about 5 ppm of a zwitterionic organic catalyst compound selected from the group characterized by consisting of: a) zwitterionics of aryliminium, which have a charge net of around +3 to about -3, which are 10 represented by the formula [II]: [11] wherein R5-R7 are independently selected from the substituted or unsubstituted radicals selected from the group consisting of radicals of H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, heterocyclic ring, silyl, nitrogen, halogen, cyano, sulfonate , alkoxy, keto, carboxylic, and carboalkoxy; ^ in this formula is also present the radical represented by the 20 formula: where Zp "is covalently bound to T0, and Zp" is selected from the group consisting of -CO2", -SO3", -OSO3", -SO2" and -OS02"and p j ij *** * ** is 1, 2 or 3; To is selected from the group consisting of alkyl, cycloalkyl, aryl, alkaryl, aralkyl and substituted or unsubstituted heterocyclic ring, saturated or unsaturated; b) zwitterionics of oxaziridinium, which have a net charge of around +3 to about -3, which are represented by the formula [IV]: [IV] Wherein R5-R7 are independently selected from the substituted or unsubstituted radicals selected from the group consisting of radicals of H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, heterocyclic ring, silyl, • nitrogen, halogen, cyano, sulfonate, alkoxy, keto, carboxylic, and carboalkoxy; in this formula is also present the radical represented by the 15 formula: -T0- 2? where Zp "is covalently bound to To, and Zp" is selects from the group consisting of "C02", "S03", "OS03-, -S02- and -OS02- and p is 1, 2 or 3; TO is selected from the group consisting of alkyl, cycloalkyl, Aryl, alkaryl, aralkyl and substituted or unsubstituted, saturated or unsaturated heterocyclic ring; c) mixtures thereof. 2. - The bleaching system according to claim 1, further characterized in that said bleaching system also i., 3 «¿jjfajfaáa.1, M? ¿? *? a.¿., * i **** ^ tkjt¿k?, *. ** ít * m? * * tjtfc < < , JJ ^ st | ^ M > ^ aa.jArifaahá. -, ******,? s ¿. comprises from about 2.0 ppm to about 1200 ppm of one or more peroxygen sources. 3. The bleaching system according to claim 1, further characterized in that said bleaching system further comprises from about 0.5 ppm to about 300 ppm of one or more peracids. 4.- The bleaching system in accordance with the claim 1, further characterized in that said bleaching system further comprises from about 1.0 ppm to about 600 ppm of one or 10 more peroxygen compounds. 5.- The bleaching system in accordance with the claim 2, further characterized in that said source of peroxygen is selected from F group consisting of: (a) preformed peracid compounds which are selected from the group consisting of acids and percarboxylic salts, acids and 15 percarbon salts, acids and perimidic salts, acids and peroxymonosulfuric salts, and mixtures thereof; (b) sources of hydrogen peroxide selected from the group consisting of perborate compounds, percarbonate compounds, perphosphate compounds and mixtures of the same ittk, and a bleach activator. 20 6.- The bleaching system in accordance with the claim 1, further characterized in that said zwitterionic organic catalyst is present in a concentration of about 0.01 ppm to about 3 ppm. 7. The bleaching system in accordance with the claim 6, further characterized in that said zwitterionic organic catalyst compound is present in a concentration of from about 0.1 ppm to about 2 ppm. 8. The bleaching system in accordance with the claim 7, further characterized in that said zwitterionic organic catalyst compound is present in a concentration of from about 0.2 ppm to about 1 ppm. The bleaching system according to claim 1, further characterized in that said zwitterionic organic catalyst compound is selected from the group consisting of: a) zwitterionic aryliminium, having a net charge of about +3 to about -3, which are represented by the formula [XII]: [xiq 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 R26 is independently selected from the substituted or unsubstituted radical which is selected from the group consisting of H, alkyl, cycloalkyl, aryl, fused aryl, heterocyclic ring, fused heterocyclic ring, nitrogen, halogen, cyano, •• ^ ^ "^ - sulfonate, alkoxy, keto, carboxylic, and carboalkoxy, and either of the two adjacent R26 substituent atoms may be combined to form a fused aryl, fused carbocyclic ring or fused heterocyclic ring, R25 may be a substituted radical or unsubstituted which is selected from the group of radicals H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, heterocyclic ring, silyl, nitrogen, halogen, cyano, sulfonate, alkoxy, keto, carboxylic, and carboalkoxy; in this formula is also present the radical represented by the # formula: Where ZP "is covalently bound to T0, and Zp" is selected from the group consisting of -C02", -S03", -OS03", -S02" and -OS02"and p is 1, 2 or 3; is selected from the group consisting of where q is an integer from 1 to 8; R29 is independently selected from substituted or unsubstituted radicals which are selected from the group consisting of H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, alkylene heterocyclic ring, alkoxy, arylcarbonyl, carboxyalkyl and linear amide groups • 20 or branched; G is selected from the group consisting of (1) -O-; (2) -N (R30) -; and (3) -N (R30R31) -; R27, R28, R30 and R31 are substituted or unsubstituted radicals that are independently selected from the group consisting of H, oxygen, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, alkyl, ring heterocyclic, alkoxys, arylcarbonyl groups, carboxyalkyl groups and amide groups; any of R25, R26, R27, R28, R30 and R31 can be joined together with any other R25, R26, R27, R28, R30 and R31 to form part of a common ring, any germ R27-R28 can be combined to form a 5 carbonyl; any adjacent R27-R31 can be joined to form an unsaturated portion; and further characterized in that any group of substituents R27-R31 may be combined to form a molten, substituted or unsubstituted unsaturated moiety; b) zwitterionics of oxaziridinium, having a net charge of about +3 to about -3, which are represented by the formula [XIV]: where m is 1 to 3 when G is present and m is 1 to 4 when m is not present; and n is an integer from 0 to 4; each R26 'is independently selected from the substituted or unsubstituted radical which is selected from the group consisting of radicals of H, alkyl, cycloalkyl, aryl, aryl 20 molten, heterocyclic ring, fused heterocyclic ring, nitrogen, halogen, cyano, sulfonate, alkoxy, keto, carboxylic, and carboalkoxy, and either of the two adjacent R26 substituent atoms can be combined to form a molten aryl, fused carbocyclic ring or ring fused heterocyclic; R25 it may be a substituted or unsubstituted radical selected from the group of radicals consisting of H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, heterocyclic ring, silyl, nitrogen, halogen, cyano, sulfonate, alkoxy, keto, carboxylic, and carboalkoxy; in this formula is also present the radical represented by the formula: • where Z'p "is covalently linked to TO, and Z'p" is selected from the group consisting of -C02", -S03", -OS03", -S02" and -OS02"and p 10 is 1 or 2; T0 is selected from the group consisting of: 15 where q is an integer from 1 to 8; R29 is independently selected from substituted or unsubstituted radicals which are selected from the group consisting of H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, alkylene heterocyclic ring, alkoxy, arylcarbonyl, carboxyalkyl and straight or branched amide groups; G is selected from the group consisting of (1) -O-; (2) -N (R30) -; 20 and (3) -N (R30'R31 ') -; R27 ', R28', R30 'and R31' are substituted or unsubstituted radicals which are independently selected from the group consisting of H, oxygen, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, alkyl, heterocyclic ring, alkoxy, arylcarbonyl groups, carboxyalkyl groups and groups * L ****. ***, ~ jh-Sa-s «afe» aa »< «S .. ^ * - * i-a **, ^ m ****** ^ ** ** ****** amide; any of R25 ', R26', R27 ', R28', R30 'and R31' can be joined together with any other R25 ', R26', R27 ', R28', R30 'and R31' to form part of a ring common, any germline R27 - R28 'can be combined to form a carbonyl; any adjacent R27-R31 can be joined to form an unsaturated portion; and further characterized because any group of Substituents R27-R31 can be combined to form a portion unsaturated fused, substituted or unsubstituted; and c) mixtures thereof. 10. The bleaching system in accordance with the claim 9, further characterized in that the zwitterionic organic catalyst compound is arylminium unzwitterionic of the formula [Xll] further characterized in that R25 is H or methyl, R26 is independently selected from H, alkyl and alkoxy, and by the radical represented by the formula: Zp "is -C02", -S03"or -OS03" and p is 1 or 2. 11. The bleaching system in accordance with the claim 10, further characterized in that said zwitterionic organic catalyst compound is unzwitterionic of arylminium of the formula [Xll] further characterized in that the radical represented by the formula: - T o, "2? Zp "is -C02", -S03"or -OS03" and p is 1, and To is selected from the group consisting of: »I fu 111 - 'fÉr -' * A ~ - A where q is an integer from 2 to 4; and each R29 is independently and individually selected from the group consisting of H and alkyl and substituted or unsubstituted aryl of linear or branched C-i-C-iß. 12. The bleaching system according to claim 1, further characterized in that said bleaching system further comprises a surfactant. 10 13. The bleaching system in accordance with the claim 1, further characterized in that said bleaching system further comprises an enzyme. • 14. The bleaching system in accordance with the claim 1, further characterized in that said bleaching system further comprises a chelating agent. . 15. The bleaching system in accordance with the claim 2, further characterized in that said source of peroxygen and said zwitterionic organic catalyst compound are present in said bleach system in a molar ratio not greater than 1: 1. 16. The bleaching system in accordance with the claim 1, created by the process comprising: a) providing a washing solution; and b) adding to said wash solution a bleaching composition comprising an amount of the zwitterionic organic catalyst compound. selected from the group consisting of: i) zwitterionics of aryliminium, which have a net charge of about +3 to about -3, which are represented by the formula [III]: [ll] wherein R5-R7 are independently selected from the substituted or unsubstituted radicals of the group consisting of radicals of H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, heterocyclic ring, silyl, nitrogen, halogen, cyano, sulfonate, alkoxy, keto, carboxylic, and carboalkoxy; The radical represented by the formula is also present in this formula: where Z'p "is covalently bonded to To, and Zp" is selected from the group consisting of -C02", -S03", -OS03", -S02" and -OS02"and p is 1, 2, or 3 To is selected from the group consisting of alkyl, cycloalkyl, aryl, alkaryl, aralkyl and substituted or unsubstituted, saturated or unsaturated heterocyclic ring, ii) zwitterionics of aryliminium, having a net charge of about +3 to about -3. , which are represented by the formula [IV]: [iv] wherein R5-R7 are independently selected from the substituted or unsubstituted radicals of the group consisting of radicals of H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, heterocyclic ring, silyl, nitrogen, halogen, cyano, sulfonate, alkoxy, keto, carboxylic, and carboalkoxy; The radical represented by the formula is also present in this formula: where Z'p is covalently bound to T'0, and Z'p "is selected from the group consisting of -C02", -S03", -OS03", -S02"and -OS02" and p is 1, 2; or 3; T'0 is selected from the group consisting of alkyl, cycloalkyl, aryl, alkaryl, aralkyl and substituted or unsubstituted, saturated or unsaturated heterocyclic ring; 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. 17. A method for washing fabrics requiring washing, characterized in that it comprises contacting said fabric with a washing solution having a bleaching system as claimed in claim 1. 18. The method according to claim 17, further characterized in that said fabric is a colored fabric. 19. The method according to claim 17, further characterized in that said method is carried out in a washing machine automatic 20. A bleaching system for washing fabrics requiring cleaning characterized in that it comprises: a) a source of peroxygen; and b) a zwitterionic organic catalyst compound selected from the group consists of: i) zwitterionics of aryliminium, which have a net charge of about +3 to about -3, which are represented by the formula [II]: [H] wherein R5-R7 are independently selected from the substituted or unsubstituted radicals of the group consisting of radicals of H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, heterocyclic ring, silyl, nitrogen, halogen, cyano, sulfonate, alkoxy, keto, carboxylic, and carboalkoxy; The radical represented by the formula is also present in this formula: -T - ^ where Zp "is covalently linked to To, and Zp" is selected from the group consisting of -C02", -S03", -OS03 ', -S02"and -OS02" and p is 1, 2; or 3; TO is selected from the group consisting of alkyl, cycloalkyl, aryl, alkaryl, aralkyl and substituted or unsubstituted, saturated or unsaturated heterocyclic ring; I) zwitterionics of oxaziridinium, which have a net charge of about +3 to about -3, which are represented by the formula [IV]: [IV] wherein R5-R7 are independently selected from the substituted or unsubstituted radicals of the group consisting of radicals of H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, heterocyclic ring, silyl, nitrogen, halogen, cyano, sulfonate, alkoxy, keto, carboxylic, and carboalkoxy; The radical represented by the formula is also present in this formula: - T "- - Z.eT where Z'p "is covalently linked to TO, and Z'p" is selected from the group consisting of -C02", -S03", -OS03", -S02" and -OS02"and p is 1, 2; or 3; TO is selected from the group consisting of alkyl, cycloalkyl, aryl, alkaryl, aralkyl and substituted or unsubstituted, saturated or unsaturated heterocyclic ring, iii) mixtures thereof, further characterized in that said source of peroxygen and said catalyst compound zwitterionic organic they are present in said bleaching system in a molar ratio not greater than 1: 1. 21. The bleaching system in accordance with the claim 20, further characterized in that said peroxygen source and said zwitterionic organic catalyst compound are present in said bleaching system in a molar ratio of about 30,000: 1 to about 10: 1. 22. The bleaching system in accordance with the claim 21, further characterized in that said peroxygen source and said zwitterionic organic catalyst compound are present in said bleaching system in a molar ratio of from about 10,000: 1 to about 50: 1. F 23. The bleaching system in accordance with the claim 22, further characterized in that said peroxygen source and said zwitterionic organic catalyst compound are present in said bleaching system in a molar ratio of from about 5,000: 1 to about 100: 1. 24. The bleaching system in accordance with the claim F 23, further characterized in that said peroxygen source and said zwitterionic organic catalyst compound are present in said bleaching system in a molar ratio of about 3,500: 1 to about 150: 1. * i laJ *********. * - ... . - ^ ..... a. -A, • - > - • *** - 25. A bleaching system for washing fabrics requiring cleaning characterized in that it comprises: a) a peracid; and b) a zwitterionic organic catalyst compound selected from the group consisting of: i) aryliminium zwitterionics, having a net charge of about +3 to about -3, which are represented by the formula [II]: [11] wherein R5-R7 are independently selected from the substituted or unsubstituted radicals of the group consisting of radicals of H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, heterocyclic ring, silyl, nitrogen, % halogen, cyano, sulfonate, alkoxy, keto, carboxylic, and carboalkoxy; The radical represented by the formula is also present in this formula: 15 - where Zp "- is covalently linked to To, and Zp" is selected from the group consisting of -C02", -S03", -OS03", -S02" and -OS02"and p is 1, 2; 3, T0 is selected from the group consisting of alkyl, cycloalkyl, aryl, alkaryl, aralkyl and substituted or unsubstituted, saturated or unsaturated heterocyclic ring, ii) zwitterionic oxaziridinium, having a net charge of about +3 to about -3, which are represented by the formula [IV]: * - A [ll] wherein R5-R7 are independently selected from the substituted or unsubstituted radicals of the group consisting of radicals of H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, heterocyclic ring, silyl, nitrogen, halogen, cyano, sulfonate, alkoxy, keto, carboxylic, and carboalkoxy; The radical represented by the formula is also present in this formula: - T o- "2? ^ w where Zp "- is covalently linked to TO, and Z'p" is selected from the group consisting of -C02", -S03", -OS03", -S02" and -OS02"and p 15 is 1, 2; or 3; TO is selected from the group consisting of alkyl, cycloalkyl, aryl, alkaryl, aralkyl and substituted or unsubstituted, saturated or unsaturated heterocyclic ring, iii) mixtures thereof, further characterized in that said peracid and said catalyst compound Zwitterionic organic are present in said bleaching system in a molar ratio not greater than 1: 1.