CZ2002723A3 - Washing detergent compositions with controlled release of their components and method for using such washing detergent compositions - Google Patents

Abstract

The present invention relates to a method for the controlled availability of formulation components, such as organic catalysts, into a wash solution. More particularly, the present invention relates to products and bleaching compositions containing such formulation components and laundry methods employing such formulation components.

Description

• ·· ····· · · ····

Washing preparations with controlled release of their components and method of using such washing preparations

Technical field

The present invention relates to a process for the controlled release of laundry detergent ingredients, such as organic catalysts, into a laundry detergent solution. In particular, the present invention relates to articles and bleaching compositions comprising these ingredients, and to methods for washing fabrics using such ingredients.

BACKGROUND OF THE INVENTION

Oxygen bleaches have become increasingly popular in recent years, both in household and personal hygiene products, as they facilitate stain and dirt removal. Bleaching agents are particularly advantageous for their stain removal capacity, the ability to clean fabrics with faded dirt, bleaching ability, disinfectant efficiency, as well as their ability to inhibit dye transfer. Oxygen bleaches have found particular application in detergent compositions, dishwasher detergents and solid surface cleaners. However, oxygen bleaching agents have somewhat limited efficacy. Some of their frequently occurring drawbacks are deteriorating the color of textile materials and damaging washing machines. In addition, oxygen-containing bleaches are extremely temperature-dependent. When used in a colder solution,

• ··········· bleaching effect lower. Temperatures above 60 ° C are usually required to achieve the proper performance of the oxygen bleach.

In order to solve the above-mentioned problem of temperature-dependency, a type of substances known as bleach activators has been developed. Bleach activators, which are usually perhydrolyzable acyl derivatives with leaving groups, such as oxybenzenesulfonates, react with the active oxygen species, usually hydrogen peroxide, or an anion thereof, to produce a more efficient peroxyacid oxidizing agent. This is a peroxyacid derivative which then oxidizes stains or impurities on the contaminated substrate. However, the bleach activators are also somewhat temperature dependent. Bleach activators are more effective in warm water at temperatures in the range of 40 to 60 ° C. At a water temperature below about 40 ° C, the peroxyacid derivative loses some of its bleaching effects.

As described in U.S. Patent Nos. 5,360,568, 5,360,569 and 5,370,826, to Madison et al., Attempts have been made to develop a bleach system effective at lower water temperatures. However, the dihydroisoquinolinium bleach-promoting agents described in these patents, in combination with peroxygen substances, are subject to undesirable decomposition, particularly in the presence of a laundry detergent component.

U.S. Patent Nos. 5,576,282 and 5,817,614 to Miracle et al. Disclose further attempts to develop organic catalyst bleaching systems that are effective at lower water temperatures and do not cause discoloration of fabrics.

However, delayed (controlled) release of ingredients such as the organic catalysts of the present invention are not described in the prior art.

In view of this, researchers have attempted to develop a method to mitigate the decomposition (or controlled decomposition) of an organic catalyst, particularly prior to contact with an oxidizable spot.

• · · ·

Thus, there remains a need for an effective method of releasing organic catalysts and compositions comprising organic catalysts which exhibit effective bleaching properties even at a lower temperature, are sufficiently stable to undesirable organic catalyst decomposition, and provide maximum peroxyacid efficacy at an early stage of the wash cycle.

SUMMARY OF THE INVENTION

BRIEF DESCRIPTION OF THE INVENTION

This object is achieved by the processes of the present invention, which are directed to methods of releasing organic catalysts, especially bleach-promoting compounds, bleaching agents, modified amines, modified amine oxides, sulfonimines, phosphonimines, Nacylimines and / or thiodiazole dioxides.

Examples of advantages provided by the organic catalyst release methods of the present invention are: excellent bleaching performance even at lower water temperatures; avoiding the decomposition of organic catalysts, which usually occurs during pre-blending prior to the addition of the fabric to be cleaned (i.e., stained fabrics); the possibility of bleaching fabrics with peroxyacid spots before the release of organic catalysts in order to maximize the concentration of peroxyacid when it affects stains on fabrics; reducing the peroxyacid concentration during bleaching, thereby reducing the rate of decomposition of the organic catalyst by the excess of peroxyacid present in the wash solution.

According to one aspect of the present invention, there is provided a method of washing soiled fabrics, wherein the controlled release of an organic catalyst into a wash solution comprising a fabric is defined in a manner defined below. Test Protocols I, II and / or III, in conjunction with or without a peroxygen source, preferably in conjunction with a peroxygen source.

According to another aspect of the present invention, a bleaching agent is provided upon release into a wash solution comprising an organic catalyst that becomes available (chemically available, i.e., capable of reacting with other compounds) by controlled release as defined in Test Protocols I, II and / or below. or III, in conjunction with or without a peroxygen source, preferably in conjunction with a peroxygen source.

According to yet another aspect of the present invention, there is provided an article comprising an organic catalyst that becomes available (chemically available, i.e., capable of reacting with other compounds) controlled release as defined in Test Protocols I, II and / or III below, and which upon release to the scrubbing solution causes bleaching with simultaneous inhibition of dye transfer, with or without a peroxygen source, preferably in conjunction with a peroxygen source.

According to yet another aspect of the present invention, there is provided an article comprising an organic catalyst that becomes available (chemically available, i.e., capable of reacting with other compounds) controlled release as defined in Test Protocols I, II and / or III below, and which upon release to the washing solution causes bleaching in conjunction with or without a peroxygen source, preferably in conjunction with a peroxygen source, further comprising instructions for using an organic catalyst to clean the soiled fabric, wherein the instructions for use include the step of releasing an article comprising an organic catalyst, in conjunction with or without a source of peroxygen, into a wash solution comprising a fabric in such a way that at least most of said organic catalyst is released by means of a release agent into the The washing solution after inserting the fabric into the washing solution.

Surprisingly, it has been found that an organic catalyst that becomes available (chemically available, i.e. capable of reacting with other compounds) in a controlled release as defined by the test protocols I, II and / or III described below, in a wash solution containing a peroxygen source and soiled fabric it has a higher bleaching capability compared to an organic catalyst that is readily available in the wash solution (meaning chemically available, i.e. capable of reacting with other compounds).

By controlling the availability of the organic catalysts by the process of the invention in a wash solution containing a peroxygen source and fabric by controlled release as defined by Test Protocols I, II and / or III below, it causes the peroxygen / peroxyacid source to cause bleaching during the initial portion of the wash. cycle, when its concentration is highest, while at the same time preventing exposure of these organic catalysts to the highest concentration of peroxygen / peroxyacid, thereby reducing the decomposition of these organic catalysts. Organic catalysts may become available (chemically available, i.e., capable of reacting with other compounds, in this case peroxyacids), in a controlled release manner as defined in Test Protocols I, II and / or III below. Once the organic catalysts are available in the wash solution, they can react with the remaining available peroxyacids to form oxygen transfer agents (bleaching agents) that can oxidize stains. As a result, the peroxygen / peroxyacid source and organic catalyst can be optimized.

Without wishing to be bound by any theory, it is believed that organic catalysts, particularly bleach-promoting compounds, react with a source of peroxygen, preferably a peroxyacid, to form oxygen transfer agents (bleaching agents). Different degradation methods can lead to the decomposition of either bleach-promoting compounds or oxygen transfer agents, leading to decomposition. · «· ·

A product which can also react with a peroxygen / peroxyacid source.

Controlling the availability of organic catalysts and thus controlling the contact time between organic catalysts by any source of peroxygen / peroxyacids in the wash solution allows these peroxygen / peroxyacids that are present in the wash solution to have maximum bleaching effect on selected spots on fabrics before come into contact with organic catalysts.

Under normal washing conditions, oxygen in the form of a peroxyacid is often present at the end of the wash cycle because the peroxyacid reacts more slowly with stains than the oxygen transfer agent. At the end of the wash cycle, the concentration of available oxygen is lower, resulting in a lower degree of bleaching as well as depletion of the remaining peroxyacid after the wash. During the wash cycle (after perhydrolysis), the concentration begins to decrease as a result of peroxyacid bleaching of the stains. The peroxyacid bleaching is a relatively slow process (from a kinetic point of view, especially at a lower wash bath temperature), and therefore it is necessary to increase the washing time and peroxyacid concentration to achieve the maximum degree of stain removal. It is important that the oxidizable spots can be treated with high concentrations of peroxyacids, and then the organic catalyst can act on the remaining oxidizable spots. It is known that peroxyacids react rapidly with organic catalysts, and the bleaching agents thus formed react rapidly with oxidizable spots.

Accordingly, it is an object of the present invention to provide a controlled release organic catalyst release method as defined in Test Protocols I, II and / or III which achieve improved performance even at lower wash solution temperatures while reducing unwanted peroxyacid decomposition and maximizing efficiency peroxyacids at the beginning of the wash cycle; a method for washing contaminated fabrics with controlled release of the organic catalyst into a fabric-containing washing solution according to the method defined in Test Protocols I described below,

II and / or III; a bleaching composition comprising an organic catalyst that is sustained release by controlled release as defined in test protocols I, II and / or III described below; and an article comprising an organic catalyst that is gradually released into a wash solution already containing the soiled fabric by controlled release as defined in Test Protocols I, II and / or III described below. These and other objects, features and advantages of the invention will be apparent to those skilled in the art from the following description and claims.

Unless otherwise stated, all concentrations, ratios and proportions herein are by weight. All documents cited herein are hereby incorporated by reference.

DETAILED DESCRIPTION OF THE INVENTION

The present invention describes novel and highly useful methods of releasing organic catalysts (bleach enhancers, bleaching agents, modified amines, modified amine oxides, sulfonimines, phosphonimines, thiodiazole dioxides, and mixtures thereof) by controlled release into a wash solution containing a soiled fabric as defined in test protocols I, II and / or III described below.

The controlled release of the organic catalysts of the present invention achieves improved bleaching performance even in low temperature processes while mitigating (or controlling) undesirable decomposition. Consequently, the organic catalysts and methods of their use according to the present invention are excellent in reducing their unwanted decomposition, resulting in increased catalytic activity and consequently improved bleaching effect. Organic Catalysts and Methods of Their Use According to the Invention of Organic Catalysts The present invention further maximizes peroxyacid efficiency at the beginning of the wash cycle, thereby increasing overall efficiency. The controlled release methods defined in the test protocols I, II and / or III described below allow the organic catalysts to be chemically available, i.e. capable of reacting with other compounds in the wash solution in a controlled manner (i.e., at a defined point in time). lower than the total amount of organic catalyst) and not at once (i.e., the total amount of organic catalyst is available at a defined time).

Definition

To become available as used herein means to become chemically available, i.e., capable of reacting with other compounds.

The term peroxygen source, as used herein, means materials that produce eroxygenic substances and which may be, inter alia, peroxygenic substances themselves. Examples of such agents are bleach activators, peroxyacids, percarbonates, peroxyborates, hydrogen peroxide, bleach enhancers, and / or bleaching agents (e.g., oxaziridinium compounds).

As used herein, a peroxygen compound means peroxyacids and peroxides (e.g., hydrogen peroxide, alkyl hydroperoxides and the like).

The term "peroxyacid" as used herein means various peroxyacids such as percarboxylic acids and / or peroxosulfuric acid (trademark OXONE), and salts thereof.

The methods of releasing the organic catalysts of the present invention, which are carried out in conjunction with or without conventional peroxygen bleaching agents, preferably in conjunction with conventional peroxygen bleaching agents, provide the aforementioned increased elevation. ·· 9 9 9 9 9 9 bleaching efficiency and significantly reduce unwanted decomposition.

Organic catalysts

Examples of organic catalysts such as bleach activators and bleaching agents are described in U.S. Patent Nos. 5,041,232, 5,045,223, 5,047,163, 5,310,925, 5,413,733,

360 568, 5 482 515, 5 550 256, 5 360 569, 5 478 357, 5 370 826

442 066, 5 576 282, 5 760 222, 5 753 599, 5 652 207 and 5 817 614, in published international patent applications WO 98/23602,

WO 95/13352, WO 95/13353, WO 95/13351, WO 97/06147 and WO 98/23717, and in EP 728 182.

The organic catalysts of the present invention and bleaching compositions (products) containing such organic catalysts that are particularly suitable for use in the processes of the present invention are organic catalysts and preparations containing such organic catalysts that meet the conditions of Test Reports I, II and / or III described below.

Preferably, the organic catalysts of the invention are bleach-promoting compounds based on imino compounds, modified amines, modified amine oxides, sulfonimines, phosphinimines, thiodiazole dioxides, and mixtures thereof.

I. Bleach Promotion Compounds

The bleach enhancing compounds, preferably the bleach enhancing imine compounds of the present invention are aryliminium cations, aryliminium polyions having a charge in the range of +3 to -3, and aryliminium zwitterions, with a charge in the range of +3 to -3.

Preferred organic catalysts of the present invention and for use in the bleaching compositions of the present invention are aryliminium zwitterionic bleach enhancers or corresponding oxaziridinium bleaching agents because, unlike aryliminium cations and / or oxaziridinium cations, zwitterions are effective whitening agents without undesirably damaging the colors on fabrics.

Aryliminium cations and polyions

Aryliminium cations and aryliminium polyions having a charge in the range of +3 to -3 have the general formula [I]:

R [I] wherein R ² and R ³ are independently selected from H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, heterocyclic compound residue, silyl, nitro, halo, cyano, sulfo, alkoxy, keto, carboxy and carboalkoxy; R ¹ and R ⁴ are selected from substituted or unsubstituted, saturated or unsaturated groups selected from the group consisting of H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, heterocyclic compound residue, silyl, nitro, halo, cyano, alkoxy, keto groups carboalkoxy; X 'is a suitable charge-balancing proion, preferably compatible with a bleaching agent; and v is 1 to 3.

Preferably, aryliminium cations and aryliminium polyions having a charge in the range of +3 to -3 have the general formula [XI]:

[Xi] wherein m is 1 to 3 when G is present, and m is 1 to 4 when G is absent; n is an integer from 0 to 4; any of R ²⁰ is independently selected from substituted or unsubstituted groups selected from the group consisting of H, alkyl, cycloalkyl, aryl, fused ring aromatic, heterocyclic ring, fused ring heterocycle, nitro, halo, cyano , sulfo, alkoxy, keto, carboxy, and carboalkoxy, and the combination of any two R ²⁰ vicinal substituents may produce a fused-ring aromatic compound, a fused-ring carbocyclic compound, or a fused-ring heterocyclic compound; R ¹⁸ may be a substituted or unsubstituted group selected from the group consisting of H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, heterocyclic compound residue, silyl, nitro, halo, cyano, sulfo, alkoxy, keto, carboxy, and carboxy; R ¹⁹ is a group selected from substituted or unsubstituted, saturated or unsaturated groups which are H, alkyl, cycloalkyl, alkaryl, aralkyl, and the heterocyclic compound residue; the group G is selected from the group consisting of: 1) -O-; 2) -N (R ²³⁾ -; and 3) -N (R ²³ R ²⁴ ) -; R ²¹ -R ²⁴ are substituted or unsubstituted groups independently selected from the group consisting of H, oxygen, straight or branched C 1 -C 12 alkyl, alkylenes, alkoxy, aryl, alkaryl, aralkyl, cycloalkyl and heterocyclic radicals; provided that any one of R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ -R ²⁴ may be associated with any other R ¹⁸ , R ¹⁹ ; R ²⁰ ; R ²¹ -R ²⁴ to form part of a common cycle; any geminal groups R ²¹ -R ²² may combine with each other to form carbonyl; any of the vicinal groups R ²¹ -R ²⁴ may combine to form a double bond; and at the same time any of the groups R ²¹ -R ²⁴ may combine with each other to form a substituted or unsubstituted fused unsaturated group; X 'is a suitable charge-compensating counterion, preferably a bleach-compatible counterion; and v is a natural number of 1 to 3.

More preferably, the aryliminium cations and aryliminium polyions are those charged in the range of +3 to -3 of the general formula [XI] wherein R ¹⁸ is H or methyl and R ¹⁹ is H or substituted or unsubstituted saturated or unsaturated C 1 -C 11 alkyl.

b. Aryliminium zwitterions

Aryliminium zwitterions having a charge in the range of +3 to -3 have the general formula [II]:

R '[H] wherein R ⁵ -R ⁷ are independently selected from substituted or unsubstituted groups selected from the group consisting of H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, heterocyclic compound residue, silyl, nitro, halogen, cyano, sulfo , alkoxy, keto, carboxy, and carboalkoxy; they also include a group of the formula;

where Z _p is covalently bonded to T _o, and is selected from the group consisting of -CC> 2-, -SO 3, -OSO 3, -SO 2 -0S0 ₂ and p is either 1, 2 or 3; the group T _o is selected from the group consisting of substituted or unsubstituted saturated or unsaturated alkyl, cycloalkyl, aryl, alkaryl, aralkyl, and the rest of the heterocyclic compound.

Preferably, the aryliminium zwitterions having a charge in the range of +3 to -3 have the general formula [XII]:

wherein m is 1 to 3 when G is present, and m is 1 to 4 when G is absent; n is an integer from 0 to 4; each R ²⁶ is independently selected from substituted or unsubstituted groups selected from the group consisting of H, alkyl, cycloalkyl, aryl, fused ring aromatic, heterocyclic ring, fused ring heterocycle, nitro, halo, cyano , sulfo, alkoxy, keto, carboxy, and carboalkoxy, and any two vicinal R ²⁶ substituents can combine to form the remainder of the condensed ring aromatic compound, the fused-ring carbocyclic compound, or the fused-ring heterocyclic compound; R ²⁵ may be a substituted or unsubstituted group selected from the group consisting of H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, heterocyclic compound residue, silyl, nitro, halo, cyano, sulfo, alkoxy, keto, carboxy, and carboxy; they also include a group of the general formula:

wherein the group Z _p is covalently bonded to the group To and is selected from the group consisting of -CO ₂ -, -SO ₃ , -OSO ₃ , -SO ₂ - and -OSO ₂ '; and p is either 1, 2 or 3; the group T _o is selected from the group consisting of:

R ²⁹

I - (C) q - 29 wherein q is a natural number of 1 to 8; R ²⁹ is independently selected from substituted or unsubstituted groups selected from the group consisting of unbranched or branched H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, alkylene, heterocyclic compound residue, alkoxy, arylcarbonyl, carboxyalkyl and amide groups; the group G is selected from the group consisting of: 1) -O-; 2) -N ( ^R30 ) -; and 3) N (r ³⁰ r ³¹ ) -; r ²⁷ , r ² % r ³⁰ _and r ³¹ are substituted or unsubstituted groups independently selected from the group consisting of H, oxygen, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, alkylenes, heterocyclic compound, alkoxy, arylcarbonyl, carboxyalkyl, and amide groups; any of R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , R ³⁰ and R ³¹ may be joined to any other R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , R ³⁰ and R ³¹ to form part of a common cycle; any geminal groups R ²⁷ -R ²⁸ may combine with each other to form carbonyl; any of the vicinal R ²⁷ -R ³¹ groups may join to form a double bond; and at the same time any of the groups R ²⁷ -R ³¹ may combine with each other to form a substituted or unsubstituted fused unsaturated group.

More preferably, the zwitterionic aryliminium ions are those having a range of +3 to -3 of the general formula [ XI] wherein R ²⁵ is H or methyl and R ²⁵ is H or methyl, and in the group represented by the general formula:

- T _o - wherein Z _p 'is -CO ₂ , -SO 3' or -OSO 3 and _p is 1 or 2, Z _p 'is more preferably -SO 3' or -OSO 3 ^- and _p is 1.

II. Modified amines and / or amine oxides

The modified amines and / or amine oxides of the present invention are modified amines and modified amine oxides having a charge in the range of +3 to -3.

a. modified amines

The modified amines of the invention have the general formulas [V] and [VI]:

[V] [VI] wherein R ⁹ -R ¹⁰ are independently selected from substituted or unsubstituted groups selected from the group consisting of H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, heterocyclic compound residue, silyl, nitro, halo, cyano; Sulfo, alkoxy, keto, carboxy and carboalkoxy groups and positive or negative charge groups; when R ⁸ and R ¹¹ are present, they are a group selected from the group consisting of substituted or unsubstituted saturated or unsaturated H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, heterocyclic compound residue, silyl, nitro, halo, cyano , alkoxy, keto and carboalkoxy groups and positive or negative charge groups; R ¹² is a leaving group whose protonated form has a pK _{and a} value (in aqueous medium) between 37> pK _and >-2; wherein, when R ⁸ -R ¹² groups are present, they may combine with each other to form a fused ring aromatic compound, a fused ring carbocyclic compound, or a fused ring heterocyclic compound; and also includes a group of the general formula:

It

where Z _p- is covalently bonded to T _o, and is selected from the group consisting of -CO2-, -S0 _3, -OSO 3 * -SO ₂ and -OSO ₂ ^_ p is either 1, 2 or 3; , T _o is selected from the group consisting of substituted or unsubstituted, saturated or unsaturated alkyl, cycloalkyl, aryl, alkaryl, aralkyl, and heterocyclic ring.

Preferably, the modified amines have the general formulas [XV] and [XVI]:

[XV]

[xvi] wherein m is 1 to 3 when G is present, and m is 1 to 4 when G is absent; and n is an integer from 0 to 4; R ³⁴ is a group selected from the group consisting of substituted or unsubstituted saturated or unsaturated hydroxy, hydroperoxy, alkoxy, peralkoxy, carboxy, percarboxy, sulfo, and persulfo; R ³⁵ is independently selected from substituted or unsubstituted groups selected from the group consisting of H, alkyl, cycloalkyl, aryl, fused ring aromatic, heterocyclic ring, fused ring heterocycle, nitro, halo, cyano, sulfo , alkoxy, keto, carboxy, and carboalkoxy, and any two R ³⁵ vicinal substituents may combine to form the remainder of the fused-ring aromatic compound, the fused-ring carbocyclic compound, or the fused-ring heterocyclic compound; R ³³ may be a substituted or unsubstituted group selected from the group consisting of H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, heterocyclic compound residue, silyl, nitro, halo, cyano, sulfo, alkoxy, keto, carboxy, and carboxy; R ³³ may be a substituted or unsubstituted saturated or unsaturated group selected from the group consisting of H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, heterocyclic compound moiety, and also includes a group of the formula:

wherein the group Z _p 'is covalently bonded to a group To and is selected from the group consisting of -CO ₂ -, -SO ₃ ', -OSO ₃ , -SO ₂ and -SO ₂ ', • · · · · and ρ is either 1 , 2 or 3; the group T _o is selected from the group of groups consisting of:

R ³⁸

AND.

- (C) q—

R ³⁸ wherein q is a natural number of 1 to 8; R ³⁸ is independently selected from substituted or unsubstituted groups selected from the group consisting of straight or branched H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, alkylene, heterocyclic compound residue, alkoxy, arylcarbonyl, carboxyalkyl amide groups; the group G is selected from the group consisting of: 1) -O-; 2) -N (R ³⁹ ) -; and 3) -N (R ³⁹ R ⁴⁰ ) -; R ³⁶ , R ³⁷ , R ³⁹ and R ⁴⁰ are substituted or unsubstituted groups independently selected from the group consisting of H, oxygen, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, alkylenes, heterocyclic compound, alkoxy, arylcarbonyl, carboxyalkyl, and amide groups; any of R ³² , R ³³ , R ³⁴ , R ³⁵ , R ³⁶ , R ³⁷ , R ³⁹ and R ⁴⁰ may be associated with any other R ³² , R ³³ , R ³⁴ , R ³⁵ , R ³⁶ , R ³⁷ , R ³⁹ and R ⁴⁰ to form part of a common cycle; any geminal groups R ³⁶ R ³⁷ may combine with each other to form carbonyl; any of the vicinal groups R ³⁶ , R ³⁷ , R ^39, and R ⁴⁰ may combine to form a double bond; and at the same time any of R ³⁶ , R ³⁷ , R ³⁹ and R ⁴⁰ may combine with each other to form a substituted or unsubstituted fused unsaturated group.

Examples of such modified amines are those with R ³⁴ selected from the group consisting of substituted or unsubstituted saturated or unsaturated hydroxy, hydroperoxy, alkoxy, peralkoxy, carboxy, percarboxy, sulfo, and persulfo groups.

Preferably, R ^{34 is} selected from the group consisting of substituted or unsubstituted saturated or unsaturated hydroxy, hydroperoxy, alkoxy and peralkoxy groups. The following are examples of such modified amines of the present invention, but these examples are not intended to limit or otherwise define the subject matter of the present invention.

More preferably, in the modified amines represented by the general formulas [XV] and [XVI], the group R ^{34 is a} leaving group whose protonated form has a pK _{and a} value (in aqueous medium) falling within the following ranges: 30> pK _and >0; more preferably 23 > pK _and > 3; even more preferably 21 > pK _and > 9; most preferably 17> pK _and > 11.

Preferably, in the modified amines represented by the general formulas [XV] and [XVI], R ^{12 is} selected from the group consisting of substituted or unsubstituted saturated or unsaturated hydroxy, hydroperoxy, alkoxy and peralkoxy groups. More preferably, in the amines represented by the general formulas [XV] and [XVI], said R ¹² group is selected from the group consisting of hydroxy or hydroperoxy.

Even more preferred modified amines of formulas [XV] and [XVI] are outside of these modified amines having a charge of +1 to 1 wherein R ³² is H or Me; R ³⁴ is a group selected from the group consisting of hydroxy and hydroperoxy groups; R ³⁵ is independently selected from the group consisting of H, alkyl, nitro, halo, sulfonato, alkoxy, and carboalkoxy radicals and / or Z _p- is _-CO2-, -SO 3 or OSO _third

The R ^{12 group} in these modified amines is an leaving group (LG) whose protonated form has a pK _{and a} value (in aqueous medium) that falls within the following range: 37> pK _and >-2; preferably 30 > pK _and > 0; more preferably 23 > pK _and > 3; even more preferably 17 > pK _and > 11; most preferably the group R ^LZ leaving group selected from the group consisting of substituted or unsubstituted, saturated or unsaturated hydroxy, perhydroxy, alkoxy and peralkoxy radicals; and any of R ⁸ -R ¹² may combine to form a fused ring aromatic compound, a fused ring carbocyclic compound, or a fused ring heterocyclic compound.

b. modified amine oxides

The modified amine oxides of the present invention have the general formulas [VII] to [X]:

wherein R ⁸ -R ¹⁰ are independently selected from substituted or unsubstituted groups selected from the group consisting of H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, heterocyclic ring radical, silyl, nitro, halo, cyano, sulfo, alkoxy, keto, carboxy and carboalkoxy groups and positive or negative charge groups; R ⁿ is a group selected from the group consisting of substituted or unsubstituted, saturated or unsaturated H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, heterocyclic ring, silyl, nitro, halo, cyano, sulfonato, alkoxy, keto, carboxylic, and groups carrying positive or negative charges; R ¹² is a leaving group whose protonated form has a pK _{and a} value (in aqueous medium) between 37> pK _and >2; wherein, when R ⁸ -R ¹² groups are present, they may combine with each other to form a fused ring aromatic compound, a fused ring carbocyclic compound, or a fused ring heterocyclic compound; and also includes a group of the general formula:

where Z _p is covalently bonded to T _o is selected from the group consisting of -C 0 ~ _2, -SO ₃ '-OSO _3, -SO ₂ and -OSO ₂ and p is either 1, 2 or 3; , T _o is selected from the group consisting of substituted or unsubstituted, saturated or unsaturated alkyl, cycloalkyl, aryl, alkaryl, aralkyl, and heterocyclic ring.

Preferably, in the modified amine oxides of formulas [VII] to [X], the R ¹² group is a leaving group whose protonated form has a pK _{and a} value (in aqueous medium) that falls within this group. · · »·« «« «« «* * · · · · · · · · ··· ·· ··· range: 30>pKa>0; more preferably 23 > pKa >3; even more preferably 21 > pK _and > 9; most preferably 17 > pKa > 11.

Preferably, in the modified amine oxides of formulas [VII] to [X], the group R ^{12 is} selected from the group consisting of substituted or unsubstituted saturated or unsaturated hydroxy, hydroperoxy, alkoxy and pera-oxy groups. More preferably, in the modified amine oxides of formulas [VII] to [X], R ^{12 is} selected from the group consisting of hydroxy or hydroperoxy groups.

The modified amine oxides also have the general formulas [XVII] to [XX]:

wherein m is 1 to 3 when G is present, and m is 1 to 4 when G is absent; n is an integer from 0 to 4; R ³⁴ is a group selected from the group consisting of substituted or unsubstituted saturated or unsaturated hydroxy, hydroperoxy, alkoxy, pera-oxy, carboxy, percarboxy, sulfo, persulfo; the group R ³⁵ is independently selected from substituted or unsubstituted groups selected from the group consisting of H, alkyl, cyclo, β, β, β, β, β, β, β, β, β, and β; Λ alkyl, aryl, fused-ring aromatic, heterocyclic, fused-ring, nitro, halo, cyano, sulfo, alkoxy, keto, carboxy, and carboalkoxy groups, and any two R ³⁵ vicinal substituents may combine to form the remainder of the fused-ring aromatic compound, the fused-ring carbocyclic compound, or the fused-ring heterocyclic compound; R ³² may be a substituted or unsubstituted group selected from the group consisting of H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, heterocyclic compound residue, silyl, nitro, halo, cyano, sulfo, alkoxy, keto, carboxy; R ³³ may be a substituted or unsubstituted saturated or unsaturated group selected from the group consisting of H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, heterocyclic compound moiety, and also includes a group of the formula:

_T ₀ —Z?

where Z _p is covalently bonded to T _o, and is selected from the group consisting of -C 0 ₂ "<-SO _3, -OSO 3, -S0 _2" and -OCS _2, and p is either 1, 2 or 3; _the group T is selected from the group of substances of the general formula:

R ³⁸

I - (C) q - R ³⁸ wherein q is a natural number of 1 to 8; R ³⁸ is substituted ·

·· «·· * · *« 4: 4 4 * 4 • 4 «4 4 * to 4 * · * to» 49 · 4 • 44 »· 4 · 4 ·

Or an unsubstituted group selected from the group consisting of H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, alkylene, heterocyclic compound residue, alkoxy, arylcarbonyl, carboxyalkyl and amide groups; the group G is selected from the group consisting of: 1) -O-; 2) -N (R ³⁹ ) -; and

3) -N (R ³⁹ R ⁴⁰ ) R ³⁶ , R ³⁷ , R ³⁹ and R ⁴⁰ are substituted or unsubstituted groups independently selected from the group consisting of H, oxygen, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, alkylene, radical heterocyclic compounds, alkoxy groups, arylcarbonyl groups, carboxyalkyl groups and amide groups; any of R ³² , R ³³ , R ³⁴ , R ³⁵ , R ³⁶ , R ³⁷ , R ³⁹ and R ⁴⁰ may be associated with any other R ³² , R ³³ , R ³⁴ , R ³⁵ , R ³⁶ , R ³⁷ , R ³⁹ and R ⁴⁰ to form part of a common cycle; any geminal groups R ³⁶ -R ³⁷ may combine with each other to form carbonyl; any of the vicinal groups R ³⁶ , R ³⁷ , R ³⁹ and R ⁴⁰ may combine to form a double bond; and at the same time any of R ³⁶ , R ³⁷ , R ³⁹ and R ⁴⁰ can combine with each other to form a substituted or unsubstituted fused unsaturated group;

Examples of such modified amine oxides are those with R ³⁴ selected from the group consisting of substituted or unsubstituted saturated or unsaturated hydroxy, hydroperoxy, alkoxy, peralkoxy, carboxy, percarboxy, sulfo, and persulfo groups.

Preferably, R ^{34 is} selected from the group consisting of substituted or unsubstituted saturated or unsaturated hydroxy, hydroperoxy, alkoxy and peralkoxy groups.

OH

More preferably, in the modified amine oxides of formulas [XVII] and [XX], the group R ^{34 is a} leaving group whose protonated form has a pK _{and a} value (in aqueous medium) in the range: 30> pK _and >0; more preferably 23 > pK _and > 3; even more preferably 21 > pK _and > 9; most preferably 17> pK _and > 11.

Preferably, in the modified amine oxides of formulas [XVII] to [XX], R ^{34 is} selected from the group consisting of substituted or unsubstituted saturated or unsaturated hydroxy, hydroperoxy, alkoxy and peralkoxy groups. More preferably, in the modified amine oxides of formulas [XVII] to [XX], the group R ^{34 is} selected from the group consisting of hydroxy or hydroperoxy groups.

Even more preferred modified amine oxides of formulas [XVII] to [XX] are modified amine oxides of charge +1 to -1 wherein R ³² is H or Me; R ³⁴ is a group selected from the group consisting of hydroxy and hydroperoxy groups; R ³⁵ are independently selected from the group consisting of H, alkyl, nitro, halo, sulfonato, alkoxy, carboxyl and carboalkoxy radicals and / or Z _p "is -CO 2", -SO ₃ or -OSO 3.

The group R ¹² in the modified amine oxides is a leaving group (LG) whose protonated form has a pK _{and a} value (in aqueous medium) which falls within the following range: 37> pK _and >-2; preferably 30 > pK _and > 0; more preferably 23 > pK _and > 3; even more preferably 17 > pK _and > 11; Most preferably, R ^{12 is a} leaving group selected from the group consisting of substituted or unsubstituted saturated or unsaturated hydroxy, hydroperoxy, alkoxy and peralkoxy groups; and any of R ⁸ to R ¹² may combine with each other to form a fused ring aromatic compound, a fused ring carbocyclic compound, or a fused ring heterocyclic compound.

Examples of suitable modified amine compounds of the invention (modified amines and / or modified amine oxides) (and pK _and proton forms of R ¹² (in aqueous medium)) are compounds of the general formula:

ρΚ _α = -0.25 pK _and = 4.76

pX _to ~ 13 pX _to ~ 10.5 pK _to ~ 11.6 • · ··· · · · · · «

The modified amino compounds of the present invention, acting in conjunction with the peroxygen source, provide a very effective bleach system. Peroxygen sources are well known in the art and the peroxygen source used in the methods of the invention may be any well known sources thereof, including peroxygen compounds, as well as compounds that provide an effective amount of peroxygen in situ when used by the consumer. Peroxygen sources can be, but are not limited to, hydrogen peroxide, in situ formation of peroxyacid anions formed by the reaction of a hydrogen peroxide source and a bleach activator, a peroxyacid compound or a mixture of suitable peroxygen sources. It will be apparent to one skilled in the art that other sources of peroxygen may be used without departing from the scope of the present invention. Preferably, the source of peroxygen is an organic and / or inorganic peroxyacid.

IV. Sulfonimines, phosphonimines, N-acylimines and thiodiazole dioxides

The sulfonimines, phosphonimines, N-acylimines and thiodiazole dioxides of the present invention are compounds of formulas [XXIa], [XXIb], [XXII], and [XXII]; [XXIII]:

[XXIIa] [XXII] [XXIII] wherein R ⁴¹ -R ⁴⁴ , if present, are independently selected from substituted or unsubstituted saturated or unsaturated groups selected from the group consisting of H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, heterocyclic compound, silyl, nitro, halo, cyano, sulfo, alkoxy, keto, carboxy, and carboalkoxy; wherein any of the R ⁴¹ -R ⁴⁴ groups may be linked to any other R ⁴¹ -R ^{44 group} to form part of a common cycle, including the remainder of the aromatic compound with fused cycles, the remainder of the carbocyclic compound with fused cycles or the remainder of the heterocyclic compound with fused cycles.

II. Bleaching agents

Bleaching agents (oxaziridinium compounds, oxaziridines) can also be used directly in the processes of this invention. The bleaching agents of the present invention are oxaziridinium cations, oxaziridinium polyions having a charge in the range of +3 to 3, oxaziridinium zwitterions having a charge in the range of +3 to -3, oxaziridine sulfonimine derivatives, oxaziridine phosphonimine derivatives, oxaziridine dioxide derivatives thiodiazoles and mixtures thereof.

Organic catalysts, especially aryliminium cations, aryliminium polyions, aryliminium zwitterions, sulfonimines, phosphonimines, and thiodiazole dioxides are characterized by enhanced bleaching efficiency in conjunction with the peroxygen source. Without wishing to be bound by any theory, it is believed that organic catalysts react with a source of peroxygen to produce more active bleaching agents, which are quaternary oxaziridinium and / or oxaziridine compounds, as illustrated by the following examples of the reactions of the compounds:

The oxaziridinium and / or oxaziride compounds may have higher or more desirable activity at lower temperatures than the peroxygen agent.

Oxaziridinium cations and polyions

Oxaziridinium cations and polyions having a charge in the range of +3 to -3 have the general formula [III]:

[III] • wherein R ² ', R ³ ' are independently selected from substituted or unsubstituted groups selected from the group consisting of H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, heterocyclic compound residue, silyl, nitro, halo, cyano , sulfo, alkoxy, keto, carboxy, and carboalkoxy; R ¹ 'and R ⁴ ' are selected from the group consisting of substituted or unsubstituted saturated or unsaturated, H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, heterocyclic compound residue, silyl, nitro, halo, cyano, alkoxy, keto, and keto groups; carboalkoxy; and X 'is a suitable charge-compensating counterion, and preferably a bleach-compatible counterion; and v is a natural number of 1 to 3.

Preferably, oxaziridinium cations and polyions having a charge in the range of +3 to -3 have the general formula [XIII]:

wherein m is 1 to 3 when G is present, and m is 1 to 4 when G is not present; n is an integer from 0 to 4; each of R ²⁰ 'is independently selected from substituted or unsubstituted groups selected from the group consisting of H, alkyl, cycloalkyl, aryl, fused ring aromatic, heterocyclic ring, fused ring heterocycle, nitro, halogen, cyano, sulfo, alkoxy, keto, carboxy and carboalkoxy, and any two vicinal groups

R ²⁰ 'may combine with each other to form a fused ring aromatic compound, a fused ring carbocyclic compound, or a fused ring heterocyclic compound; R ¹⁸ 'may be a substituted or unsubstituted group selected from the group consisting of H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, heterocyclic compound residue, silyl, nitro, halo, cyano, sulfo, alkoxy, keto, carboxy, and carboxy; R ¹⁹ 'may be a substituted or unsubstituted saturated or unsaturated group selected from the group consisting of H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, and the heterocyclic compound moiety, G is selected from the group consisting of: 1) -O-; 2) -N (R ²³ ') -; and 3) -N (R ²³ 'R ²⁴ ') -; R ²¹ '-R ²⁴ ' are substituted or unsubstituted groups independently selected from the group consisting of H, oxygen, straight or branched C 1 -C 12 alkyls, alkylenes, alkoxy, aryl, alkaryl, aralkyl, cycloalkyl and heterocyclic radicals; provided that any one of R ¹⁸ ' _of R ¹⁹ ', R ²¹ 'R ²⁴ ' may be linked to any other R ¹⁸ ', R ¹⁹ ', R ²¹ '-R ²⁴ ' to form part of a common cycle; any geminal groups R ²¹ '-R ²² may combine with each other to form carbonyl; any of the vicinal groups R ²¹ -R ²⁴ 'may be joined to form a double bond; and at the same time any of the groups R ²¹ '-R ²⁴ ' can combine with each other to form a substituted or unsubstituted fused unsaturated group; and at the same time any of the groups R ²¹ -R ²⁴ may combine with each other to form a substituted or unsubstituted fused unsaturated group; X is a suitable charge-balancing counterion, preferably a bleach-compatible counterion; and v is a natural number of 1 to 3.

More preferably, the oxaziridinium cations and oxaziridinium polyions having a charge in the range of +3 to -3 of the compound of formula [XIII] are those wherein R ¹⁸ 'is H or methyl and R ¹⁹ is H or substituted or unsubstituted saturated or unsaturated alkyl and cycloalkyl.

b. Oxaziridinium zwitterions

Oxaziridinium zwitterions having a charge in the range of +3 to -3 have the general formula:

R ⁵ l! L © γθ

Toz · [IV] wherein R ⁵ 'to R ⁷ ' are independently selected from substituted or unsubstituted groups selected from the group consisting of H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, heterocyclic compound residue, silyl, nitro, halo, cyano , sulfo, alkoxy, keto, carboxy, and carboalkoxy; they also include a group of the general formula:

—T

wherein the group ζ'ρ "is covalently bonded to the group t ' _o and is selected from the group consisting of -CO ₂ . -SO ₃ ', -OSO ₃ , -SO ₂ and -OSO ₂ '; p is either 1, 2 or 3; the group τ'ο is selected from the group consisting of substituted or unsubstituted saturated or unsaturated alkyl, cycloalkyl, aryl, alkaryl, aralkyl and the rest of the heterocyclic compound.

Preferably, the oxaziridinium zwitterions having a charge in the range of +3 to -3 of the compound of general formula [XIV]:

₇ , θ where m is 1 to 3 when G is present, and m is 1 to 4 if G is not present; n is an integer from 0 to 4; any of R ²⁶ 'is independently selected from substituted or unsubstituted groups consisting of H, alkyl, cycloalkyl, aryl, fused ring aromatic, heterocyclic ring, fused ring heterocycle, nitro, halo, cyano, sulfo, alkoxy, keto, carboxy, and carboalkoxy groups, and any two vicinal R ²⁶ 'groups may combine to form a fused ring aromatic compound, a fused ring carbocyclic compound, or a fused ring heterocyclic compound; R ²⁵ 'may be a substituted or unsubstituted group selected from the group consisting of H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, heterocyclic compound residue, silyl, nitro, halo, cyano, sulfo, alkoxy, keto, carboxy and carboxy; and also includes a group of the general formula:

-It-:

• Ζ'θ where the group Z ' _p is covalently bonded to the group T' _o and is selected • (I ·· Φ φ Φ Φ ·· · · φ · φ · * φφφ ·· φ φ «φφφ φ ·

- 34 -:

Φ φ · Φ · · · Φ · Φ Φ Φ ΦΦ souboru souboru souboru Φ souboru Φ from the set of groups consisting of -C0 ₂ ”, -SO3“, -OSO3 '/ -S0 ₂ ' and OSO ₂ ”, and is either 1 or 2; group T 'is selected from _the group consisting of the groups of formula:

29 '

I - (C) q - * 29 'R ^2y wherein q is a natural number of 1 to 8; R ²⁹ 'is independently selected from substituted or unsubstituted groups selected from the group consisting of unbranched or branched H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, alkylene, heterocyclic compound residue, alkoxy, arylcarbonyl, carboxyalkyl and amide groups; the group G is selected from the group consisting of: 1) -O-; 2) -N ( ^R30 ') ^- ; and 3) N (R ³⁰ 'R ³¹ ') R ²⁷ ', R ²⁸ ', R ³⁰ 'and R ³¹ ' are substituted or unsubstituted groups independently selected from the group consisting of H, oxygen, alkyl, cycloalkyl, alkaryl, aryl, aralkyls, alkylenes, heterocyclic compound radicals, alkoxy groups, arylcarbonyl groups, carboxyalkyl groups and amide groups; any of R ²⁵ ', R ²⁶ ', R ²⁷ ', R ²⁸ ', R ³⁰ 'R ³¹ ' may be associated with any other R ²⁵ ', R ²⁶ ', R ²⁷ ', R ²⁸ ', R ³⁰ 'and R ³¹ ' to form part of a common cycle; any geminal groups R ²⁷ '-R ²⁸ ' may be combined with each other to form carbonyl; any of the vicinal groups R ²⁷ '-R ³¹ ' may be joined to form a double bond; and at the same time any of the groups R ²⁷ '-R ^J ''may combine with each other to form a substituted or unsubstituted fused unsaturated group.

More preferred aryliminium zwitterionic charge of from about +3 to about -3, compounds of the formula [XIV], which are those compounds in which the group R ²⁵ 'is H or methyl, and wherein the group of formula:

• toto · toto · toto * toto toto toto toto toto toto toto toto toto toto toto toto toto toto toto toto toto toto

Z 'is -CO 2, -SO 3' or -OSO 3 ', and p is 1 or 2.

c. Sulfonimines of oxaziridines, phosphonimines, N-acylimines and thiodiazole dioxides

The sulfonimines of oxaziridines [XXIVa], phosphonimines [XXIVb], N-acylimines [XXV] and thiodiazole dioxides [XXVI] and [XXVII] of this invention are compounds of the general formulas:

[XXIVa]

R ⁴³ [XXIVb]

42 '

O.

R ⁴³ O [XXV]

44 '

[XXVI]

wherein R ⁴¹ to R ⁴⁴ , if present, are independently selected from substituted or unsubstituted groups selected from the group consisting of H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, heterocyclic compound residue, silyl, nitro, halo, cyano, sulfo, alkoxy, keto, carboxy, carboalkoxy, any of R ⁴¹ to R ⁴⁴ may be linked to any of

- tt fcfc · fcfc fcfc fcfc fcfc fcfc fcfc fcfc fcfc fcfc With another group R ⁴¹ to R ⁴⁴ to form part of the common cycle, including the remainder of the aromatic compound with fused cycles, the remainder of the carbocyclic compound with fused cycles or the remainder of the heterocyclic compound with fused cycles.

Suitable examples of anionic counterions X are: BFfo, OTS ', and other anionic counterions described in WO 97/06147,

WO 95/13352, WO 95/13353, WO 95/13351, WO 98/23717, U.S. Pat. Nos. 5,360,568, 5,360,559, 5,482,515, 5,550,256, 5,478,357,

370 826, 5 442 066, EP 728 182 B1 and in UK patents 1 215 656. Preferably, the anionic counterion is compatible with the bleaching agent.

No counter ions are associated with non-charged structures.

For structures that carry a negative charge, suitable cationic counterions X ^{+ include,} but are not limited to, Na ⁺ , K ^+, and H ⁺ .

Suitable examples of counterions for the multivalent charge structures are the anionic and cationic counterions mentioned above.

Other organic catalysts

In addition to the bleach promoting compounds, bleaching agents and modified amines and amine oxides described above, organic catalysts can be any of the prior art compounds that are capable of reacting with peroxyacids to form oxygen transfer agents (and cause bleaching).

Concentration of organic catalysts

The organic catalysts of the invention may be added to the scrubbing solution in concentrations ranging from 0.00001 to 0.00% by weight, based on the total weight of the composition, preferably in the range from 0 to 100% by weight. 0001 to 2% by weight, based on the total weight of the composition, more preferably in the range of 0.005 to 0.5% by weight, based on the total weight of the composition, even more preferably in the range of 0.01 to 0.2% by weight, to the total weight of the preparation. Most preferably, in the range of 0.02% to 0.1% by weight, based on the total weight of the composition.

Preferably the bleaching compositions of the present invention, an amount of organic catalyst to a final concentration of bleach boosting compound in a wash solution is from l to 10 @ ⁷ 5.10 ^"4%.

If peroxygen and organic catalysts are present in the bleaching compositions of the present invention, the bleaching compositions of the present invention further preferably contain an amount of peroxygen and an organic catalyst such that the final molar ratio of said peroxygen to organic catalyst in the wash solution is in the wash solution. preferably greater than 1: 1, more preferably greater than 10: 1, even more preferably greater than 50: 1. Preferred ranges of molar ratios of peroxygen to cationic organic catalyst are in the range of 30,000: 1 to 10: 1, preferably in the range of 10,000: 1 to 50: 1, more preferably in the range of 5,000: 1 to 100: 1, and even more preferably in the range of 3500: 1 to 150: 1.

By way of example, conversion values (in%) for use of the product at a concentration of 0.1% are given: In a 0.1% wash solution of the product containing 0.2 wt% organic catalyst, the resulting organic catalyst concentration is 0.0002%. Similarly, in a 0.35% wash solution of an article containing 0.2 wt% organic catalyst, the resulting organic catalyst concentration is 0.00065%.

Particularly suitable for carrying out the methods of releasing the organic catalyst of the present invention and the method of releasing bleaching compositions (articles) containing the organic catalyst are organic catalysts and compositions comprising such catalysts that meet the preferred methods of bleaching a contaminated substrate.

In an aqueous medium containing a source of peroxygen and an organic catalyst which are compounds of the above structures, said medium containing active oxygen from the peroxygen substance in a concentration range of from 5.10 ^-6 to 2.5.10 ² % by volume and the concentration of said organic catalyst is 1.10 to 5.10 ^{-4 -7%,} preferably from 1.10 ^-6 to 3.10 ^4%, more preferably 1.10 to 2.10 ^{_4 6%,} and most preferably 2.10 "to 1.10 ^{6 '4%.}

These preferred methods of bleaching contaminated substrates in an aqueous environment in the presence of a peroxygen source and an organic catalyst are particularly preferred for those applications where maintaining color stability of the contaminated substrate is important. In such a case, it is necessary to choose an embodiment (for example with concentrations of 1.10 ⁶ to 3.10 ⁴ %) which achieves an acceptable color fastness of the fabric. In other applications where the color fastness of the contaminated substrate is not so important, higher concentrations can be used.

Decomposition of organic catalysts

The organic catalysts, especially the bleach-promoting compounds of the present invention, are decomposed by various decomposition methods including, but not limited to, transition to aromatics. The aromatization reaction of 6-membered bleach-promoting cyclic compounds is well known in the art, exemplified by the method described in Hanquet et al., Tetrahedron, 49, 423-438 (1993) and the following method:

θ

OH

Ή

Inactive · · · * · · active active active active active active active active active active active active active active active

An example of another degradation method is the attack of a nucleophilic agent to a bleach-promoting compound and / or a bleaching agent, which may be, inter alia, an attack of a hydroxide anion, a perhydroxide anion, a carboxylate anion, a percarboxylate anion and other nucleophilic agents present under washing conditions. For example, a decomposition reaction of a 6-membered oxaziridinium cycle that may reduce bleaching efficiency may take place as follows:

Methods of controlled release of organic catalysts

Surprisingly, it has been found that the organic catalyst, which is gradually released by the controlled release as defined in the test protocols I, II and / or III below, is characterized by increased bleaching capability compared to the organic catalyst which is used in a wash solution containing fabric without controlled release. test protocols I, II and / or III below. Furthermore, it has been found that an organic catalyst that is progressively released by controlled release described in Test Protocols I, II and / or III below to a wash solution containing peroxyacid and soiled fabric is characterized by increased bleaching capability compared to an organic catalyst ingested in the wash solution. containing a non-controlled-release fabric as defined in Test Protocols I, II and / or III below.

Any suitable means and / or methods of releasing the organic catalysts of the present invention by controlled release as defined in Test Protocols I, II and / or III may be used in the methods of the invention.

The following are examples of controlled release agents and / or methods that fall within the scope of this invention.

Means of controlled release

The release agent used in the processes of the present invention may be any agent capable of controlling the availability of the organic catalyst of the present invention by sequentially and in a controlled manner as defined in Test Protocols I, II and / or III, releases into the wash solution.

Suitable release agents are controlled release agents, such as those suitable for encapsulation or agglomeration, or another type of controlled release agent suitable for use with the organic catalyst of the present invention, capable of causing controlled release, controlling the availability of the organic catalyst, and The process according to claim 1, wherein the organic catalyst is gradually released into the scrubbing solution in a controlled manner as defined in the test protocols I, II and / or III below, as described below. The controlled-release agent preferably controls the availability of the organic catalyst until the peroxygen source, if present, has been added to the system, and preferably has been present in the system for a time sufficient to cause a bleaching effect and / or thereafter The fabric was added to the wash solution.

Encapsulated organic catalysts

As already mentioned, a suitable release agent of the present invention is an encapsulated organic catalyst which is added to the wash solution, with or without detergent ingredients, before or after the peroxygen source is added to the solution, and / or before or after the soiled fabric has been added to the wash solution. The encapsulated organic catalysts are bleaching compositions containing the organic catalyst of the present invention, and most of the bleaching compositions do not release most of the organic catalyst into the wash solution until the peroxygen is added to the wash solution, and preferably until sufficient time has elapsed. so that its bleaching effects can be felt and / or until the soiled fabric has been added to the wash solution. For example, if the encapsulated organic catalyst was added to the scrubbing solution before adding the soiled fabric to the scrubbing solution, then the encapsulated organic catalyst would delay the release of the organic catalyst until the fabric was added to the solution. Usually, the time is in the range of from 2 minutes, more preferably from 1 minute, even more preferably from 1 second to 10 minutes, preferably to 7 minutes, more preferably to 5 minutes. In exceptional cases, this period can be up to 24 hours or more.

In another case, if encapsulated organic catalysts are added to the scrubbing solution containing the soiled fabric, the encapsulation of the organic catalysts preferably prevents the release of the organic catalysts until the peroxyacid bleaching effects present in the scrubbing solution are manifested. minutes, more preferably from 1 minute, even more preferably from 1 second to 10 minutes, preferably up to 7 minutes, more preferably within 5 minutes.

Any suitable encapsulating agent known to those skilled in the art may be used. Examples of such encapsulant compositions suitable for encapsulating the organic catalysts of the present invention are microspheres made of polymers such as thermoplastics, polyacrylonitrile, polymethacrylonitrile, mixtures thereof and / or siliceous materials such as glass. Industrial microspheres are manufactured by the Swedish company Expancel (Akzo Nobel Company) under the trademark EXPANCEL®; by PQ Corp. under the designation PM 6545, PM 6550, PM 7220,

PM 7228, EXTENDOSPHERES (R), LUXSIL (R), Q-CEL (R), SPHERICEL (R); and Malinckrodt under the trademark ALBUMEX®.

Other suitable encapsulating agents are biopolymers such as starch, polyethylene glycols and paraffin waxes described in U.S. Patent No. 5,703,034 to the Procter & Gamble Company of Offshack et al.

The encapsulated organic catalysts comprise one or more organic catalysts of the invention and may further comprise one or more additional detergent ingredients, which may be filler salts, surfactants, other bleaching agents, enzymes, preferably bleach-resistant enzymes, chelating agents, extenders, dye transfer inhibiting agents, fragrances, fabric softeners, soil release agents and brighteners.

An example of a suitable form of the encapsulated organic catalyst is a gel pad.

Agglomerates containing organic catalyst

As already mentioned, another suitable release agent of the invention is an agglomerate comprising the organic catalyst of the invention added to the wash solution before or after the peroxygen source has been added to the wash solution and / or before, or after the soiled fabric has been added to this wash solution. The agglomerated organic catalysts comprise bleaching compositions with the organic catalyst of the present invention, the release of most of the organic catalyst from the bleaching compositions into the scrubbing solution is delayed until a peroxygen source is added to the solution, and preferably until the peroxygen source is present. bleaching effects and / or until a soiled fabric has been added to the wash solution.

For example, if the agglomerate containing the organic catalyst is added to the wash solution before adding the soiled fabric to the wash solution, the agglomerate will delay the release of the organic catalyst until the fabric is added to the wash solution. Usually, this time is in the range of 2 minutes, more preferably 1 minute, more preferably 1 second to 10 minutes, preferably 7 minutes, more preferably 5 minutes. However, in some cases, this period may be up to 24 hours or more.

Alternatively, if the agglomerate containing the organic catalyst is added to the wash solution after the soiled fabric has been added to the solution, the agglomerate will preferably delay release of the organic catalyst until the peroxyacid present in the wash solution bleaches the stains on the fabric. Usually, the time is in the range of 2 minutes, more preferably 1 minute, even more preferably 1 second to 10 minutes, preferably 7 minutes, more preferably 5 minutes.

Any suitable agglomerating agents known to those skilled in the art can be used. Examples of agglomerating agents suitable for agglomerating the organic catalysts of this invention are solid water-soluble ionizable materials such as organic acids, salts of organic and inorganic acids, and mixtures thereof. Examples of such agglomerating agents are described in U.S. Patent 5,540,855 to Baillely et al. ač. No. 5,482,642 to Agar et al., Both assigned to the Procter & Gamble Company.

The agglomerates comprising the organic catalyst may comprise one or more organic catalysts according to the invention and may further comprise one or more detergent ingredients, namely filler salts, surfactants, other bleaching agents, enzymes, preferably bleach-resistant enzymes, chelating agents, extenders , dye transfer inhibiting agents, fragrances, fabric softeners, soil release agents, and brighteners.

• · · · * * * * * * * * * * *

Bleaching agents containing an organic catalyst

In addition to the above encapsulated forms and agglomerates, the organic catalysts of the present invention can be used in conjunction with peroxygen sources in other bleaching compositions regardless of their form. Organic catalysts may, for example, be used in laundry adjuvants.

The bleach-promoting compounds of the present invention can be used in a bleaching composition with or without a peroxygen source. In the bleaching compositions of the present invention, the peroxygen source may be present in concentrations ranging from 0.1 to% by weight based on the total weight of the composition, preferably ranging from 1 to 40% by weight based on the total weight of the composition, and organic the catalyst may be present in concentrations ranging from 0.00001 to 10% by weight based on the total weight of the composition, and preferably in the range from 0.0001 to 2% by weight based on the total weight of the composition, more preferably in the range from 0.005 to 10%. 0.5 wt.%, Based on the total weight of the composition, more preferably in the range of 0.01 to 0.2 wt.%, Based on the total weight of the composition. Most preferably, in the range of 0.02 to 0.1% by weight, based on the total weight of the composition.

By way of example, the conversion values (in%) for use of the product at a concentration of 0.1% are as follows: In a 0.1% wash solution of the product containing 0.2 wt% organic catalyst, the resulting organic catalyst concentration is 0.0002%. Similarly, the product solution containing 0.2 wt. % organic catalyst is a final organic catalyst concentration of 0.00065%.

Preferred concentrations of bleaching compounds are given for bleaching compounds having a molecular weight of about 300 g / mol, but bleaching compounds may have molecular weights ranging from 150 to 1000 g / mol, or even for oligomeric or polymeric bleaching compounds. And higher. For example, if in the bleaching compositions of the present invention, the bleach boosting compound is present in the range from 0.005 to 0.5%, the molar concentration of bleach boosting compound will range from 1,7.10 to 1,7.10 ^{-5 -8%.} If the organic catalyst used in the bleaching compositions of the present invention has a higher molecular weight, the preferred molar concentration will remain unchanged, but the preferred weight concentration (expressed as a percentage) will be reasonably higher. For example, the concentration range of the bleaching compound with a molecular weight of about 600 g / mol will be in the range of 0.01 to 1.0%. For oligomeric or polymeric bleach enhancers, the more preferred molar concentration is based on monomeric units containing an iminium or oxaziridinium active group.

Particularly suitable for carrying out the methods of releasing the organic catalyst of the present invention and the method of releasing bleaching compositions (articles) comprising the organic catalyst are organic catalysts and compositions comprising such catalysts which comply with preferred methods of bleaching a contaminated substrate in an aqueous medium containing a peroxygen source and an organic catalyst. which are compounds of the above structures, wherein said medium contains active oxygen from a peroxygen substance in a concentration range of 5.10 ^-6 to 2.5.10 ^-2 volume. %, and the concentration of said organic catalyst is 1.10 ^-7 to 5.10 ^-4 %, preferably 1.10 ^-6 to 3.10 ^-4 %, more preferably 1.10 ^-6 to 2.10 ^-4 %, and most preferably

2.10 ^{- 6} to 1.10 ^-4 %.

These preferred methods of bleaching contaminated substrates in an aqueous environment in the presence of a peroxygen source and an organic catalyst are particularly preferred for those applications where maintaining color stability of the contaminated substrate is important. In this case, it is necessary to choose the design (for example with concentrations)

1.10 ^{- 6} to 3.10 ^-4 %), which achieves acceptable fabric color fastness. In other applications where the color fastness of the contaminated substrate is not so important, it is possible to add 46 • ♦ ···· ♦

use higher concentrations.

The organic catalysts of the present invention which are particularly suitable for use in the bleaching compositions of the present invention may preferably be sequentially released into a wash solution containing the bleached compositions in a controlled release manner as defined in Test Protocols I, II and / or III described below. Likewise, bleaching compositions containing organic catalysts may be prepared in such a way that the organic catalysts contained therein can be gradually released into a wash solution containing these bleaching compositions in a controlled release manner as defined in Test Protocols I, II and / or III below.

The bleaching compositions of the present invention can be advantageously used in washing, cleaning of solid surfaces, bleaching of textiles and / or bleaching of cellulose, for antimicrobial and / or disinfectant purposes, as well as for cosmetic purposes for dental care, teeth, hair and skin. Due to the unique advantages of both increased efficiency at lower temperatures and reduced unwanted decomposition, the organic catalysts of the present invention are ideally suited for use as laundry bleach and / or bleach dye (e.g., dye transfer inhibiting agents) as bleach. contained in detergents or bleaching detergent additives. The organic catalyst of the invention can be used in granular form, in powder form, in the form of cubes, paste, foam, gel and in the form of a liquid substance.

Thus, the bleaching compositions of the present invention may also comprise other various detergent ingredients suitable for use in laundry applications. Such ingredients are detergent surfactants, other bleaching agents including other bleach catalysts, extenders, chelating agents, enzymes, polymeric soil release agents, brighteners, and various other detergent ingredients. The compositions, including these various other ingredients thereof, preferably have a pH in the range of from 6 to 12, more preferably in the range of from 8 to 10.5 in the form of a 1% solution.

Preferably, the bleaching compositions comprise at least one detergent surfactant, at least one chelating agent, at least one enzyme for use in detergents, and preferably have a pH in the range of from 6 to 12, more preferably in the range of from 8 to 12, 10.5.

Suitably, the bleaching composition further comprises a peroxygen source as described in more detail below. Bleaching agents are powder or liquid formulations comprising a source of hydrogen peroxide or a source of peroxygen as described in more detail below.

If the bleaching agent contains, inter alia, a source of hydrogen peroxide, it is desirable that the bleaching agent is present in the form of a laundry detergent and the same applies to bleach activators, which are described in detail below.

In another embodiment of the present invention, there is provided a method of washing soiled fabrics. This preferred method comprises contacting the fabric with a wash solution. The canine may be any fabric that can be washed under normal user wash conditions. The wash solution of the process comprises a bleaching agent described herein. The water temperature is preferably in the range of 0 to 50 ° C or higher. The ratio of fabric weight to water weight is preferably in the range of 1: 1 to 15: 1.

The wash solution may further comprise at least one additional detergent component selected from the group consisting of a detergent surfactant, another bleaching agent, a chelating agent, an enzyme for use in detergents, and mixtures thereof. The washing solution containing 1% bleaching agent preferably has a pH in the range of 8 to 10.5.

According to another aspect of the present invention, a laundry detergent composition is provided. This laundry detergent contains an organic catalyst that has been described in detail earlier. This laundry adjuvant is ideally suited for use in a washing process in which increased bleaching efficiency is desired. Such a case may be

• Low temperature.

Particularly suitable components of the laundry detergent compositions of the present invention are the organic catalysts of the present invention. Particularly suitable for use in laundering are the adjuvants of the invention which are capable of controlled release into the laundering solution as defined in Test Reports I,

II and / or III described below. Also, the organic catalysts may be released into the wash solution by controlled release, as defined in the test protocols I, II and / or III described below. Auxiliary laundry detergent compositions containing organic catalysts may be prepared in such a way that the organic catalysts are released into a wash solution containing the auxiliary detergent compositions by controlled release as defined in the test protocols I, II and / or described below.

III.

Suitably, the laundry detergent composition further comprises a peroxygen source, which is described in detail below. The laundry detergent composition may also be a powder or liquid composition comprising a source of hydrogen peroxide or a source of peroxygen, as described in detail below.

If the laundry detergent composition comprises a source of hydrogen peroxide, it is desirable to further include a bleach activator as described in detail below.

Preferably, the laundry detergent composition is packaged in a form suitable for addition to a laundry detergent solution containing a peroxygen source and characterized by increased bleaching performance. Such a package may be a tablet, gel pad or other packaging unit containing a certain amount of powder or liquid. Fillers or carriers that increase the volume of the formulation may also be included. Suitable fillers or carriers may include, but are not limited to, various sulfates, carbonates and silicates, as well as talc, clay, and the like. The fillers or carriers of the liquid preparations may be water or lower primary and secondary alcohols including polyols and diols. Examples of such substances are methanol, ethanol, propanol and isopropanol. Other alcohols may also be used. The formulations may contain 5 to 90% of such substances. Acidic fillers may be used to lower the pH.

Preferred are bleaching compositions comprising:

(a) a bleaching system comprising a pegengr source; and (b) an organic catalyst;

wherein the organic catalyst is released into a wash solution containing said bleach by controlled release in the manner defined in Test Reports I, II and / or III.

Bleaching system

The bleaching compositions of the present invention preferably contain a bleaching system in addition to the organic catalyst of the present invention. Bleaching systems usually contain a source of peroxygen. Peroxygen sources are well known in the art and the peroxygen source used in the methods of the present invention may comprise any of these well known sources, including peroxygen compounds, as well as compounds that provide an effective amount of peroxygen in situ under conditions customary to use by the customer. The peroxygen source may be, inter alia, a hydrogen peroxide source, anionic peroxyacids formed in situ by the reaction of a hydrogen peroxide source and a bleach activator, peroxyacid precursors, or mixtures of suitable peroxygen sources. It will be apparent to those skilled in the art that other sources of peroxygen may be used without departing from the scope of the present invention.

Preferably, the peroxygen source is selected from the group consisting of:

(i) peroxyacid precursors selected from the group consisting of percarboxylic acids and their salts, peroxycarbonic acid and its salts, peroxyacid imides of their salts, peroxosulfuric acid and salts thereof, and mixtures thereof; and (ii) a hydrogen peroxide source selected from the group consisting of peroxyborate compounds , percarbonate compounds, peroxyphosphorous compounds and mixtures thereof, and bleach activator.

If peroxygen sources (peroxyacids and / or hydrogen peroxide source) are present, their concentration is usually greater than 1% by weight, preferably in the range of 5 to 30% by weight, preferably at most 20% by weight. If bleach activators are present, their concentration is generally greater than 0.1% by weight, preferably 0.5% to 60% by weight, preferably at most 40% by weight, based on the weight of the bleaching agent containing the bleaching agent, and a bleach activator.

Peroxyacid precursors

By the term peroxyacid precursor as used herein is meant any suitable compound that is stable and which, under the conditions customary in the use of the product by the customer, provides an effective amount of the peroxyacid anion. Of course, the organic catalysts of the present invention can be used in conjunction with peroxyacid precursors selected from the group consisting of percarboxylic acids and salts thereof, peroxycarbonic acid and salts thereof, peroxyacid acid imides and salts thereof, persulfuric acid and salts thereof, and mixtures thereof, examples of which are described in U.S. Patent No. 5,576,282 to Miracle et al.

One type of suitable organic peroxyacid is a compound of the formula:

wherein R is alkylene or substituted C 1 -C 22 alkylene or phenylene or substituted phenylene, and Y is hydrogen, halogen, alkyl, aryl, -C (O) OH or -C (O) OOH.

Organic peroxyacids suitable for use in the procedures of

of the invention may contain either one or two peroxy groups and may be either aliphatic or aromatic. When the organic peroxycarboxylic acid is an aliphatic, unsubstituted peroxyacid, it has the general formula:

Y- (CH ₂ ) n -C -O-OH wherein Y may be, for example, H, CH ₃ , CH ₂ Cl, C (O) OH, or C (O) OOH; and n is an integer from 0 to 20. In the case of an organic aromatic peroxycarboxylic acid, the general formula of the following unsubstituted peroxyacid is:

Y-C 1 -C -O-OH wherein Y may be, for example, hydrogen, alkyl, haloalkyl, halogen, C (O) OH or C (O) OOH.

Typical monoperoxyacids suitable for use in the present invention are alkylperoxyacids and arylperoxyacids such as:

(i) peroxybenzoic acid and peroxybenzoic acids substituted on the aromatic ring, for example peroxy-anaphtoic acid, perphthalic acid (and its magnesium salt hexahydrate) and ocarboxybenzamidoperoxyhexanoic acid (sodium salt);

ii) aliphatic acids, substituted aliphatic acids, and arylalkylmonoperoxyacids such as peroxylauric acid, peroxystearic acid, N-nonanoylaminoperoxycaproic acid, (NAPCA), N, N- (3-octylsuccinoyl) aminoperoxycaproic acid (SAPA) and N, N-phthaloylaminic acid );

(iii) peroxyacid amides, for example peronic acid monononylamide

- 52 to toto to to to 9 9 9 y y y y y y y y y y y y y y y y y y y y y y y y y y y y y y y y y y y y y y y y y

Typical diperoxy acids suitable for use in the methods of this invention are alkyldiperoxy acids and aryldiperoxy acids such as:

iv) 1,12-diperoxydodecanedioic acid;

v) 1,9-diperoxyazelaic acid;

vi) diperoxybrasilic acid; diperoxysebacic acid and diperoxyisophthalic acid;

(vii) 2-decyldiperoxybutane-1,4-dioic acid;

(viii) 4,4'-sulfonylbisperoxybenzoic acid.

These bleaching agents are described in U.S. Patent No. 4,483,781 to Hartman, issued Nov. 20, 1984, U.S. Patent No. 4,634,551 to Burns et al., European Patent Application No. 0 133 354 to Banks. et al. published Feb. 20, 1985, and U.S. Patent No. 4,412,934 to Chung et al., issued November 1, 1983. Sources of 6-nonylamino-6-oxoperoxycaproic acid and other agents are described in U.S. Patent No. 4,634,551. , issued Jan. 6, 1987 to Burns et al. Persulfate compounds such as OXONE, manufactured by E.I. DuPont de Nemours, Wilmington, DE, can also be used as a suitable source of peroxysulfuric acid.

b. Sources of hydrogen peroxide

The source of hydrogen peroxide may be any suitable source of hydrogen peroxide present at such concentration as disclosed in U.S. Patent No. 5,576,282. The source of hydrogen peroxide may, for example, be selected from the group consisting of perborate, percarbonate, perphosphate and mixtures thereof. substances.

Sources of hydrogen peroxide are described in detail in Kirk Othmer's Encyclopedia of Chemical Technology, 4th edition (1992, John Wiley & Sons), Volume 4, pp. 271-300 in the Bleaching chapter. φ i · · · · * * * • • • »» »» »

♦ ♦ ·

Φ Φ * · φφφφ

Agents (Survey), and include, but are not limited to, various forms of sodium peroxyboronic acid and sodium percarbonate salts, including various coated and modified forms thereof.

The preferred source of hydrogen peroxide for use in the methods of the invention may be any conventional source of hydrogen peroxide, including hydrogen peroxide itself. The source may be, for example, sodium perborate (hydrates thereof, preferably mono- or tetrahydrate), carbonate peroxyhydrate or the like, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, or sodium peroxide may not be used. Also available are oxygen sources such as persulfate bleach (e.g., OXONE, manufactured by DuPont). Sodium perborate monohydrate and sodium percarbonate are particularly preferred. Mixtures of any conventional source of hydrogen peroxide may also be used.

Preferred percarbonate bleaches consist of solid particles having an average particle size in the range of 500 µm to 1,000 µm, with a maximum of 10% by weight of the particles being less than 200 µm and a maximum of 10% by weight of the particles being greater than 1250 µm. The percarbonate can also be coated with silicate, borate or water-soluble surfactants. Percarbonate is produced by various manufacturers such as EMC, Solvay and Tokai Denka.

The compositions of the invention may also contain chlorine bleaching agents as a bleaching agent. Such bleaching agents are well known in the art and include, but are not limited to, sodium diisocyanurate (NaDCC). However, these chlorine bleaching compositions are less suitable for enzyme preparations.

b. Bleach Activators

Preferably, the peroxygen source is present in the formulation together with the activator (peroxyacid precursor). These activators are present in concentrations ranging from 0.01% by weight, preferably in the range of 0.01% by weight.

54 limits from 0.5% by weight, more preferably in the range of 1 to 15% by weight, preferably up to 10% by weight, more preferably up to 8% by weight, based on the weight of the composition. The term bleach activator as used herein means any compound which, when used in conjunction with a peroxide source, causes in situ formation of the peroxyacid corresponding to the bleach activator in question. Various examples of activators are described in U.S. Patent No. 5,576,282, U.S. Patent No. 4,915,854, and U.S. Patent No. 4,412,934. Other typical bleaching agents and activators suitable for use in the present invention are also described in U.S. Pat. U.S. Patent No. 4,634,551.

Preferred activators are selected from the group consisting of tetraacetyl ethylenediamine (TAED), benzoylcaprolactam (BzCL), 4-nitrobenzoylcaprolatam, 3-chlorobenzoylcaprolactam, benzoyloxybenzenesulfonate (BOBS), nonanoyloxybenzenesulfonate (NOB), benzoylvalerolactam (BZVL), octanoyloxybenzenesulfonate (Cs-OBS), perhydrolyzable esters and mixtures thereof, most preferably from benzoylcaprolactam and benzoylvalerolactam. Particularly preferred bleach activators at a pH in the range of from 8 to 9.5 are those whose leaving groups are OBS or VL.

Preferred hydrophobic bleach activators are nonanoyloxybenzene sulfonate (NOBS), 4- [N- (nonanoyl) aminohexanoyloxy] benzene sulfonate sodium (NACA-OBS), described in U.S. Patent No. 5,523,434, lauroyloxybenzene sulfonate (LOBS), or C12-OB

10-undecenoyloxybenzenesulfonate (UDOBS or Cu-OBS with a double bond at the 10-position) and decanoyloxybenzoic acid.

Preferred bleach activators are those described in U.S. Patent No. 5,698,504 to Christie et al., Issued December 16, 1997; in U.S. Patent No. 5,695,679 to Christie et al. issued December 9, 1997; U.S. Patent No. 5,686,401 to Willey et al., issued Nov. 11, 1997; U.S. Patent No. 5,686,014 to Hartshorn et al., issued November 11, 1997; U.S. Patent No. 5,405,412 to Willey et al., issued April 11, 1995; U.S. Patent No. 5,405,413 to Willey et al., issued Nov. 11, 1995; U.S. Patent No. 5,130,045 to Mitchel et al., issued July 14, 1992; and U.S. Patent No. 4,412,934 to Chung et al., issued Nov. 1, 1983; and U.S. Patent Application Serial Nos. 08 / 709,072 and 08 / 066,564, all of which are incorporated herein by reference.

The molar ratio of peroxygen bleach compound (expressed as AvO) to bleach activators in the present invention generally ranges from 1: 1 to 20: 1, more preferably from 10: 1 to 1: 1, preferably up to 3: 1.

Quaternary substituted bleach activators may also be used. The bleaching compositions of the present invention preferably comprise substituted quaternary bleach activators (QSBA) or substituted quaternary peroxyacid (QSP), more preferably the former. Preferred QSBs are further described in U.S. Patent No. 5,686,015 to Willey et al., Issued Nov. 11, 1997; U.S. Patent No. 5,654,421 to Taylor et al., issued Aug. 5, 1997; U.S. Patent No. 5,460,747 to Gosselink et al., issued Oct. 24, 1995; in U.S. Pat

No. 5,584,888 to Miracle et al., issued December 17, 1996; and U.S. Patent No. 5,578,136 to Taylor et al., issued November 26, 1996, all of which are incorporated herein by reference.

Highly preferred bleach activators suitable for use in the present invention are the amide derivatives disclosed in U.S. Patent No. 5,698,504, U.S. Patent No. 5,695,679, and U.S. Patent No. 5,686,014, which have already been ciphered in U.S. Pat. above. Preferred examples of such bleach activators are (6-octanamidocaproyl) oxybenzenesulfonate, (6-nonanamidocaproyl) oxybenzenesulfonate, (6-decanamido caproyl) oxybenzenesulfonate, and mixtures thereof.

Other suitable activators described in U.S. Patent No. 5,698,504, U.S. Patent No. 5,695,679, and the U.S. Patent • ftft • · ft ·

No. 5,686,014, cited previously, and U.S. Patent No. 4,966,723, Hodge et al., issued Oct. 30, 1990, are activators of the benzoxazine type, such as those in which C ₆ H ₄ bonded at positions 1,2 of the group -O (O) 00 (?) =?

Depending on the type of activator used and its use, a good bleaching effect can be achieved in bleaching systems whose pH is in the range of from 6 to 13, preferably in the range of from 9.0 to 10.5. Generally, activators are used in a pH range close to neutral pH slightly lower than neutral pH. To achieve these conditions, alkaline substances and buffers may be used.

The acyl lactam activators described in US Patent No. 5,698,504, US Patent No. 5,695,679, and US Patent No. 5,686,014, which are cited hereinabove, are very suitable for use in the methods of the invention. This is particularly true for caprolactam acyl derivatives (see for example WO 94-28102 A) and valerolactam acyl derivatives (see U.S. Patent No. 5,503,639 to Willey et al., Issued April 2, 1996 and incorporated herein by reference).

d. Organic peroxides, especially diacyl peroxides

In addition to the bleaching agents described above, the bleaching agents of the present invention may be other organic peroxides. Organic peroxides are described extensively in Kirk Othmer, Encyclopedia of Chemical Technology, Vol. 17, John Wiley and Sons, 1982, pages 27-90, and in particular pages 63-72. When diacyl peroxide is used, it is preferable to use a substance which exhibits minimal adverse effects on coating.

e. Metal bleach catalysts

The bleaching agents may also contain, inter alia, metal bleach catalysts, preferably manganese and cobalt bleach catalysts.

One type of metal-containing bleach catalyst is a catalyst system comprising a transition metal cation with defined bleach catalytic activity, such as copper, iron, titanium, ruthenium, chromium, molybdenum, or manganese cations, as well as a cationic metal cation with low or no bleach catalytic activity such as are cations of zinc or aluminum, and a masking agent with defined cation complexity constants of catalytic and auxiliary metals, especially ethylenediaminetetraacetic acid, ethylenediaminotetramethylenephosphonic acid, and water-soluble salts thereof. These catalysts are disclosed in U.S. Patent No. 4,430,243 to Bragg, issued Feb. 2, 1982.

i. Manganese complexes

If desired, the compositions of the invention may contain manganese compounds as catalysts. Such compounds and concentrations at which they are used are well known in the art and include, but are not limited to, the manganese-based catalysts described in U.S. Patent No. 5,576,282 to Miracle et al., Issued November 19, 1996; U.S. Patent No. 5,246,621 to Favre et al., issued September 21, 1993; U.S. Patent No. 5,244,594 to Favre et al., issued September 14, 1993; U.S. Patent No. 5,194,416 to Jureller et al., issued March 16, 1993; U.S. Patent No. 5,114,606 to Van Vliet et al., issued May 19, 1992; and European Patent Application Nos. 549,271 Til,

549,272 A1, 544,440 A2 and 544,490 Al; Preferred examples of these catalysts include Mn ^IV 2 (UO), ₃ (U) ₃ (1,4, 7-trimethyl-4,7triazacyklononan) ₂ (PF _{6) 2,} Mn ^IIT 2 (UO) i (u-OAc) 2 (1,4,7-trimethyl-1,4,7-triazacyclononane) 2 (C1O4) 2, Mn ^IV 4 (µO) ₆ (1,4,7-triazacyclononane) ₄ (C1O ₄ ) ₄ , Mn ^IIT Mn ^IV 4 (µO ) i (u-QAc) ₂ . (1,4,7-trimethyl-1,4,7 triazacyclononane) ₂ (C1O ₄ ) ₃ , Mn ^IV (1,4,7-trimethyl-1,4,7-triazacyclononane) - (OCH ₃ ) ₃ PF ₆ ), and mixtures of these substances. Other metal-based bleach catalysts are those disclosed in U.S. Patent No. 4,430,243, which is incorporated herein by reference, and in U.S. Patent No. 5,114,611, van Kralingen, issued May 19, 1992. The use of manganese complexes with various ligands, whitening enhancers are also described in the following US patents: U.S. Patent No. 4,728,455 to Rerek, issued March 1, 1988; U.S. Patent No. 5,284,944 to Madison, issued Feb. 8, 1994; U.S. Patent No. 5,246,612 to Van Dijk et al., issued Mar. 21, 1993; U.S. Patent No. 5,256,779 to Kerschner et al., issued October 26, 1993; U.S. Patent No. 5,280,117 to Kerschner et al., issued Jan. 18, 1994; U.S. Patent No. 5,274,147 to Kerschner et al., issued Dec. 28, 1993; U.S. Patent No. 5,153,161 to Kerschner et al., issued October 6, 1992; and U.S. Patent No. 5,227,084 to Martens et al., issued July 13, 1993.

ii. Cobalt complexes

Cobalt-containing bleach catalysts suitable for use in the methods of the present invention are known, for example, in U.S. Patent No. 5,597,936 to Perkins et al., Issued Jan. 28, 1997; U.S. Patent No. 5,595,967 to Miracle et al., issued Jan. 21, 1997; U.S. Patent No. 5,703,030, Perkins et al., issued Dec. 30, 1997; and in MLTobe, Base Hydrolysis of Transition-Metal Complexes, Adv. Inorg. Bioinorg. Moss. 2, 1-94 (1983). The most preferred cobalt catalysts suitable for use in the present invention are pentamokobaltité salts having the formula [Co (NH _{3) 5} 0Ac] T _y, wherein OAc is an acetate anion, and T _y is a further anion, especially chloride pentamokobaltitý, [Co ( NH _{3) 5} 0Ac] Cl _2; as well as [Co (NH _{3) 5} 0Ac] (OAc) _2; [Co (NH ₃ ) ₅₀ Ac] (PF ₆ ) ₂ ; [Co (NH ₃ ) ₅ QAc] SO ₄ ;

[Co (NH _{3) 5} 0Ac] (KBF _{4) 2;} and [Co (NH _{3) 5} 0Ac] _{(NO3) 2} (herein referred to as PAC).

These cobalt catalysts can be readily prepared by known methods such as those cited in U.S. Patent Nos. 5,597,936, 5,595,967, and 5,703,030 cited therein and in the references cited therein. and U.S. Patent No. 4,810,410, to Diakun et al., issued Mar. 7, 1989, WL. Jolly J., Synthesis and Characterization of · · · · · · · · · · · · · · ·

Inorganical Compounds, pp. 461-3, (Prentice-Hall; 1970); and in Chem. Ed. 66 (12), 1043-45 (1989); Inorg. Chem., 18, 1497-1502 (1979); Inorg. Chem. 21, 2881-2885 (1982); Inorg. Chem., 18, 2023-2025 (1979); Inorg. Synthesis, 173-176 (1960); and Journal of Physical Chemistry. 56, 22-25 (1952).

iii. Transition metal complexes with macropolycyclic rigid ligands

The compositions of the invention may also contain as a bleach catalyst a transition metal complex with a macropolycyclic rigid ligand. The phrase macropolycyclic rigid ligand is sometimes abbreviated hereinafter as MRL. The amount used is a catalytically effective amount, preferably 1.10 ^"7% or more, for example up to 99.9%, more typically 1.10 ^-7% or more, preferably from 5.10 'to 5.10 ^{6% -2%.}

Suitable transition metals, for example Mn, are set forth below. Macropolycyclic means MRL is both macrocyclic and polycyclic. Polycyclic means at least bicyclic. The term rigid, as used herein, means superstructure and linked by cross-links. Rigid means limited flexibility: see D.H. Busch., Chemical Reviews., 93, 847-860 (1993), incorporated herein by reference. The term rigid as used herein means that the MRL must have a significantly higher rigidity than the macrocycle (parent macrocycle), which is otherwise identical (having the same cycle size and type and the same number of atoms in the main cycle) but without superstructure (especially without linking or preferably crosslinking groups) found in the MRL. For the determination of comparative rigidity of macrocycles with and without superstructure, the free form of macrocycles (a form to which the metal is not bound) is used. Rigidity is a property known to be useful in comparing macrocycles; suitable methods for determining, measuring, or comparing rigidity are those using computer technology (see, for example, Zimmer, Chemical Reviews. 95, (38), 2629-60).

2648 (1995) or Hancock et al., Inorganica Chimica Acta. 164: 73-84.

Preferred MRLs are those with special types of ultrarigid cross-linked ligands. An example of a cross link is shown in 1.11. The transverse bond is a -CH ₂ CH ₂ group. This transverse bond forms a bridge between N ¹ and N ⁸ in the structure shown. For comparison, it can be shown that a bridge on the same side, for example a bridge connecting the atoms N ¹ and N ¹² in 1.11, would not be a cross link and such a structure would not be preferred.

Suitable metals of complexes with rigid ligands are Mn (II), Mn (III), Mn (IV), Mn (V), Fe (II), Fe (III), Fe (IV), Co (I), Co (II) ), Co (III), Ni (II), Ni (II), Ni (III), Cu (I), Cu (II), Cu (III), Cr (II), Cr (III), Cr (IV) ), Cr (V), Cr (VI), V (III), V (IV), V (V), Mo (IV),

Mo (V), Mo (VI), W (IV), W (V), W (VI), Pd (II), Ru (II), Ru (III), and Ru (IV). Preferred transition metal bleach catalysts of the present invention are manganese, iron and chromium.

More generally, MRLs suitable for use in the processes of the present invention (and corresponding transition metal catalysts) preferably include:

(a) at least one main cycle of a macrocycle containing four or more heteroatoms; and

b) a covalently bonded metal-free superstructure capable of increasing the rigidity of the macrocycle, preferably selected from

(i) superstructures such as linkers;

(ii) cross-linking superstructures, such as cross-linking linkers; and iii) combinations thereof.

The term superstructure as used herein is defined in the literature by publications written by Busch, see, for example, the articles of this author in Chemical Reviews.

Preferred superstructures of the present invention not only increase the rigidity of the parent macrocycle, but also promote the orientation of the macrocycle that allows it to coordinate with the metal in the slit. Suitable superstructures may be strikingly simple, for example, linkers similar to those shown in Figures 1 and 2 may be used.

(CH ₂ ) _{n of} Figure 1 wherein n is a natural number, for example of 2 to 8, preferably a natural number of less than 6, usually 2 to 4, or

Fig. 2 wherein m and n are natural numbers 1 to 8, more preferably 1 to 3; Z is N or CH; and T is a compatible substituent, for example H, alkyl, trialkyl ammonium, halogen, nitro, sulfo, and the like. The aromatic ring at 1.10 can be replaced by an aliphatic ring in which the Z atom joining the ring can be N, O, S or C.

An example of a suitable MRL is:

tm · ·

This MRL, suitable and highly preferred for use in the methods of the present invention, is a methyl-substituted cyclamide linked by cross-links (with all tertiary nitrogen atoms). Formally, this ligand is called 5,12-dimethyl-1,5,8,12-tetraaza-bicyclo [6.6.2] hexadecane using the extended Bayer system. See Guide to the IUPAC Nomenclature of Organic Compounds: Recommendations 1993, edited by R.-Panico, W.H. Powell and J.C. Richer, Blackwell Scientific Publications, Boston, 1993, in particular Chapter R-2.4.2.1.

The transition metal-containing bleach catalysts with macrocyclic rigid ligands suitable for use in the compositions of this invention may generally be known compounds meeting the definition herein, as well as, more preferably, any of a number of new compounds specifically developed for use in laundry or cleaning the processes of the invention, exemplified by the following compounds:

dichloro-5,12-dimethyl-1,5,8,12-tetraaza-bicyclo [6.6.2] manganese hexadecane, diaquo-5,12-dimethyl-1,5,8,12-tetraaza-bicyclo [6.6. (2) hexadecane manganese hexafluorophosphate, aquo-hydroxy-5,12-dimethyl-1,5,8,12-tetraaza-bicyclo [6.6.2] hexadecane manganese hexafluorophosphate,

Diaquo-5,12-dimethyl-1,5,8,12-tetraaza-bicyclo [6.6.2] hexadecane manganese tetrafluoroborate, dichloro-5,12-dimethyl-1,5 8,12-tetraaza-bicyclo [6.6.2] hexadecane manganese hexafluorophosphate, dichloro-5,12-di-n-butyl-1,5,8,12-tetraaza-bicyclo [6.6.2] manganese hexadecane, dichloro- 5,12-dibenzyl-1,5,8,12-tetraaza-bicyclo [6.6.2] manganese hexadecane, dichloro-5-n-butyl-12-methyl-1,5,8,12-tetraaza-bicyclo [6.6] .2] manganese hexadecane, dichloro-5-n-octyl-12-methyl-1,5,8,12-tetraaza-bicyclo [6.6.2] manganese hexadecane, dichloro-5-n-butyl-12-methyl-1; 5,8,12-tetraaza-bicyclo [6.6.2] manganese hexadecane.

For practical reasons, the compositions of the present invention can be packaged and the cleaning methods of the present invention can be performed so as to provide a concentration in aqueous wash solutions correspondingly. at least one part of active bleach catalyst per 100 million parts of water, and that the concentration is preferably in the range of 1.10 ^-6 to 2.5.10 ^-4 %, more preferably in the range of 5.10 ^-6 to 1.10 ^-3 %, and most preferably in the range from 1.10 ^-5 to 5.10 ^-4 . In order to obtain these concentrations in the aqueous solutions used in automatic washing machines, the compositions according to the invention usually contain 0.0005 to 0.2% by weight, more preferably 0.004 to 0.08% by weight of a bleaching catalyst, in particular a manganese or cobalt catalyst, based on the total weight of the cleaning agent.

The peroxygen source is preferably a hydrogen peroxide source and is selected from the group consisting of perborate compounds, percarbonate compounds, perphosphate compounds, and mixtures thereof, and further comprises a bleach activator.

The bleach activator is preferably selected from the group consisting of the previously described hydrophobic bleach activators.

The purpose of such a bleaching agent is to alleviate the undesirable decomposition of the organic catalyst and to cause the peroxyacid bleaching effect on the soiled fabric to be applied prior to the release of the organic catalyst.

Ingredients of detergents

Although not absolutely necessary in the practice of the present invention, it is desirable that the bleaching compositions of the present invention include various conventional excipients listed below as suitable for use in the bleaching compositions of the present invention, the presence of which in preferred embodiments of the present invention. The invention may, for example, increase the achieved cleaning efficiency and are suitable for treating the substrate to be cleaned or for modifying the properties of the bleaching composition. These are fragrances, dyes and the like. The nature of these additional components and their concentration depends on the physical form of the formulation and the nature of the cleaning process for which they are to be used. Unless otherwise specified, the bleaching compositions herein may be a granular or powdered universal or specialty cleansing agent, especially laundry detergents in liquid, gel or paste form, and universal detergents, especially high performance liquid type detergents, liquid detergents for delicate fabrics. , preparations for manual dishwashing or delicate preparations for dishwashing, especially these preparations with high sudsing; dishwashing preparations, including various types thereof in the form of tablets, granules and liquids and rinse aid aids, liquid cleaning and disinfecting agents, including bactericidal types and handwashing products, detrgents for washing laundry in the form of cubes, mouthwashes, detergents dentures, car wash shampoo or car shampoo, bathroom and toilet cleaners; hair shampoos and hair lotions; shower gels, bath foams and metal cleaners; as well as cleaning aids such as bleach additives, stain removal sticks, or sticks to treat heavily soiled areas on fabrics prior to washing.

Surfactants

The bleaching compositions of the present invention comprise a surfactant or surfactant system, which surfactant may be selected from nonionic and / or anionic and / or cationic surfactants and / or ampholytic and / or zwitterionic and / or semi-ionic surfactants. polar nonionic surfactants.

The surfactant is usually present in a concentration ranging from 0.1 wt%, preferably from 1 wt%, more preferably from 5 wt%, based on the total weight of the bleaching composition to 99.9 wt%, preferably to 80 wt%, more preferably up to 35 wt%, and most preferably up to 30 wt%, based on the total weight of the bleaching composition.

These surfactants may be nonionic, anionic, ampholytic, zwitterionic, or cationic. Mixtures of these surfactants may also be used. Preferred bleaching compositions comprise anionic surfactants or mixtures of anionic surfactants with another surfactant, especially nonionic surfactants.

The surfactant is preferably of a type compatible with the enzyme components present in the composition. In liquid or gel formulations, the most preferred surfactants are those which promote or at least reduce the stability of the enzymes present in the formulations.

Examples of suitable nonionic, anionic, cationic, ampholytic, zwitterionic ionic and semi-polar nonionic surfactants are described in U.S. Patent Nos. 5,707,950 and 5,576,282. Additional examples of suitable surfactants may be found in the reference in McCutcheon, Emulsifiers and Detergents, North American Edition, 1997, McCutcheon Division, MC Publishing Company, U.S. Patent Nos. 3,929,678 and 4,259,217; Surfactants Science, Marcel Dekker, Inc., New York and Basel; in Handbook of Surfactants, M.R. Porter, Chapman and Hall,

2nd ed., 1994; in the Surfactants in Consumer Products manual.

edited by J. Falbe, Springer-Verlag, 1987; and Surface Active Agents and Detergents (Volumes I and II, Schwartz, Perry, and Berch).

Highly preferred nonionic surfactants are polyhydroxy fatty acid amide derivatives having the general formula:

R ² -C (O) -N (R ^X ) -Z, wherein R ¹ is H, or C 1-4, a hydrocarbon radical, 2-hydroxyethyl, 2-hydroxypropyl or a mixture of these substituents, R ² is a hydrocarbon radical 05-31, and Z is a polyhydroxy derivative of a hydrocarbon moiety having a non-linear hydrocarbon chain and at least 3 hydroxyls directly bonded to the chain, or an alkoxylated derivative thereof. R ¹ is preferably methyl, R ² is unbranched alkyl or alkenyl Cn-15, optionally alkyl or alkenyl C 16 -is such as alkyls derived from coconut fatty acids or mixtures of these substituents, and Z is a substituent derived from reduced sugars such as glucose, fructose, maltose, lactose reduction amination reaction.

Highly preferred anionic surfactants are alkylalkoxylated sulphate surfactants which are water-soluble salts or acids of the formula R0 (A) _m SC> 3M, wherein R is an unsubstituted C10-C24 alkyl or a C10-C24 hydroxyalkyl group. preferably an alkyl or hydroxyalkyl having a C12-em C20Z preferably an alkyl or hydroxyalkyl having a C ₂ -C EM _8, A is propoxy or ethyloxyskupina, m is greater than zero, typically between 0.5 and 6, more preferably 0.5 to 3, and M is H or a cation which may be, for example, a metal (e.g., sodium, potassium, lithium, calcium, magnesium and the like), ammonium or substituted ammonium cation. Also included are alkylethoxylated sulfates as well as alkyl-propoxylated sulfates.

When an anionic surfactant is present in the bleaching compositions, the compositions of the present invention, in particular laundry detergents, typically contain more than 1 wt%, more preferably more than 3 wt%, of the anionic surfactant and the concentration of the anionic surfactant. % of the substance is at most 40% by weight, more preferably at most 20% by weight.

Highly preferred cationic surfactants suitable for use in the present invention are the water-soluble quaternary ammonium compounds of the formula:

R ₁ R ₂ R ₃ R ₄ N ⁺ X wherein R 1 is C ₈ -C ₁₆ alkyl R 2, R 3 and R ₄ are independently C 1 -C ₄ alkyl, C 1 -C ₄ hydroxyalkyl, benzyl, and - (C ₂ H ₄₀ ) _x H where x has a value of 2 to 5, and X is an anion. Most of R ₂ , R ₃ or R ₄ is benzyl.

When cationic surfactants are included in the bleaching compositions of the present invention, their concentration is greater than 0.2 wt%, more preferably greater than 1 wt% and less than 25 wt%, more preferably less than 8 wt%.

When ampholytic surfactants are included in the bleaching compositions of the present invention, their concentration is greater than 0.2 wt%, more preferably greater than 1 wt% and less than 15 wt%, more preferably less than 10 wt%.

When zwitterionic surfactants are included in the bleaching compositions of the present invention, their concentration is greater than 0.2 wt%, more preferably greater than 1 wt% and less than 15 wt%, more preferably less than 10 wt% .

When the semipolar nonionic surfactants are present in the bleaching compositions of the present invention, their concentration is greater than 0.2% by weight, more preferably greater than 1% by weight and less than 15% by weight, more preferably less than 10% by weight. .

The bleaching compositions of the present invention may also contain from 0.001 to 100% of one or more (preferably a mixture of two or more) branched, medium molecular weight, preferably branched, alkyl alkoxyalcohols of the formula:

·· ······· · · · · · · · · · · ·

RR ¹ R ²

CH ₃ CH 2 (CH ₂ ) _w CH (CH ₂ ) _{J (} CH (CH 2) _y CH (CH ₂ ) _z (EO / PO) 4 H branched alkyl sulfates having an average molecular weight of the formula:

RR ¹ R ²

I I I

CH ₃ CH ₂ (CH ₂ ) _w CH (CH ₂ ) _x CH (CH ₂ ) _y CH (CH ₂ ) _from OSO3M and branched average molecular weight alkyl sulphates of the general formula:

RR ¹ R ² III

CH ₃ CH ₂ (CH ₂ ) _w CH (CH 2) _x CH (CH ₂ ) _y CH (CH ₂ ) _z (EO / PO) _{m and} OSO ₃ M where the total number of carbon atoms in the branched primary alkyl groups R ¹ , and R ² , but without the carbon atoms to which the alkoxy groups (EO / PO) are bonded, is 14 to 20, and wherein for this surfactant mixture the average total carbon atoms in the branched primary alkyl groups of the above formula 14.5 to 17.5 (preferably greater than 15 to 17); R ¹ , R ¹ and R ² are independently selected from the group consisting of hydrogen, C 1 -C ₃ alkyls, and mixtures thereof, and preferably all of these substituents are methyl; when all R ¹ , R ¹ , and R ² are not hydrogen and when z is 1, either R or R ^{1 is not} hydrogen. M is a water-soluble cation and or more than one type of cation, for example a mixture of sodium and potassium cations. Index w is an integer from 0 to 13; x is an integer from 0 to 13; y is an integer from 0 to 13; z is 1 or a natural number greater than 1; the sum of w + x + y + z is a number ranging from 8 to 14. EO and PO are ethyleneoxy and propyleneoxy groups of the following formulas:

• • • •

CH ₃ CH ₃

II -CHCH2O- or _-CH2 CHOJako alkoxy group attached to branched chain alkyl with an average molecular weight, however, to use other alkoxy, inter alia 1,3-propyleneoxy, butoxy, and mixtures thereof.

The branched average molecular weight surfactants are preferably mixtures forming a surfactant system. Thus, if the surfactant system comprises an alkoxylated surfactant, the m index indicates the average degree of alkoxylation in this surfactant mixture. The index m is at least 0.01, preferably the index is at least 0.1, more preferably at least 0.5, most preferably the index is in the range of 1 to 30, preferably to 10, more preferably to 5. For a branched surfactant system with an average molecular weight containing only alkoxylated surfactants, the m index is an average degree of alkoxylation * equal to m, or it may be a specific chain with alkoxylation (e.g. ethoxylation and / or propoxylation) of a number of units exactly equal to m .

Preferred branched average molecular weight surfactants of the present invention suitable for use in the surfactant systems of the present invention have the general formula:

čh ₃

CH ₃ (CH ₂ ) _and CH (CH 2) b CH 2 (EO / PO) _m OSO ₃ M or the general formula:

ch ₃ ch ₃ 1 I

CH ₃ (CH 2) d CH (CH 2) _e CHCH ₂ (EO / PO) _n ) SO _J M where a, b, d, and e are natural numbers for which a + b is 10 to 16 and ad + e is 8 to 14; M is selected from the group consisting of sodium, potassium, magnesium, ammonium or substituted ammonium cation, and mixtures thereof.

The surfactant systems of the present invention comprising branched, medium molecular weight surfactants are preferably prepared in two embodiments. A first preferred embodiment comprises branched average molecular weight surfactants made from starting materials containing 25% or less branched average molecular weight alkyl. Therefore, before admixing other conventional surfactants, the branched surfactant component will be a branched chain average molecular weight of 25% or less of the surfactant molecules that are branched.

The second preferred embodiment comprises branched average molecular weight surfactants made from starting materials containing 25% to 70% of branched average molecular weight alkyl. Therefore, before admixing other conventional surfactants, the mid-chain branched surfactant component will contain 25% to 70% of the branched surfactant molecules.

The bleach surfactant systems of the present invention may also contain 0.001 wt%, preferably at least 1 wt%, more preferably at least 5 wt%, most preferably 10 to 100 wt%, preferably up to 60 wt%, more preferably up to 30% by weight, based on the total weight of these systems, of one or more (preferably a mixture of two or more) branched alkyl surfactants which are aryl sulfonate surfactants, preferably aryl surfactants with benzene cycles of the general formula

wherein L is an acyclic hydrocarbon radical of 6 to 18 carbon atoms; R ¹ , R ² , and R ³ are independently hydrogen or C 1 -C ₃ alkyl, unless R ¹ and R ² are attached to the end of L; M is a water-soluble cation with charge q, and b have values such that the charge neutrality condition is met.

Other detergent ingredients

The following are examples of other detergent ingredients (co-builders) that are suitable as components of the bleaching compositions of the present invention, especially detergents used for fabric washing. These other ingredients include, but are not limited to, extenders, optical brighteners, soil release polymers, dye transfer agents, dispersants, enzymes, suds suppressors, dyes, fragrances, filler salts, hydrotropes, photoactivators, fluorescent agents, fabric conditioning agents, hydrolyzable surfactants, preservatives, antioxidants, chelating agents, stabilizers, fabric shrinking agents, fabric squeezing agents, germicides, fungicides, anticorrosive agents, and mixtures thereof.

Adjusters

The bleaching compositions of the present invention preferably comprise one

or more detergent builders or detergent builder systems. When present, the builder content is usually at least 1% by weight, preferably at least 5% by weight, more preferably in the range of 10 to 80%, preferably up to 50% by weight, more preferably up to 30% by weight, based on the total weight of the preparation.

The concentration of the extender may vary within wide limits depending on the end use of the formulation and its physical form. When extending agents are present, the formulations generally comprise at least 1% extender. Conventional extender contents are in the range of 5 to 50% by weight, more usually in the range of 5 to 30% by weight, based on the total weight of the formulation. Granular formulations usually contain 10 to 80 wt%, more typically 15 to 50 wt% detergent builder. However, lower or higher contents of extenders are not excluded.

Inorganic detergent builders or phosphorous detergent builders include, but are not limited to, the alkali ammonium and alkanolammonium salts of polyphosphates (exemplified by tripolyphosphates, pyrophosphates, and glassy polymeric metaphosphates), phosphonates, phytic acid, silicates, carbonates, and carbonates (including sulfites). However, extenders that do not contain phosphorus compounds are required in some areas. Significantly, the compositions of the present invention surprisingly work well, even in the presence of so-called weak extenders such as citrates, or when zeolites or layered silicates are used as extenders.

Examples of silicate extenders are alkali metal silicates, especially alkali metal silicates having a SiO ₂ : Na ₂ O ratio in the range of 1.6: 1 to 3.2: 1 and layered silicates, such as sodium layered silicates, described in U.S. Patent 4,664,839, by Rieck, issued May 12, 1987. Crystalline layered silicate manufactured by Hoechst has the trade name NaSKS-6 (commonly abbreviated herein as SKS-6). Unlike zeolite extenders, the NaSKS-6 silicate extender does not contain aluminum. NaSKS-6 is a layered silicate with a 5-Na ₂ SiO ₂ structure. It can be prepared by the methods described in documents DE-A-3 417 649 and DE-A-3 742 043. SKS-6 is a highly preferred layered silicate suitable for use in the processes of the present invention, but other such layered silicates such as these compounds of formula NaMSi _x 02 _{x + 1} . yH ₂ O wherein M is a cation of sodium or hydrogen, x is a number in the range 1.9 to 4, preferably 2, and y is a number in the range 0 to 20, preferably 0. Very suitable for use in the methods of the invention there are various other layered silicates manufactured by Hoechst including NaSKS-5, NaSKS-7 and NaSKS-11, which are α, β, and γ forms of silicates. As mentioned above, the most preferred for use in the methods of the invention is S-Na ₂ SiO ₅ (NaSKS-6). Other silicates may also be suitable, such as magnesium silicate, which may serve as a brittleness reducing agent in granular formulations, as a stabilizer for oxygen bleaching formulations, and as a component of foam control systems.

Examples of the use of carbonate builders, which are alkali metal and alkaline earth metal carbonates, are described in German Patent Application No. 2,321,001, published November 15, 1973.

Aluminosilicate builders are suitable for use in the present invention. Aluminosilicate builders are an important component in most conventional high performance granular detergents, and can also be important liquid detergent builders. Aluminosilicate extenders are substances of the general empirical formula:

[M _z (zA10 ₂ ) _y ] -xH ₂ 0 where z and y are natural numbers that are equal to or greater than

6, the molar ratio of z to y is in the range of 1.0 to 0.5, and x is a natural number from 15 to 264.

Suitable aluminosilicate ion exchangers are also produced. These aluminosilicates can be crystalline or amorphous and can either be naturally occurring aluminosilicates or can be synthesized. A method for producing aluminosilicate ion exchangers is disclosed in U.S. Patent No. 3,985,669 to Krummel et al., Issued October 12, 1976. Preferred synthetic crystalline aluminosilicate ion exchangers suitable for use in the methods of the present invention are manufactured under the designation Zeolite A, Zeolite ® ( Β), Zeolite MAP and Zeolite X. A particularly preferred crystalline aluminosilicate ion exchanger has the general formula:

Na ₁₂ [(A10 ₂₎ i2 (Si0 ₂₎ I _2] H ₂ 0 wherein x is from 20 to 30, especially 27. This material is known as Zeolite A. For use in the present invention are also useful dehydrated zeolites (x = 0-10). Preferably, the particle size of these aluminosilicates is 0.1-10 µm.

Organic detergent builders useful in the present invention may be various polycarboxylate compounds. The term polycarboxylate as used herein refers to compounds having a plurality of carboxy groups in the molecule, preferably at least 3 carboxy groups. The polycarboxylate builder may generally be included in the formulation in acid form, but may also be included in the formulation in the form of a neutral salt. When a salt is used, it is an alkali salt such as sodium potassium and lithium salt, or an alkanolammonium salt.

Polycarboxylate builders are various types of substances. One important type of polycarboxylate extenders are the ether polycarboxylates, including oxydisuccinates, described in U.S. Patent No. 3,128,287 to Berg, issued April 7, 1964;

No. 3,635,830 to Lamberti et al., issued Jan. 18, 1972; and U.S. Patent No. 3,936,448 to Lamberti, issued Feb. 3, 1976. See also TMS / TDS extenders described in U.S. Pat. No. 4,663,071, Bush et al., Issued May 5, 1987. Suitable ether polycarboxylates are the cyclic compounds, especially the alicyclic compounds described in U.S. Patent No. 3,923,679 to Rapko, issued December 2, 1975; U.S. Patent 4,158,635, Crutchfield et al., issued June 19, 1979; U.S. Patent 4,120,874, Crutchfield et al., issued October 17, 1978; and U.S. Patent No. 4,110,903 to Crutchfield et al., issued July 25, 1978.

Other useful detergent builders include etherhydroxypolycarboxylates, copolymers of maleic anhydride with ethylene or vinyl methyl ethers, 1,3,5-trihydroxybenzene-2,4,6-trisulfonic acid and carboxymethyloxysuccinic acid, various alkali metal salts, ammonium salts and substituted ammonium salts of ethylene acetic acid and ethylacetate salts. nitrilotriacetic acids as well as polycarboxylates such as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid, carboxymethylsuccinic acid and soluble salts thereof.

Citrate builders, for example citric acid and its soluble salts (especially sodium salt), are polycarboxylate builders of particular importance to conventional high performance liquid detergents due to their availability from renewable natural sources and due to their biodegradability. Citrates can also be used in granular formulations, especially in combination with zeolite and / or layered silicate based extenders.

Oxydisuccinates are also suitable in the compositions of the present invention.

Also suitable for use in the bleaching compositions of the present invention are 3,3-dicarboxy-4-oxa-1,6-hexanedioates and derivatives thereof described in U.S. Patent No. 4,566,984 to Bush, issued Jan. 28, 28, 1986. extender based on succinic acid 76 «» 99 9 * · <

• 9 · 9

995 are, inter alia, C5-C20 alkyl and alkenylsuccinic acids and their salts. A particularly preferred compound of this type is dodecenylsuccinic acid. Examples of succinic acid extenders are lauryl succinate, myristyl succinate, palmityl succinate, 2-dodecenyl succinate (preferred), 2-pentadecenyl succinate and the like. Preferred extenders of this type are the laurylsuccinates described in the European patent application

No. 86200690.5 / 0 200 263, published Nov. 5, 1986.

Other suitable polycarboxylates are described in U.S. Patent 4,144,226, Crutchfield et al., Issued September 13, 1979, and U.S. Patent 3,308,067, Diehl, issued March 7, 1967. See also Diehl, U.S. Pat. No. 3,723,322.

Fatty acids, for example C12-C18 monocarboxylic acids, may also be included in the compositions of the present invention, either alone or in combination with the aforementioned extenders, particularly citrate and / or succinate extenders, thereby enhancing the effect of the extenders. Such use of fatty acids generally results in a decrease in foaming, which should be taken into account when determining the overall composition of the formulation.

Where phosphorus-containing extenders can be used, and especially in detergent bars used for handwashing, various alkali metal phosphates such as the well-known sodium triphosphate, sodium pyrophosphate and sodium orthophosphate may be used. Phosphonate extenders such as ethane-1-hydroxy-1,1-diphosphonate and other known phosphonates can also be used (see, for example, U.S. Patent Nos. 3,159,581; 3,213,030; 3,422,021; 3,400,148 and 3,422,137).

Chelating agents

The bleaching compositions of the present invention may also contain one or more iron and / or manganese removal chelating agents. These chelating agents may be selected from the group consisting of aminocarboxylates, aminophosphonates, polysubstituted

«· • · Φ • · • · • • • * • • • · « • • • · · • • • · • · • • · • · • • · • • »Λ • · • t ·

Aromatic chelating agents, mixtures of these substances, all of which are described in more detail below. Without being bound by theory, we believe that the advantage of these materials is in their extraordinary ability to remove iron and manganese ions from washing solutions by forming soluble chelates.

Examples of suitable chelating agents and concentrations in use are set forth in U.S. Patent Nos. 5,576,282 and 5,728,671.

The biodegradable chelating agent preferred for use in the methods of the present invention is ethylenediamine disuccinate HDDS, especially its [S, S] isomer described in U.S. Patent No. 4,704,233 to Hartman and Perkins, issued November 3, 1987.

The compositions of the present invention may also contain water-soluble salts of methyl glycine diacetic acid (MGDA) or the acid itself as chelating agents or as extenders used simultaneously with, for example, insoluble extenders such as zeolites, layered silicates and the like.

When used, the chelating agents will generally have a concentration of from about 0.1% to about 15% by weight of the bleaching compositions of the present invention, more preferably about 3.0% by weight.

Dye transfer inhibiting agents

The bleaching compositions of the present invention may also contain one or more dye transfer inhibiting compounds or agents to inhibit the transfer of dissolved or suspended dyes during laundering and fabric conditioning from one fabric to another.

Suitable polymeric dye transfer inhibiting agents are polyvinylpyrrolidones, polyamine N-oxides, copolymers of Nvinylpyrrolidone and N-vinylimidazole, polyvinyloxazolidones and polyvinylimidazoles or mixtures thereof. Examples of such dye transfer inhibiting agents are described in U.S. Patent Nos. 5,707,950 and 5,707,951.

»Fe fe fe fe fe fe fe fe fe t t t t t t t t t t t t t t t t * ··· »· ··· ·

Other suitable dye transfer inhibiting agents are crosslinked polymers. Crosslinked polymers are polymers whose backbones are to some degree linked together. The respective linkers may be of a chemical or physical nature, with the active groups present on both the backbone and the branches. Crosslinked polymers are described in Journal of Polymer Science, 22, 1035-1039.

In one embodiment, the cross-linked polymers are prepared to form a three-dimensional rigid structure that can retain dyes in its pores.

In another embodiment, the crosslinked polymers can swell dyes.

Suitable cross-linked polymers are described in European Patent Application No. 94870213.9, which is currently pending.

The addition of such polymers also increases the efficiency of the enzymes contained in the bleaching compositions of the present invention.

Dye transfer inhibiting agents are capable of complexing or absorbing dye-forming molds washed out of fabrics before they can bind to other components of the laundry system.

When present, the dye transfer inhibiting agents in the bleaching compositions of the present invention are present in concentrations ranging from 0.0001 wt%, more preferably from 0.01 wt%, most preferably from 0.05 wt% to 10 wt%. %, more preferably up to 2 wt.%, most preferably up to 1 wt.%.

Dispersanty

The bleaching compositions of the present invention may also contain dispersants. Water-soluble organic salts of polymeric or copolymeric acids are suitable, wherein the respective polycarboxylic acids contain at least two carboxyl groups separated by a maximum of two carbon atoms.

Polymers of this type are described in GB-A-1,596,756. Examples of such salts are polyacrylates of molecular weight

* ·· ·· «· • · * • · • « • · » »· • · «· »'· · · · · · ··· a and a a · a

2000 to 5000 and their copolymers with maleic anhydride having a molecular weight of 1000 to 100 000.

In particular, copolymers of acrylates and methyl acrylates having a molecular weight of 4000 in a concentration ranging from 0.5 to 20% by weight can be added to the compositions of the invention.

The compositions of the invention may comprise a calcium soap peptizing agent having a lime soap dispersant power (LSDP) as defined below, at most 8, preferably at most 7, most preferably at maximum 6. The calcium soap base is preferably present in a concentration of 0 to 20% by weight.

The numerical measure of the calcium soap dispersing efficiency is given by the calcium soap dispersing efficiency (LSDP) determined using the calcium soap dispersing efficiency test described in the prior art in H.C. Borghetty and C.A. Bergman, J.

Am. Oil. Chem. Soc., 27, 88-90 (1950). This calcium soap efficacy test commonly used by those skilled in the art is described, for example, in the following review publications: WN Linfield, Surfactant Science Series, Volume 7, p. 3; WN Linfield, Tenside Surf. det., 27, 159-163 (1990); and MK Nagarajan, WF Masler, Cosmetics and Toiletries, 104, 71-73, (1989). LSDP is expressed as a percentage by weight of the dispersant to sodium oleate required to disperse the calcium soap deposits formed by 0.025 g of sodium oleate in 30 ml of water with an equivalent hardness equivalent to 0.333% CaCO ₃ (Ca: Mg = 3: 2).

Surfactants with good peptic activity of calcium soap are some amine oxides, betaines, sulfobetaines, alkyl ethoxy sulfates and ethoxylated alcohols.

Examples of surfactants having a maximum LSDP of 8 suitable for use in the present invention are C 16 -C 18 dimethylaminoxides, C 12 -C 18 alkyl ethoxy sulfates having an average degree of ethoxylation of 1 to 5, especially C 12 -C 15 alkyl ethoxy sulfate surfactants having an degree of ethoxylation 3 (LSDP) = 4), and C14-C15 ethoxylated alcohols with an average degree of ethoxylation of either 12 (LSDP = 6) or 30, manufactured by BASF GmbH under the trade names Lutensol A012 and Lutensol A030.

Polymeric calcium soaps with peptizing effects suitable for use in the practice of this invention are described in the prior art by M. K. Nagarajan and W. F. Masler, Cosmetics and Toiletries, 104, pp. 71-73, (1989).

Hydrophobic bleaching agents such as 4- [N-octanoyl-6-aminohexanoyl] benzenesulfonate, 4- [N-nonanoyl-6-aminohexanoyl] benzenesulfonate, 4- [N-decanoyl-6-aminohexanoyl, may also be used as calcium soaps with peptizing effects. ] benzenesulfonate and mixtures thereof; and nonanoyloxybenzene sulfonate together with hydrophilic / hydrophobic bleaching agents.

Enzymes

The bleaching compositions of the present invention may contain, in addition to amylase, one or more enzymes that enhance the efficiency of fabric cleaning and / or fabric care. These enzymes may be proteases, amylases, cellulases and lipases. They can be added to the bleaching compositions in the form of non-aqueous liquids, suspensions or beads. Another suitable type of enzyme comprises enzymes in the form of a dense suspension of the enzyme in nonionic surfactants, such as enzymes manufactured by Novo Nordisk under the trade name SL or microencapsulated enzymes produced by Novo Nordisk under the trade name LDP. Suitable enzymes and concentrations for use are described in U.S. Patent No. 5,576,282.

Particularly suitable for use in the methods of the invention are the enzymes added to the compositions of the invention in the form of conventional enzyme beads. These beads generally have a size in the range of from 100 to 1000 µm, more preferably from 200 to 800 µm, and are suspended in the non-aqueous liquid phase of the formulation. As has been found, the beads in the compositions of the present invention are particularly stable in comparison with other forms of enzymes in terms of maintaining long enzymatic activity. Formulations using enzymes in the form of beads, therefore, do not need to contain conventional enzyme stabilizers, which must often be used when enzymes are added to liquid aqueous detergents.

Examples of suitable enzymes are hemicellulases, peroxidases, proteases, cellulases, xylanases, lipases, phospholipases, esterases, cutinases, pectinases, keratanases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases, pentosanases, hyaluronases, malanases, malanasides, ianasase, malanases, chondroitinase, laccase, and known amylases, or mixtures thereof. A preferred combination for use in the methods of the invention is a bleaching composition comprising a mixture of conventional enzymes such as protease, lipase, cutinase and / or cellulase in conjunction with amylase.

Examples of such suitable enzymes are described in U.S. Patent Nos. 5,576,282, 5,728,671, and 5,707,950

Suitable proteases are subtilisins, which are obtained from some B. subtilis and B. licheniformis (subtilisin BPN and BPN ') bybacteria. A suitable protease obtained from a Bacillus strain having a maximum activity at pH 8-12 is produced as ESPERASE® by Novo Industries A / S, Denmark, hereinafter referred to as Novo. The preparation of this enzyme and analogous enzymes is described in GB 1 243 784 from Novo. Other suitable proteases are Alcalse®, Durazym® and Savinase®, manufactured by Novo and Maxatase®, Maxacal®, Properase® and Maxap® (Maxacal is produced by proteosynthesis) from Gist-Brocades. Proteolytic enzymes are also modified bacterial serine proteases, one of which is described in European Patent Application No. 87 303761.8, filed April 28, 1987 (in particular at pages 17, 24 and 98), and is referred to herein as Protease B, and others in European Patent Application No. 199,404, Venegas, published October 29, 1986, relating to a modified bacterial serine proteolytic enzyme, which is herein referred to as Protease A. More preferably, the enzyme is referred to herein as Protease C, and which is a variant of an alkaline serine protease obtained from a Bacillus strain, wherein the lysine at position 27 is replaced by arginine, the tyrosine at position 104 is replaced by valine, the serine at position 123 is replaced by asparagine and alanine in position 274 is replaced by threonine. Protease C is described in EP 90915958: 4, which corresponds to WO 91/06637, published May 16, 1991. Genetically modified variants of enzymes, in particular Protease C, can also be used in the methods of the invention. See also Proteases NCIMB 40338 for use in a high pH environment obtained from Bacillus strains described in WO 93/18140 of Novo form. Enzymatic detergents containing a protease, one or more other enzymes, and a reversible protease inhibitor are described in WO 92/03529 to Novo. If desired, a protease with reduced adsorption and increased hydrolysability as described in WO 95/07791 to Procter & Gamble may be used. Recombinant trypsin-type proteases for use in detergents suitable for use in the methods of the invention are described in WO 94/25583 to Novo.

The protease encoded as Protease D is a variant of a carbonyl hydrolase comprising amino acid sequences of unknown nature derived from the starting carbonyl hydrolase by substituting different amino acids for different amino acids at position +76 in said carbonyl hydrolase, preferably also in combination with substitutions of one or more amino acid residues at positions +99, +101, +103, +104, +107, +123, +27, +105, +109, +128, +128, +135, +156, +166, +195, +197, +204 , +206, +210, +216, +217, +218, +222, +260, +265, and / or +274 corresponding positions according to Bacillus amyloliquefaciens subtilisin numbering as described in WO 95/10615 by Genencor International, published April 20, 1995. Also suitable for use in the methods of the invention are the proteases disclosed in EP 251 446 and WO91 / 06637 and the BLAP® protease described in WO91 / 02792. The content of proteolytic enzymes in the bleaching compositions of this invention is 0.0001 to 2% by weight, preferably 0.001% by 0.2% by weight, more preferably from 0.005 to 0.1% by weight. % based on the total weight of the preparation.

Suitable proteases are also described in WO 95/30010, Procter & Gamble Company, published Nov. 9, 1995; WO 95/30011, Procter & Gamble Company, published November 9, 1995; and International Patent Application WO 95/29979, Procter & Gamble Company, published November 9, 1995.

Other particularly useful proteases are multiply substituted protease variants in which amino acid residues are replaced by other naturally occurring amino acid residues at positions corresponding to position 103 of the subtilisin obtained from Bacillus amyloliquefaciens, and wherein further amino acid residues are replaced by other naturally occurring amino acid residues in one or more positions corresponding to positions 1, 3, 4, 8, 9, 10, 12, 13, 16, 17, 18, 19, 20, 21, 22, 24, 27, 33, 37, 38, 42, 43, 48, 55, 57, 58, 61, 62, 68, 72, 75, 76, 77, 78, 79, 86, 87, 89, 97, 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, 246, 247, 248, 249, 251, 252, 253, 254, 255, 256, 257, 258, 259, 260, 261, 262, 263, 265, 268, 269, 270, 271, 272, 274 a

275 of the subtilisin obtained from Bacillus amyloliquefaciens, wherein in said protease variant the amino acid residue is substituted at positions corresponding to positions 103 and 76, substitution of the amino acid residues with other amino acid residues at positions 27, 99, 101, 104,

107, 109, 123, 128, 166, 204, 206, 210, 216, 217, 218, 222, 260

265 or 274 of the subtilisin obtained from Bacillus amyloliquefaciens and / or multiple substituted protease variants in which the amino acid residues are replaced by other naturally occurring amino acid residues at positions corresponding to positions 62, 212, 230, 232, 252 and 257 of the Bacillus-derived subtilisin. j quefaciens as described in the international patent applications of Procter & Gamble Company WO 99/20727, WO 99/20726 and WO 99/20723, all of which were filed on October 13, 1998. More preferably, the protease is one of the following variants with these: combinations of substitutions:

12/76/103/104/130/222/245/261;

62/103/104/159/232/236/245/248/252;

62/103/104/159/213/232/236/245/248/252;

62/101/103/104/159/212/213/232/236/245/248/252;

68/103/104/159/232/236/245;

68/103/104/159/230/232/236/245;

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;

68/103/104/159/210/232/236/245/248/252;

68/103/104/159/213/232/236/245;

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.

More preferably, the protease is one of the following variants with the following combinations of substitutions:

12R / 76D / 103A / 104T / 130T / 222S / 245R / 261D; 62D / 103A / 104I / 159D / 232V / 236H / 245R / 248D;

62D / 103 A / 1041 / 159D / 213R / 232V / 236H / 245R / 248D;

71 / 103A / 104I / 159D / 209W / 23 2V / 23 6H / 245R;

68A / 76D / 103A / 1041 / 159D / 213R / 232V / 236H / 245R / 260A;

A / 103 A / 1041 / 159D / 213E / 232V / 236H / 245R / 248D; 68A / 103A / 1041 / 159D / 183D / 232V / 236H / 245R / 248D / 252K;

68A / 103 A / 1041 / 159D / 232V / 236H / 245R; 68A / 103A / 104I / 159V / 230V / 232V / 236H / 245R; 68A / 103A / 104I / 159D / 232V / 236H / 245R / 257V;

68A / 103A / 104I / 159D / 213G / 232V / 236H / 245R / 248D;

68A / 103A / 104I / 159D / 185D / 232V / 236H / 245R / 248D;

68A / 103A / 104I / 159D / 185D / 210L / 232V / 236H / 245R / 248D; 68A / 103 / 104I / 159D / 21OL / 232V / 236H / 245R / 248D / 252K;

68A / 103 A / 1041 / 159D / 213G / 232V / 236H / 245R;

98L / 103 71/1041 / 159D / 232V / 236H / 245R / 248D;

98L / 102A7102A / 104I / 159D / 212G / 232V / 236H / 245R / 248D / 252K;

101G / 103A / 104I / 159D / 232V / 236H / 245R / 248D / 252K;

102A / 103A / 1041 / 159D / 232V / 236H / 245R / 248D / 252K;

103 71/1041 / 159D / 230V / 236H / 245R;

103 71/1041 / 159D / 232V / 236H / 245R / 248D / 252K;

103 A / 1041 / 159D / 217E / 232V / 236H / 245R / 248D / 252K;

103 7Y / 1041 / 130G / 159D / 232V / 236H / 245R / 248D;

103A / 1041 / 131V / 159D / 232V / 236H / 245R / 248D / 252K;

103A / 104I / 159D / 213R / 232V / 236H / 245R / 248D; and 103 71/1041 / 159D / 232V / 236H / 245R.

Most preferably, the protease is a variant with this combination of substitutions: 101/103/104/159/232/236/245/248/252, preferably 101G / 103A / 1041 / 159D / 232V / 236H / 245R / 248D / 252K.

• · · · ·

Cellulases suitable for use in the methods of the invention are both bycterial cellulases and fungal derived cellulases. Their optimum efficiency is preferably at a pH in the range of 5 to 9.5. Suitable cellulases are described in U.S. Patent No. 4, 435,307 to Barbesgoard et al., Which also discloses cellulase obtained from Humicola insolens. Suitable cellulases are also disclosed in GB-A-2.075.028; GB-A-2.095.275 and DE-OS-2.247.832.

Examples of such cellulases are cellulases obtained from a microbial strain of Humicola insolens (Humicola grisea var. Thermoidea), in particular from the DSM 1800 species of this microorganism strain.

Other suitable cellulases are cellulases obtained from Humicola insolens with a molecular weight of about 50 kDa, with an isoelectric point of 5.5, containing 415 amino acid residues; and an endoglucanase having a molecular weight of about 43 kDa from Humicola insolens DSM 1800, exhibiting cellulase properties. This preferred endoglucanase comprises the amino acid sequence described in WO 91/17243. Suitable cellulases are EGIII cellulases obtained from Trichoderma longibrachiatum, described in WO 94/21801 by Genencor, published Sep. 29, 1994. Particularly suitable cellulases are cellulases which are color-friendly to treated fabrics. Examples of such cellulases are cellulases described in the European patent application

No. 91202879.2, published Nov. 6, 1991 (Novo). Carezyme and Celluzyme, manufactured by Novo Nordisk A / S, are also particularly suitable. See also WO91 / 17243.

Peroxidases known in the art are, for example, horseradish peroxidase, ligninase and haloperoxidase such as chloro bromo-peroxidase. Peroxidase-containing bleaching agents are described, for example, in US Patent Nos. 5,576,282, 5,728,671 and 5,707,950, in International Patent Applications WO 89/099813,

WO 89/09813, European Patent Application No. 91202882.6, filed Nov. 6, 1991, and European Patent No. 96870013.8, issued Feb. 20, 20, 1886. A laccase is also suitable.

·· · ···· · · · ·

Preferred peroxidase enhancers are substituted phenthiazines and phenoxazines, particularly 10phenothiazinepropionic acid (PPT), 10-ethylphenothiazine-4-carboxylic acid (EPC), 10-phenoxazinepropionic acid (POP), 10methylphenoxazine (described in WO 94/12621) and substituted syrups (C ₃ -C ₅ alkylsyringates) and phenols. Preferred sources of hydrogen peroxide are sodium percarbonate and hydrogen peroxide.

These peroxidases are usually present in the bleaching compositions in concentrations of from 0.0001 to 2% by weight, based on the total weight of the bleaching composition.

Other preferred enzymes that may be included in the bleaching compositions of this invention are lipases. Lipases suitable for use in detergents are those enzymes produced by the Pseudomonas family of microorganisms such as Pseudomonas stutzeri ATCC 19.154, described in British Patent No. 1,372,034. This lipase is manufactured by Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trademark Lipase P Amano, hereinafter referred to as Amano-P. Other suitable industrially digested lipases are Amano-CES, a lipase from Chromobacter viscosum, for example Chromobacter viscosum var. lipolyticum NRRLB 3673, manufactured by Toyo Jozo Co., Tagata, Japan; Chromobacter viscosum lipases manufactured by Biochemical Corp., USA. and Disoynth Co., The Netherlands, and lipases from Pseudomonas gladioli.

Particularly suitable lipases are lipases such as M1 Lipase® and Lipomax® (Gist-Brocades), Lipolyse® and Lipolase ultra® (Novo), which are very effective when used in combination with the compositions of the invention.

Cutinases [EC 3.1.1.50] are suitable, which can be considered as a special kind of lipase, namely lipases that do not require interfacial activation. The addition of cutinase to bleaching agents is described, for example, in WO 88/09367 (Genencor).

··· · · · · · ·

Lipases and / or cutinases are normally present in the bleaching compositions at concentrations from 0.0001 to 2% by weight, based on the total weight of the bleaching composition.

The presence of known amylases (and and / or β) may be due to their ability to remove stains of sugary materials. WO 94/02597 to Novo Nordisk A / S published February 3, 1994 discloses cleaning compositions containing amylase mutants. See also WO 94/18314, Genencor, published August 18, 1994, and WO 95/10603, Novo Nordisk A / S, published April 20, 1995. Other amylases suitable for use in bleaching compositions are the α-amylases, and βamylase. α-amylases are known in the art and include, but are not limited to, those described in U.S. Patent Nos. 5,003,257, European Patent 252,666, International Application WO 91/00353, French Patent FR 2,676,456, U.S. Pat. European Patent Specifications 285 123, 525 610, 368 341 and British Patent No. 1,296,839 (Novo). Other suitable amylases are enhanced stability amylase, including Purafact ox AM® amylase described in International Application WO 94/18314, published August 18, 1994, and International Application WO 96/05295, Genencor, published February 22, 1996, and amylase variants Novo Nordisk A / S, described in WO 95/10603, published April 1995.

Examples of industrially produced α-amylases are Termamyl®, Ban®, Fungamyl® and Duramyl® products manufactured by Novo Nordisk A / S Denmark. WO95 / 26397 describes other suitable amylases which are α-amylases with a specific activity at least 25% higher than the specific activity of Tetmamyl® at temperatures ranging from 25 ° C to 55 ° C and at a pH in the range of 8 to 10 as measured by the determination of α-amylase activity by the Phadebas® method. Other amylolytic enzymes with improved activity and thermostability properties are described in WO 95/35382.

The formulations of the present invention may also comprise manna-fcfcfcfcfcfcfcfcfcfcfcfcfcfcfc.

zu. Preferably, the mannose used is selected from the group consisting of three enzymes capable of decomposing mannose and derivatives thereof: EC 3.2.1.25, β-mannosidase, EC 3.2.1.78: endo-1,4-β-mannosidase, referred to as mannase, and EC 3.2 .1.100: 1,4-β-mannobiosidase, and mixtures thereof. (IUPAC, Classification and Enzyme nomenclature, 1992 ISBN 0-12-227165-3 Academic Press).

More preferably, the compositions of the invention may comprise β1,4-mannosidase (E.G. 3.2.1.78) called mannase. The term mannase or galactomannase sign is a mannase enzyme officially called mannan-endo-1,4-mannosidase, whose alternative names are β-mannase and endo-1,4-mannase, and which catalyses the non-specifically ongoing hydrolysis of 1,4-D-mannosidase bonds in mannan, galactomannan, glucomannan, and galactoglucomannan.

Mannases (EC 3.2.1.78) are a group of polysaccharases that degrade mannose and its derivatives and which are capable of cleaving chains containing mannose units, ie, they are capable of cleaving glycosidic bonds in mannan, glucomannan, galactomannan and galactoglucananates. Mannanes are polysaccharides with a backbone of mannose units linked by β-1,4-bonds; glucomannans are backbone polysaccharides composed of more or less likely alternating mannose and glucose units; galactomannans and galactoglucomannans are mannans and glucomannans with galactose side chains linked by α-1,6 bonds. These compounds may be acetylated.

The degradation of galactomannan and galactoglucomannan is facilitated by complete or partial removal of galactose side chains. The degradation of acetylated mannan, glucomannan, galactomannan, and galactoglucomannan is facilitated by total or partial deacetylation. Acetyl groups can be removed by alkaline reagents or by treatment with mannan acetyl esterases. Oligomers that are released by the action of mannanases or a combination of mannanase and α-galactosidase and / or mannanacetylesterase can be further degraded by treatment with β-mannosidase and / or β-glucosidase to form free maltose.

· · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · ·

Mannases have been detected in a number of Bacilius microorganisms. For example, Talbot et al., Appl. Environmental. Microbiol., 56, 3505-3510 (1990) discloses β-mannase derived from Bacillus stearothermophilus in dimeric form with a molecular weight of 162 kDa and an optimal activity at a pH in the range of 5.5 to 7.5, in Mendoza et al. et al., World J. Microbiol. Biotech., 10, 551-555 (1994) discloses a β-mannase derived from Bacillus subtilis with a molecular weight of 38 kDa, and an optimum activity at pH 5.0-5.5 and a pH of 4.8. JP03047076 describes a β-mannase derived from Bacillus sp., Having a molecular weight determined by gel filtration of 373 kDa, with an optimum activity at a pH in the range of 8 to 10 and a pI of 5.3 to 5.4. JP-63056289 describes the preparation of an alkaline, thermostable β-mannase, hydrolyzing β-1,4-Dmannopyranoside bonds, for example, in mannan to form mannooligosaccharides. JP-63036774 relates to a Bacillus FERM P-8856 microorganism that produces β-mannase and β-mannosidase at an alkaline pH range. JP-08051975 discloses alkaline βmannases originating from the alkalophilic microorganism Bacillus sp. AM-001. Purified mannase derived from Bacillus amyloliquefaciens, suitable for bleaching cellulose and paper, and a process for its preparation are described in WO 97/11164. WO 91/18974 discloses hemicellulases such as glucanase, xylanase or mannase, which are active at extreme pH and temperature. WO 94/25576 describes an enzyme from Aspergillus aculeatus, CBS 101.43, capable of producing mannase, which can be used to degrade or modify cell walls of plants or algae. WO 93/24622 discloses mannase isolated from Trichoderma reseei, suitable for bleaching lignocellulose pulps. Hemicellulose capable of degrading mannan-containing hemicelluloses is disclosed in WO 91/18974 and purified mannase derived from Bacillus amyloliquefaciens is described in WO 97/11164.

Preferably, the mannanase is an alkaline mannase described in greater detail below, more preferably a mannase of bacterial origin. The detergent compositions of the invention particularly preferably comprise an alkali mannase which may be mannase derived from Bacillus agaradhaerens NICMB 40482; mannase from Bacillus subtilis strain 168; mannase from Bacillus sp. 1633 and / or mannase from Bacillus sp. AAI12. The most preferred mannase for use in the detergent compositions of the present invention is mannase derived from Bacillus sp. 1633, filed in Danish patent application No. PA 1998 01340, which is pending at the same time as this patent application.

Alkali mannase means an enzyme having an enzymatic activity of at least 10%, preferably at least 25%, more preferably: at least 40%, with maximum activity at a pH in the range of 7-12, preferably at a pH in the range of 7.5-10, 5.

Alkaline mannase from Bacillus agaradhaerens microorganism NICMB 40482 is described in U.S. patent application Ser. No. 09 / 111,256.

i) a polypeptide produced by Bacillus agaradhaerens, NCIMB 40482; or (ii) a polypeptide comprising the amino acid sequences found at positions 32-343 of SEQ ID NO: 2 set forth in U.S. Patent Application Serial No. 09 / 111,256; or (iii) an analogue of the polypeptide of (i) or (ii) which is at least 70% homologous to said polypeptide, or derived from said polypeptide by substitution, deletion or addition of one or more amino acids, or immunologically reactive with a polyclonal antibody against said polypeptide. of the polypeptide in pure form.

Also included is a corresponding isolated mannanase polypeptide selected from the group consisting of:

a) a polynucleotide encoding a mannase polypeptide and comprising the nucleotide sequence shown as SEQ ID NO: 1 from nucleotide 97 to nucleotide 1029 of U.S. patent application Ser.

«» 91 * 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9

(b) substances homologous to (a);

c) polynucleotide molecules encoding a mannase polypeptide that is at least 70% identical to the amino acid sequence of SEQ ID NO: 2 from amino acid residue 32 to amino acid residue 343 of U.S. patent application Ser.

d) molecules complementary to a), b) or c); and

(e) nucleotide cleavage sequences of (a), (b), (c) or (d). Plasmid pSJ1678 containing a polynucleotide molecule (DNA sequence) encoding said mannase was transformed into an Escherichia coli strain which, in accordance with the Budapest Treaty on the International Recognition of the Deposit of Microorganisms for Purposes of Patent Procedure, was deposited on May 18, 1998 in Deutsche Sammlung von Mikroorganismen und Zellkulturen. Mascheroder Weg lb, D-38124 Braunschweig, Germany under number DSM 12180.

The second more preferred enzyme is mannase from Bacillus subtilis strain 168, which is described in U.S. Patent Application Serial No. 09 / 095,163. This mannase is

(i) encoded by a coding portion of a DNA sequence found in SEQ ID NO: 5 in US Patent Application No. 09 / 095,163 or an analogue thereof; and / or ii) a polypeptide comprising the amino acid sequence set forth in SEQ ID NO: 6 of U.S. Patent Application Serial No. 09 / 095,163; or (iii) an analogue of the polypeptides defined in (ii) which is at least 70% homologous to said polypeptide, or derived from said polypeptides by substitution, deletion or addition of one or more amino acids, or immunologically reactive with a polyclonal antibody against said polypeptides in pure form.

Also included is a corresponding isolated mannanase polypeptide selected from the group consisting of:

a) a polynucleotide encoding a manna polypeptide, φφφφ φφ · · · φ φ Φ <· φφφφ za and comprising the nucleotide sequence set forth as SEQ ID NO: 5 in US Patent Application Publication No. 09/95 256;

(b) substances homologous to (a);

c) polynucleotide molecules encoding a mannase polypeptide which is at least 70% identical to the amino acid sequence of SEQ ID NO: 6 of U.S. Patent Application Serial No. 09 / 095,163;

d) molecules complementary to a), b) or c); and

(e) nucleotide cleavage sequences of (a), (b), (c) or (d). A third more preferred mannase is described in Danish patent application No. PA1998 01340 .: This mannase is

i) a polypeptide produced by Bacillus sp., 1633; or ii) a polypeptide comprising the amino acid sequences set forth at positions 32-343 of Seq ID No. 2 of Danish Patent Application No. PA1998 01340; or (iii) an analogue of the polypeptide of (i) or (ii) which is at least 65% homologous to said polypeptide, or derived from said polypeptide by substitution, deletion or addition of one or more amino acids, or immunologically reactive with a polyclonal antibody against said polypeptide. of the polypeptide in pure form.

Also included is a corresponding isolated mannanase polypeptide selected from the group consisting of:

a) a polynucleotide encoding a mannase polypeptide and comprising the nucleotide sequence shown as SEQ ID NO: 1 from nucleotide 317 to nucleotide 1243 of Danish patent application No. PA1998 01340;

(b) substances homologous to (a);

(c) polynucleotide molecules encoding a mannase polypeptide which is at least 65% identical to the amino acid sequence of identification number 2 from amino acid residue 33 fl · ···· fl

94 to &quot; amino acid residue 340 &quot; of Danish Patent Application No. PA1998 01340;

d) molecules complementary to a), b) or c); and

(e) nucleotide cleavage sequences of (a), (b), (c) or (d). The plasmid pBXM3 containing a polynucleotide molecule (DNA sequence) encoding said mannase was transformed into an Escherichia coli strain which, in accordance with the Budapest Treaty on International Recognition of the Deposit of Microorganisms for Purposes of Patent, was deposited on 29 May 1998 in Deutsche Sammlung von Mikroorganismen und Zellkulturen GmbH, Mascheroder Weg Ib, D-38124 Braunschweig, Germany under number DSM 12197.

A fourth more preferred mannase is described in Danish patent application No. PA1998 01341 .: Tat mannase is

i) a polypeptide produced by Bacillus sp., 1633; or ii) a polypeptide comprising amino acid sequences located at positions up to 362 of SEQ ID NO: 2 in Danish Patent Application No. PA1998 01341; or (iii) an analogue of the polypeptide of (i) or (ii) which is at least 65% homologous to said polypeptide, or derived from said polypeptide by substitution, deletion or addition of one or more amino acids, or immunologically reactive with a polyclonal antibody against said polypeptide. of the polypeptide in pure form.

Also included is a corresponding isolated mannanase polypeptide selected from the group consisting of:

a) a polynucleotide encoding a mannase polypeptide and comprising the nucleotide sequence shown as SEQ ID NO: 1 from nucleotide 225 to nucleotide 1236 of Danish patent application No. PA1998 01341;

(b) substances homologous to (a);

(c) polynucleotide molecules encoding a polypeptide acting as a mannase that is at least 65% identical to the amino acid sequence of SEQ ID NO: 2 from amino acid residue 25; to amino acid residue 362 of Danish Patent Application No. PA1998 01341;

d) molecules complementary to a), b) or c); and

(e) nucleotide cleavage sequences of (a), (b), (c) or (d).

The plasmid pBXM3 containing a polynucleotide molecule (DNA sequence) encoding said mannase was transformed into an Escherichia coli strain which, in accordance with the Budapest Treaty on the International Recognition of Deposit of Microorganisms for Purposes of Patent, was deposited on October 7, 1998 in Deutsche Sammlung von Mikroorganismen und. Zellkulturen GmbH, Mascheroder Weg Ib, D-38124 Braunschweig, Germany under number DSM 12197.

When present in the compositions of the present invention, the mannose is preferably present in a concentration in the range of 0.0001 to 2% by weight, more preferably in the range of 0.0005 to 0.1% by weight, most preferably 0.001 to 2% by weight.

0.02 wt.%, Based on the total concentration of the formulation.

The compositions of the invention may also contain xyloglucanase. For the purposes of the present invention, xyloglucanases acting as endoglucanases specifically for xyloglucan are included in concentrations ranging from 0.001 to 1%, more preferably from 0.01 to 0.5%, based on the total weight of the preparation. Endoglucanase refers to the ability of an enzyme to hydrolyze 1,4-β-D-glycosidic bonds in any cellulose material such as cellulose, cellulose derivatives, lichenin, β-Dglucan, or xyloglucan. The ability to act as an endoglucanase or endoglucanase activity can be determined by methods known in the art, examples of which are given in WO 94/14953 and hereinafter. A unit of endoglucanase activity (e.g., CMCU, AVIU, XGU, or BGU) is defined as the ability to form 1 pmol of reducing sugar per minute from a glucan substrate, the glucane substrate being, for example, CMC (CMCU), acidic swollen Avicell (AVIU), xylo. Glucan (XGU) or Cereal-derived β-glucan (BGU). The determination of reducing sugars is carried out as described in WO 94/14953 and hereinafter. The substrate specific endoglucanase activity is determined in units per mg protein.

Enzymes having the highest XGU endoglucanase activity (xyloglucan specific activity below) are suitable. These enzymes are enzymes which:

(i) are encoded by a DNA sequence containing at least one of the following partial sequences or contained in at least one of the following partial sequences:

and) ATTCATTTGT GGACAGTGGC (sequence C. 1) (b) GTTGATCGCCATTGAACC (SEQ ID NO: 2) C) ACCCCAGCCG ACCGATTGTC (sequence C. 3) (d) CTTCCTTACC TCACCATCAT (sequence C. 4) E) TTAACATCTT TTCACCATG (Seq . 5) F) AGCTTTCCCT TCTCTCCCTT (sequence C. 6) G) GCCACCCTGG CTTCCGCTGC CAGCCTCC (Seq

(h) GACAGTAGCATCCAGCATT (SEQ ID NO: 8)

(i) AGCATCAGCC GCTTTGTAC (SEQ ID NO: 9)

(j) CCATGAAGTT CACCGTATTG (SEQ ID NO: 10)

(k) GCACTGCTTC TCTCCCAGGT (SEQ ID NO: 11)

(l) GTGGGCGGCC CCTCAGGCA (SEQ ID NO: 12)

m) ACGCTCCTCC AATTTTCTCT (SEQ ID NO: 13)

(n) GGCTGGTAG TAATGAGTCT (SEQ ID NO: 14)

o) GGCGCAGAGT TTGGCCAGGC (SEQ ID NO: 15)

(p) CAACATCCCC GGTGTTCTGG G (SEQ ID NO: 16)

(q) AAAGATTCAT TTGTGGACAG TGGACGTTGTCGCACATTG AACCAACCCC AGCCGACCGA

TTGTCCTTCC TTACCTCACC ATCATTTAAC ATCTTTTCAC CATGAAGCTT TCCCTTCTCT

CCCTTGCCAC CCTGGCTTCC GCTGCCAGCC TCCAGCGCCG CACACTTCTG CGGTCAGTGG

GATACCGCCCCGCCGGTGCTTCACCCTG TACAACGACC TTTGGGGCGA GACGGCCGGC

ACCGGCTCCC AGTGCACTGG AGTCGACTCC TACAGCGGCG ACACCATCGC

TTGTCACACC

AGCAGGTCCT GGTCGGAGTGCAGCAGCGT CAAGAGCTAT GCCAACG (SEQ ID NO: 17), or

(r) CAGCATCTCC ATTGAGTAAT CACGTTGGTG TTCGGTGGCC CGCCGTGTTG CGTGGCGGAG

GCTGCCGGGGACGGGTGGG GATGGTGGTG GGAGAGAATG TAGGGCGCCG TGTTTCAGTC

CCTAGGCAGG ATACCGGAAACCGTGTGGT AGGAGGTTTTAGGTTTCCA GGAGACGCTG

TATAGGGGAT AAATGAGATT GAATGGTGGC CACACTCAACCAACCAGGT CCTGTACATA

CAATGCATAT ACCAATTATCCTACCAAAAAAAAAAAAAAAAAAAAAAAAAA (SEQ ID NO: 18), or encoded by a DNA sequence homologous to these sequences and coding for a polypeptide with endoglucanase activity specific for xyloglucan, ) and derived from Aspergillus aculeatus, CBS 101.43, and exhibiting activity specifically for xyloglucan.

A phrase specifically for xyloglucan means that the endoglucanase enzyme exhibits the highest endoglucanase activity on the xyloglucan substrate, and preferably less than 75% of this activity, more preferably less than 50% of this activity and most preferably less than 25% of this activity on other cellulose containing substrates such as carboxymethylcellulose , cellulose, or other glucans.

Preferably, the specificity of endoglucanase to xyloglucan is further defined as the relative activity of releasing reducing sugars under optimal conditions that are met when the enzyme is incubated with xyloglucan and another test substrate. This specificity can be defined by the ratio of activity to xyloglucan to activity to β-glucan (XGU / BGU), activity to xyloglucan to activity to carboxymethylcellulose (XGU / CMCU), or activity to xyloglucan to activity to acidic swollen Avicell (XGU / AVIU), wherein the ratio is preferably greater than 50, and its value is 75, 90 or 100.

Phrases derived from as used herein,. concerns not only the endoglucanase produced by the strain.

CBS 101.43, but also endoglucanases encoded by a DNA sequence isolated from the CBS 101.43 strain and produced in a host organism transformed with said DNA sequence. The term homologous as used herein means a polypeptide encoded by DNA that hybridizes to the same substance as DNA encoding an endoglucanase enzyme specific for xyloglucan under defined specific conditions (such as pre-swelling in 5xSSC and prehybridization for one hour at -40 ° C) in 5xSSC solution, 5xDenhardt solution, and 50 µg of denatured bovine thymus DNA followed by hybridization in the same solution to which was added a sample labeled with 50 pCi of 32-P-dCTP for 18 hours at -40 ° C and washed three times in 2xSSC, 0 , 2% SDS at 40 ° C for 30 minutes). In particular, the phrase refers to DNA sequences that are at least 70% homologous to any of the above sequences encoding an endoglucanase having activity specifically for xyloglucan, and may be homologous to at least 75%, at least 80%, at least 85%, at least up to 90% or even at least 95% with any of the above sequences. The term includes the modification of any of the above DNA sequences, including nucleotide substitutions that do not produce other amino acid sequences in the polypeptide encoded by that sequence, but which correspond to the use of the codon of the host organism into which DNA containing any of the DNA sequences is introduced. different amino acid sequences and hence different structures of the corresponding proteins, which can produce an endoglucanase mutant with properties different from those of the natural enzyme. Other examples of possible modifications are inserting one or more nucleotides into the sequence, adding one or more nucleotides to either the end of the sequence, or deleting one or more nucleotides at either the end or within the sequence.

An endoglucanase exhibiting activity specifically for xyloglucan suitable for use in the methods of the invention preferably has a (as defined above) ratio of XGU / BGU, XGU / CMU and / or XGU / AVIU higher than 50, e.g. 75, 90 or 100.

• · · ············

Preferably, the endoglucanase exhibiting xyloglucan-specific activity is substantially devoid of β-glucan activity and / or exhibits at most 25%, for example 10% or 5%, of carboxymethylcellulose and / or Avicell activity at 100% xyloglucan activity. Further, the endoglucanases exhibiting xyloglucan-specific activity suitable for use in the methods of the present invention preferably substantially lack the transferase activity, which is characterized to some extent by most endoglucanases exhibiting specific activity for xyloglucan of plant origin.

An endoglucanase having specific activity for xyloglucan can be obtained from A. aculealus fungi by the method described in WO 94/14953. Microbial origin endoglucanases having specific activity for xyloglucine have also been described in WO 94/14953. Endoglucanases of plant origin exhibiting specific activity for xyloglucan are also known, but these enzymes act as transferases and are therefore less suitable than endoglucanases exhibiting specific activity for xyloglucan of microbial origin when extensive cleavage of xyloglucans is required. Another advantage of the microbial enzyme is that it can generally be obtained in larger amounts in the host of microorganisms than enzymes of a different origin.

When xyloglucanase is present in the composition of the invention, its concentration is preferably in the range of 0.0001 to 2% by weight, more preferably 0.0005 to 0.1% by weight, most preferably 0.0001 to 2% by weight.

0.02% by weight, based on the total weight of the formulation.

The above-mentioned enzymes may be of any suitable origin, i.e. of plant, animal and bacterial origin, and may be derived from fungi and yeasts. Both purified and non-purified forms thereof may be used. Mutants of natural enzymes are also useful. These mutants can be obtained, for example, by genetic engineering methods or by chemical and / or physical modification of natural enzymes. It is also common practice to obtain enzymes by host organisms in which the genetic material in which the enzyme is produced is cloned.

Said enzymes are usually present in the bleaching composition in concentrations ranging from 0.0001 to 2% by weight of the bleaching composition. Enzymes may be added as separate individual components (beads, granules, stabilized liquids and the like, containing one enzyme) or as mixtures of two or more enzymes (e.g. cogranulates).

Other suitable additives that may be added to detergents are those which inhibit the oxidation of enzymes. Examples of such enzyme oxidation inhibiting agents are ethoxylated tetraethylene polyamines.

A number of enzymes and compositions for their use as components of synthetic bleaching compositions are also described in International Patent Applications WO 93/07263 and WO 93/07260 by Genencor International and WO 89/08694 by Novo, and in U.S. Patent 3,553,139, the authors McCarty et al., Issued Jan. 5, 1971. These enzymes are further described in U.S. Patent No. 4,101,457 to Placha et al., Issued July 18, 1978, and U.S. Patent No. 4,507,219 to Hughes, U.S. Pat. issued March 26, 1985. Enzymes suitable for use in liquid detergents and their use in such formulations are described in U.S. Patent 4,261,868, Hora et al., issued April 14, 1981.

Enzyme stabilizers

Enzymes for use in detergents can be stabilized in various ways. Methods of stabilizing enzymes are described, and examples of such methods are disclosed in U.S. Patent 3,600,319 to Gedge et al., Issued Aug. 17, 1971; European Patents 199,405 and 200,586, issued to Venegas on Oct. 29, 1986. For example, enzyme stabilization systems are also described in U.S. Patent No. 3,519,570. Bacillus sp. AC 13 producing proteases, xylanases and cellulases are described in International Patent Application WO 9401532 by Novo. The enzymes useful in the process of the present invention can be stabilized by the presence of substances which are sources of water-soluble calcium and / or magnesium ions in the final compositions. Suitable enzyme stabilizers and their concentrations are described in U.S. Pat

No. 5,576,282.

Other detergent ingredients

The bleaching compositions of the present invention may also contain one or more polymeric dispersing agents, clay soil removers, dye transfer inhibiting agents, brighteners, suds suppressors, dyes, fragrances, texture modifiers, fabric softeners, carriers, hydrotropes, processing aids and / or pigments. Examples of such other detergent ingredients and concentrations are disclosed in U.S. Patent No. 5,576,282.

Methods of fabric washing

The organic catalysts and compositions containing the compounds of the invention can be used in virtually any washing or cleaning process, including soaking, prewashing and rinsing, using special rinse aid aids.

Preferably, the method of washing fabric described herein comprises contacting the fabric with a washing solution containing an organic catalyst (as such or contained in a bleaching composition) that is released into the washing solution in a controlled manner as defined in Test Protocols I, II and / or III.

Preferably, the wash solution comprises a peroxygen source.

The process according to the invention is normally carried out during the purification process. The purification process is preferably carried out at temperatures of 5 to 95 ° C, in particular at temperatures of 10 to 60 ° C. PH value · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · ·

102 of the washing solution is preferably 7 to 11. The product containing the organic catalyst

The organic catalysts and / or bleaching compositions of the present invention can be used in various fabric wash articles.

In a preferred embodiment, there is provided an article comprising the organic catalyst and / or bleaching compositions with the organic catalyst of the present invention, wherein the organic catalyst is released into a wash solution with the controlled release article defined in Test Protocols I below,

II and / or III. The product further includes instructions for use of the organic catalyst and / or bleaching composition containing the organic catalyst for cleaning the soiled fabric. This Instructions for Use describes the step of releasing an article comprising an organic catalyst and / or a bleaching composition with the oragnic catalyst, which may further comprise a source of peroxygen, into a fabric-containing washing solution in such a way that the organic catalyst is released in a controlled manner. as defined in test reports I, II and / or III below.

Sequence Listing <110> Procter & Gairble Carpany Dykstra, Robert Miracle, Gregory <120> Controlled-release detergents and how to use these detergents <130> 7749X <150> 60 / 151,002 <151> 1999-08-27 < 150> 60 / 151,004 <151> 1999-08-27 <160> 18 <170> PatentIn version 3.0 <210> 1 <211> 21 <212> EMA

103

<213> Aspergillus aculeatus <400> 1 attcatttg ggacagtga c 21 <210> 2 <211> 20 May <212> DNA <213> Aspergillus acul <400> 2 gttgatcgca cattgaacca 20 May <210> 3 <211> 20 May <212> DNA <213> Aspergillus aculeatus <400> 3 accccagccg accgattgtc 20 May <210> 4 <211> 20 May <: 212> INA <213> Aspergillus aculeatus <400> 4 cttccttacc tcaccatcat 20 May <210> · 5 <211> 20 May <212> DNA <213> Aspergillus aculeatus <400> 5 ttaacatctt ttcaccatga 20 May <210> 6 <211> 20 May <212> DNA <213> Aspergillus aculeatus <400> 6 agctttccct tctctccctt 20 <210> 7 <211> 28 <212> DNA <213> Aspergillus aculeatus

<400> 7 gccaccctgg cttcagctgc cagcctcc

28 <210> 8 <211> 20 May <212> DNA <213> Aspergillus aculeatus <400> 8 gacagtagca atccagcatt 20 May

• · · ·

104

<210> 9 <211> 20 May <212> DNA <213> Aspergillus aculeatus <400> 9 agcatcagcc gctttgcaca 20 May <210> 10 <211> 20 May <212> DNA <213> Aspergillus aculeatus <400> 10 ccatgaagtt caccgtattg 20 May <210> 11 <211> 20 May <212> DNA <213> Aspergillus aculeatus <400> 11 gcactgcttc tctcccaggt 20 May <210> 12 <211> 20 May <212> DNA <213> Aspergillus aculeatus <400> 12 gtgggcggcc cctcaggcaa 20 May <210> 13 <211> 20 May <212> DNA <213> Aspergillus aculeatus <400> 13 acgctcctcc aattttctct 20 May <210> 14 <211> 19 Dec <212> DNA <213> Aspergillus aculeatus <400> 14 ggctggtagt aatgagtct 19 Dec <210> 15 Dec <211> 20 May <212> DNA <213> Aspergillus aculeatus <400> 15 Dec ggcgcagagt ttggccaggc 20 May <210> 16 <211> 21 <212> DNA

- 105

0 0 · 0 0 0 0 0 0 0 0 0 0 0 0 0 0

<213> Aspergillus aculeatus <400> 16 caacatcccc ggtgttctgg g 21 <210> 17 <211> 347 <212> DNA <213> Aspergillus aculeatus <400> 17

aaagattcat ttgtggacag tggacgttga tcgcacattg aaccaacccc agccgaccga 60 ttgtccttcc ttacctcacc atcatttaac atctcttcac catcraagctt tcccttctct 120 cccttgccac cctggcttcc gctgccagcc tccagcgccg cacacttctg cggtcagtgg 180 gataccgcca ccgccggtga cttcaccctg tacaacgacc tttggggcga gacggccggc 240 accggctccc agtgcactgg agtcgacccc tacagcggcg acaccatcgc ttgtcacacc 300 aaaa agcaggtcct ggtcggagta gcagcagcgt caagagctat gccaacg 347 <210> 18 <211> 294 <212> DNA <213> Aspergillus aculeatus <400> 18 cagcatctcc attgagtaat cacgttggtg ttcggtggcc cgccgtgttg cgtggcggag 60 gctgccggaa gacgggtggg gatggtggtg ggagagaatg tagggcgccg tgtttcagtc 120 cctaggcagg ataccggaaa accgtgtggt aggaggttta taggtttcca ggagacgctg 180 tataggggat aaatgagatt gaatggtggc cacactcaaa ccaaccaggt cctgtacata 240 caatgcatat accaattata cctaccaaaa aaaaaaaaaa aaaaaaaaaa 294

DETAILED DESCRIPTION OF THE INVENTION

Determination of controlled catalyst release

To determine whether an organic catalyst or bleaching agent

106 of the present invention or the product comprising the organic catalyst or bleaching agent of the present invention are within the scope of the present invention.

Only when Protocol I case, Protocol II case III, and Protocol III case III, does the organic catalyst-containing product (OCCP) not fall within the scope of the present invention.

Test report

General conditions: All solutions are maintained at 25 ° C. The desired pH is adjusted using sodium carbonate or sulfuric acid. All solutions, except for small amounts (up to 5 ml) of dye bleaching Solutions (DBS) samples taken for absorbance measurement, are continuously mixed at 250 rpm. Absorbance values are measured with a reference dye solution (RDS).

A test determination is made to determine whether the preset value of any of the parameters, dbieach or Woccp, needs to be changed. .

dbieach is a parameter contained in the final assay protocol, indicating the time between bleaching (DBS) formation and data reading. The default value of dbieach parameters is 1 min, as can be seen from case I below, but this time may be longer.

Woccp is a parameter in the final assay protocol indicating the weight of an OCCP product used to form an organic catalystcontaining solution (OCCPS) product solution. The base value of these parameters is 1.00 g, but as can be seen in the case II below, this value may be lower.

CDS (concentrated dye solution) is a concentrated solution of dyes, which is a 0.3% solution of amaranth dye (Aldrich) in deionized water at ♦ · při ··· · ·

- 107 pH 10.

OCCP is an article comprising an organic catalyst (as defined previously) in which various adjuvants may be present in addition to the organic catalyst.

OCCPS is a solution of product containing organic catalyst prepared by dissolving 1.00 g of product containing organic catalyst (OCCP) in 1.0 L of deionized water at 25 ° C, the pH of which has been adjusted so that the pH of the final solution is in the range of 9.9 to 10.1.

DBS (dye bleaching solution) is a bleach solution prepared by mixing 100 ml of OCCPS with 10 ml of CDS.

Amax assay: 100 mL of deionized water at pH 10 is added to 10 mL of CDS. Amax is the absorbance of the resulting homogeneous reference dye solution (RDS) determined by UV spectroscopy at Amax (approximately 518 nm).

Proportional removal times: The proportional removal times from OCCPS are fixed (t _f ) and proportional (t _dd ). The values of t _f are 0.5, 1.5, 2.5 and 3.5 minutes. The values of t _dd are 0.25D, 0.50D and 0.75D, where D is the recommended wash time. Values t _dd less than 5 minutes may not be taken into account. For the purposes of this test, the value of D shall be at least 5 minutes, maximum 16 hours. If the recommended wash time is not specified by the OCCP manufacturer, the D value is set at 20 minutes. For example, if the wash time is 60 minutes, t _{dds of} 15, 30 and 45 minutes are used in addition to tf. For a 12 minute wash time, the relative decolouration times used are 0.5, 1.5, 2.5, 3.5, 6 and 9 minutes.

The test is performed by vide infra using the basic values d _b ieach and WQCCP. Of all the relative scavenges, the relative scavenging of Q at which the lowest absorbance is measured is determined. Amin · The time (tf or t _dd ) corresponding to the relative scavenging of Q from OCCPS is t _Q. This time corresponds to the highest 5A (Am _ax -Amin) · Depending on the Amin value, there are three cases:

Case 1: If Amin> 0.9 Amax / a new test is performed with a different dbieach value · In this new test, a sample is taken for stand108

The elimination elution at t _{Q is the} same as in the previous test, except that the stirring is carried out longer and the determination is made at 1 minute intervals until the absorbance Ami _n <0.9 Amax · Minimum mixing time DBS needed to meet the above absorbance condition defines a new dbieach time for the final determination. However, if this dbieach time is greater than 30 minutes (that is, if 10% of the bleaching effect is not achieved within 30 minutes, even at the point where δΑ is highest (when the organic catalyst is present at the highest concentration)), the OCCP does not fall under test protocol I within the scope of the present invention, however, test protocols II or III may reveal that OCCP is within the scope of the invention.

Case 2: If A ^ n <0.25 Amax, a new test is performed with a new Woccp value. This is repeated until the absorbance condition of case 3 is met (for example, the OCCP is reduced from 1.0 g to 0.5 g, then further if necessary from 0.5 g to 0.25 g, etc).

Case 3: If 0.25 An, _ax <^ 0.9 Amax, the test determination is the final determination. In this case, it is not necessary to select dbieach aw _and ccp differently from the base values.

Assay Protocol I: Prepare OCCPS as described above. The time at which OCCP is added to deionized water to form OCCPS is t = 0. 100 ml of OCCPS is withdrawn at each time of relative removal (tf or tdd), immediately during t = (tf or tdd) to t = (tf) or tdd + 0.25 min) is filtered to remove undissolved OCCP, and the filtrate is added to 10.0 ml CDS at once at t - (tf or tdd + 0.50 min). Take 1 to 5 ml of DBS formed C and immediately determine the absorbance. Absorbance of sample C was measured after the time when dbleach λ ^ χDoba at which the measured sample absorbnce C T _C. A corollary is that _C t = (tf or tdd) ⁺ 0.50 min + dbieach- Asorbance determined at time t _c is? _{T (C).} 5A _t (c> is Am _ax -A _{t (C} ). For example, if the wash time is 12 minutes, the dbieach value is 1 minute and the relative removal times are: · · · · · · · · · Are 0.5, 1.5, 2.5, 3.5, 6 and 9 minutes, then the corresponding times t _c are 2, 3, 4, 5, 7.5 and 10.5 minutes.

Absorbance time t _Ca is the absorbance time t _c that precedes the other absorbance time t _c p. It is therefore t _Ca <t _c p. Absorbance t _Ca is At (o _e ; absorbance at t _c p is A _t ( _C ) p · Depending on the values of A _t ( _C ) and a -A _{t (} c) p, there may be two cases:

Case if: If for all A _{t (} ci <x and A _{t (} c) pz that A _{t (} c) p <A _{t (} c) az and therefore that 5A _{t (} op> ÓA _t (c) az it is evidence that the product is a controlled release organic catalyst (OCCP) product and is within the scope of the present invention.

Example of case li for a 20 minute wash cycle:

t (min) tc (min) Anax ^A t (C) > At (cj content dyes (%) 0 0 1.20 100 ALIGN! 0.5 2 1.20 1.00 0.20 83 1.5 3 1.20 0.84 0.36 71 2.5 4 1.20 0.70 0.50 58 3.5 5 1.20 0.67 0.53 56 5 6.5 1.20 0.72 0.48 60 10 11.5 1.20 0.78 0.42 65 15 Dec 16.5 1.20 0.83 0.37 69

- 110 9 9 9 9 9 9 9 9 9 9 9 9 9 9 9

Case 2- ₂ - If for any pair of values A _t (cia and -A. _{T (C} ) p holds that A _t (c) p A _t (c) cu and thus 5A _{t (} op 5A _t (cxx / this is evidence that it is not a controlled organic release catalyst (OCCP) product and this Protocol I product is not within the scope of the present invention, but it may be determined that this OCCP is within the scope of the present invention according to the test protocol II and / or according to Test Protocol III This may occur, for example, in a non-OCCP product in which the OCCP fully dissolves in the OCCPS in less time than the first tf, so that the following values of A _t (o remain constant. The gradual decomposition of the organic catalyst in OCCPS (which leads to lower discoloration of DBS with increasing time) causes A _{t (} c) p> A _t ( _C ) a.

111 »to this to · · * ·« · «this to * ··« ··

Example of case I ₂ for a 20 minute wash cycle:

time (min)

Test report II

General conditions: Same as Test Report I with the following additions.

The OCSP (organic catalyst-segregated product) product followed by the organic catalyst is a product prepared in the same way as OCCP, but by first mixing all the components of the product and adding the organic catalyst last, so that the total OCSP composition is the same as the OCCP composition.

OCSPS is a solution of product with subsequently added organic catalyst solution prepared by dissolving 1.00 g of product with subsequently added organic catalyst (OCSP) in 11 deionized water at 25 ° C, the pH of which is adjusted so that the pH of the resulting solution • · ·· · «* • * * * · · · · · · ·

112 is in the range of 9.9 to 10.1.

Wocsp is a parameter in the final assay protocol indicating the weight of the OCSP product used to form the OCSPS product solution. The base value of this parameter is 1.00 g, but as is evident from the case II below, this value may be lower.

DBS2 (dye bleaching solution 2) is a bleach solution prepared by mixing 100 ml OCSPS with 10 ml CDS

The times of relative removal from OCSPS are the same as from the previously described times of relative removal of OCCPS.

Assay Protocol II: The initial step is performed according to Protocol I. The same procedure is repeated (except that OCCP is used instead of OCCP), the dbieach values are the same as in Protocol I. The time OCSP is added to deionized water to form OCSPS 100 ml of OCSPS is withdrawn at each time of relative elimination (tf or tdd), immediately filtered during t = (tf or tdd) to t = (tf or tdd + 0,25 min) to remove undissolved OCSP, and the filtrate was added to 10.0 ml CDS at one time at t = (t _f or tdd + 0.50 min). Take 1 to 5 ml of S-generated DBS and immediately determine the absorbance. The absorbance of sample S is measured after the dbieach time at λ ^ χ.

The time at which the absorbance of S is measured is t _s . Thus, t _s = (tf or tdd) ⁺ 0.50 min + dbieach-Asorbance found at time t _c is A _t ( _S ). 5A _t (s) is An, _ax - and _t (s>). For example, if the wash time is 12 minutes, the dbieach value is 1 minute and the relative removal times are 0.5, 1.5, 2.5, 3, 5, 6 and 9 minutes, then the corresponding times t _s are 2, 3, 4, 5, 7.5 and 10.5 minutes.

For t _s = t _c there are two cases depending on the values of A _{t (C} ) and Atis): '

Case III: When applied to at least one case, the _{T (S)} <A _{T (C),} and thus that OA _t (sec)> 6A _{T (C),} this indicates that it is a product of the controlled release of organic catalyst (OCCP), which •

This article is within the scope of this invention. Example case III for a 20 minute wash cycle:

time (min)

More preferably, according to Protocol II, even if at least one case, 1.2 x A _{t (S)} < A _t ( _C ) r is evidence that the product is a controlled release organic catalyst (OCCP) product ), and the product is within the scope of this invention.

Case II ₂ : If for all values A _t (s) and A _t (ci), A _t (s) A _{t (C)} and thus that AA _t (s) 5A _{t (} c) z is proof, However, it may be found that the OCCP is within the scope of the present invention according to Test Protocol I and / or Test Protocol III.

114

Test report III

General conditions: Same as Test Report I with the following additions. Peroxyacetic acid is supplied by Aldrich as a 32% by weight solution

OCSPS 'is a solution of an organic catalyst product prepared by dissolving 1.00 g of an organic catalyst product (OCCP) in 11 deionized water at 25 ° C containing 100 mg of peracetic acid whose pH is adjusted so that the pH of the resulting solution is in the range of 9 , 9 to 10.1.

Assay Protocol III: All steps are the same as protocol I except for the use of OCCPS 'instead of OCCPS.

Case IIIi: When applied to any of the values of A _t (c) and A _t (c) p that A _t (c) p <A _{T (c)} and therefore that o and _{t (c)} p> o and _t ( _C) c </ it is a proof that it is a product with a controlled availability organic catalyst (OCCP), and the product falls within the scope of this invention.

Case III ₂ : If A _t ( _C ) and a A _t (if A _{t (} c) p

A _t (c) a <and therefore 6A _t (op - 5A _t ( _C ) az is evidence that it is not an OCCP product, according to Protocol III. However, it may be found that this OCCP is within the scope of the invention according to Test Report I and / or Test Report II.

The compositions of the present invention may be prepared by any of the methods selected by a person preparing them, examples of which are described in U.S. Patent No. 5,691,297 to Nassano et al., Issued Nov. 11, 1997; U.S. Patent No. 5,574,005 to Welch et al., issued Nov. 12, 1996; U.S. Patent No. 5,569,645 to Dinniwell et al., issued Oct. 29, 1996; U.S. Patent No. 5,565,422 to Del Greco et al., issued October 15, 1996; U.S. Patent No. 5,516,448, Capeci et al., issued May 14, 1996; U.S. Patent No. 5,489,392, auto-a;

Capeci et al., Issued Feb. 6, 1996; and U.S. Pat

No. 5,486,303, Capeci et al., issued Jan. 23, 1996, all of which are incorporated herein by reference.

In addition to the above embodiments, the organic catalysts of the present invention may be included in any suitable laundry composition, examples of which include, but are not limited to, U.S. Patent No. 5,679,630 to Baeck et al., Issued October 21, 1997; U.S. Patent No. 5,565,145 to Watson et al., issued Oct. 15, 1996; U.S. Patent No. 5,478,489 to Fredj et al., issued Dec. 26, 1995; U.S. Patent No. 5,470,507 to Fredj et al., issued Nov. 29, 1995; U.S. Patent No. 5,466,802 to Panandiker et al., issued Nov. 14, 1995; U.S. Patent No. 5,460,752 to Fredj et al., issued Oct. 24, 1995; U.S. Patent No. 5,458,810 to Fredj et al., issued October 17, 1995; U.S. Patent No. 5,458,809 to Fredj et al., issued October 17, 1995; and U.S. Patent No. 5,288,431 to Huber et al., issued Feb. 22, 1994, all of which are incorporated herein by reference.

Having described the invention in detail, including preferred embodiments thereof, it will be apparent to those skilled in the art that various changes and modifications may be made therein without departing from the scope of the invention and that the invention is not limited thereto.

• · · ·

Claims (63)

116 PATENT CLAIMS A method of washing comprising contacting a contaminated fabric with an organic catalyst in a controlled release manner. 2. The process of claim 1 wherein said organic catalyst is selected from the group consisting of: (a) aryliminium cations and aryliminium polyions having a charge in the range of +3 to -3 and having the general formula [I]: R [I] wherein R ² and R ³ are independently selected from substituted or unsubstituted groups selected from the group consisting of H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, heterocyclic compound residue, silyl, nitro, halo, cyano, sulfo, alkoxy, keto, carboxy and carboalkoxy groups; R ¹ and R ⁴ are selected from substituted or unsubstituted saturated or unsaturated groups selected from the group consisting of H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, heterocyclic compound residue, silyl, nitro, halo, cyano, alkoxy, keto, and keto ; X ”is a suitable charge-compensating counterion; and v is a natural number of 1 to 3; (b) Aryliminium zwitterions having a charge in the range of +3 to -3 having the general formula [II]: • e · · 117 wherein R ⁵ -R ⁷ are independently selected from substituted or unsubstituted groups selected from the group consisting of H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, heterocyclic compound residue, silyl, nitro, halo, cyano, sulfo, alkoxy, keto groups , carboxy and carboalkoxy groups; which also includes a group of the general formula: wherein the group Z _p - is covalently bonded to the group and is selected from the group consisting of -CO ₂ , -SO 3; -OSO 3 ', -SO ₂ ^- and -SO ₂ ^-, and p is either 1, 2 or 3; , T _o is selected from the group consisting of substituted or unsubstituted, saturated or unsaturated alkyl, cycloalkyl, aryl, alkaryl, aralkyl, and heterocyclic ring; (c) modified amines having a charge in the range of -3 to +3 having the general formulas [V] and [VI]: [V] [VI] wherein R ⁹ -R ¹⁰ are independently selected from substituted or unsubstituted groups selected from the group consisting of 118 Η, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, heterocyclic compound residue, silyl, nitro, halo, cyano, sulfo, alkoxy, keto, carboxy, and carboalkoxy and positive or negative charge groups; R ⁸ and R ¹¹ , if present, are selected from the group consisting of substituted or unsubstituted saturated or unsaturated H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, heterocyclic compound residue, silyl, nitro, halo, cyano, alkoxy , keto and carboalkoxy groups and groups carrying positive or negative charges; R ¹² is a leaving group whose protonated form has a pK _{and a} value (in aqueous medium) between 37> pK _and >-2; wherein, when R ⁸ -R ¹² groups are present, they may combine with each other to form a fused ring aromatic compound, a fused ring carbocyclic compound, or a fused ring heterocyclic compound; and a group of the formula: -T _o in which Z is _p-covalently bonded to To, selected from the group consisting of -S0 ₂ -C 0 -C ₃ ~ -0S0 _3, -S0 _2, 0S0 and ₂ "and p is either 1, 2 or 3 ; , T _o is selected from the group consisting of substituted or unsubstituted, saturated or unsaturated alkyl, cycloalkyl, aryl, alkaryl, aralkyl, and heterocyclic ring; (d) modified amine oxides having a charge in the range of -3 to +3 and having the general formulas [VII] - [X]: • «· · 119 [VIII] wherein R ⁹ -R ¹⁰ are independently selected from substituted or unsubstituted groups selected from the group consisting of H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, heterocyclic compound residue, silyl, nitro, halo, cyano, sulfo, alkoxy, keto, carboxy and carboalkoxy groups and positive or negative charge groups; R ⁸ and R ¹¹ are groups selected from the group consisting of substituted or unsubstituted saturated or unsaturated H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, heterocyclic compound residue, silyl, nitro, halo, cyano, sulfo, alkoxy, carboxy and carboalkoxy groups and groups carrying positive or negative charges; R ¹² is a leaving group whose protonated form has a pK _{and a} value (in aqueous medium) between 37> pK _and >-2; wherein, when R ⁸ -R ¹² groups are present, they may combine with each other to form a fused ring aromatic compound, a fused ring carbocyclic compound, or a fused ring heterocyclic compound; and the group also includes 120 of the general formula: —T _o wherein the group Z _p - is covalently bonded to the group To and is selected from the group consisting of -CO ₂ '-SO ₃ , -OSO ₃ , -SO ₂ ", and -0SO ₂ - and p is either 1,2 or 3; , T _o is selected from the group consisting of substituted or unsubstituted, saturated or unsaturated alkyl, cycloalkyl, aryl, alkaryl, aralkyl, and heterocyclic ring; (e) sulfonimines, phosphonimines, N-acylimines and thiodiazole dioxides of the general formulas [XXIa], [XXIb], [XXII] and [XXIII]: [XX1a] [XXIb] [XXII]. [XX111] wherein R ⁴¹ -R ⁴⁴ ; when present, they are independently selected from substituted or unsubstituted saturated or unsaturated groups selected from the group consisting of H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, heterocyclic compound residue, silyl, nitro, halo, cyano, sulfo, alkoxy, keto, carboxy and carboalkoxy groups; wherein any of the R ⁴¹ -R ⁴⁴ groups may be linked to any other R ⁴¹ -R ^{44 group} to form part of a common cycle, including the remainder of the condensed ring aromatic compound, the fused-ring carbocyclic compound or the fused-ring heterocyclic compound; (f) oxaziridinium cations and polyions having a charge in the range of - 121 to +3, having the general formula [III]: [111] wherein R ² '-R ³ ' are independently selected from substituted or unsubstituted groups selected from the group consisting of H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, heterocyclic compound residue, silyl, nitro, halo, cyano, sulfo, alkoxy, keto, carboxy, and carboalkoxy; R ¹ 'and R ⁴ ' are groups selected from the group consisting of substituted or unsubstituted saturated or unsaturated, H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, heterocyclic compound residue, silyl, nitro, halo, cyano, alkoxy, keto, and keto groups carboalkoxy; and X ^- is a suitable charge-compensating counterion, and preferably a bleach-compatible counterion; (g) oxaziridinium zwitterions having a charge in the range of +3 to -3 having the general formula [VI]: wherein R ⁵ '-R ⁷ ' are independently selected from substituted or unsubstituted groups selected from the group consisting of H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, heterocyclic compound residue, silyl, nitro, halo, cyano, sulfo, alkoxy , keto groups, carboxy groups and carboalkoxy groups; they also include a group of the general formula: wherein group ^Z p is covalently bonded to T ' _o, and is selected from the group consisting of -CO2- "-SO 3", -OSO 3 ', -S0 ₂ "OSO / p is either 1, 2 or 3; , T _o is selected from the group consisting of substituted or unsubstituted, saturated or unsaturated alkyl, cycloalkyl, aryl, alkaryl, aralkyl, and heterocyclic ring; (h) oxaziridine sulfonimines [XXIVa], phosphonimines [XXIVb], Nacylimines [XXV] and thiodiazole dioxides [XXVI] and [XXVII], of the following formulas: R ⁴³ 'so ₂ r ⁴⁴ ' 42 '' N 44 '^ so ₂ y 42 ' O. 44 ' 43 ’ R ⁴³ O [XXIVb] [XXV] [XXIVa] [XXVI] wherein R ⁴¹ '-R ⁴⁴ ', if present, are independently selected from substituted or unsubstituted groups selected from the group consisting of H, alkyl, cycloalkyl, aryl , alkaryls, aralkyls, heterocyclic compound radicals, silyl, nitro, halo, cyano, sulfo, alkoxy, keto, carboxy, carboalkoxy groups, wherein any one of R ⁴¹ '-R ⁴⁴ ' may be associated with any other R ⁴¹ '- R ⁴⁴ 'to form part of a common cycle, including the remainder of the condensed ring aromatic compound, the remainder of the fused ring carbocyclic compound, or the remainder of the fused ring heterocyclic compound; and (i) and mixtures thereof. 3. The process of claim 2 wherein said organic catalyst is selected from the group consisting of: (a) aryliminium cations and aryliminium polyions having a charge in the range of +3 to -3 having the general formula [XI]: [X1] wherein m is 1 to 3 when G is present, and m is 1 to 4 if G is not present; n is an integer from 0 to 4; any of R ²⁰ is independently selected from substituted or unsubstituted groups selected from the group consisting of H, alkyl, cycloalkyl, aryl, fused ring aromatic, heterocyclic ring, fused ring heterocycle, nitro, halo, cyano , sulfo, alkoxy, keto, carboxy, and carboalkoxy, and the combination of any two R ²⁰ vicinal substituents may yield a fused-ring aromatic compound, a fused-ring carbocyclic compound, or a fused-ring heterocyclic compound; R ¹⁸ may be a substituted or unsubstituted group selected from the group consisting of H, 124 alkyl, cycloalkyl, alkaryl, aryl, aralkyl, heterocyclic compound, silyl, nitro, halo, cyano, sulfo, alkoxy, keto, carboxy, and carboalkoxy; R ¹⁹ is a group selected from substituted or unsubstituted, saturated or unsaturated groups which are H, alkyl, cycloalkyl, alkaryl, aralkyl, and the heterocyclic compound residue; the group G is selected from the group consisting of: 1) -O-; 2) -N (R ²³⁾ -; and 3) -N (R ²³ R ²⁴ ) -; R ²¹ -R ²⁴ are substituted or unsubstituted groups independently selected from the group consisting of H, oxygen, straight or branched C 1 -C 12 alkyls, alkylenes, alkoxy, aryl, alkaryl, aralkyl, cycloalkyl and heterocyclic radicals; wherein any one of R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ -R ²⁴ may be linked to any other R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ -R ²⁴ to form part of a common cycle; any geminal groups R ²¹ '-R ²² may combine with each other to form carbonyl; any of the vicinal groups R ²¹ R ²⁴ may combine to form a double bond; and at the same time any of the groups R ²¹ -R ²⁴ may combine with each other to form a substituted or unsubstituted fused unsaturated group; X 'is a suitable charge-compensating counterion; and v is a natural number of 1 to 3; (b) Aryliminium zwitterions having a charge in the range of +3 to 3 having the general formula [XII]: wherein m is 1 to 3 when G is present and m is 1 to 4 when G is not present; n is an integer from 0 to 4; any of R 125 pin ²⁶ is independently selected from substituted or unsubstituted groups selected from the group consisting of H, alkyl, cycloalkyl, aryl, fused ring aromatic compound, heterocyclic ring compound, fused ring heterocycle compound, nitro, halogen, cyano, sulfo, alkoxy, keto, carboxy, and carboalkoxy, and any two R ²⁶ vicinal substituents may combine to form a fused ring aromatic compound, a fused ring carbocyclic compound, or a fused ring heterocyclic residue; R ²⁵ may be a substituted or unsubstituted group selected from the group consisting of H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, heterocyclic compound moiety, silyl, nitro, halo, cyano, sulfo, alkoxy, keto, and carboxy; which also includes a group of the general formula: wherein a group, _Z 'is covalently bonded to T _o, and is selected from the group consisting of -C 0 ₂ "-SO 3, -OSO 3, -SO> 2- -0S0 ₂ and p is either 1, 2 or 3; _the group T is selected from the group of substances of the formula ^RJ wherein q is a natural number of 1 to 8; R ²⁹ is independently selected from substituted or unsubstituted groups selected from the group consisting of straight or branched groups; 126, H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, alkylene, heterocyclic compound, alkoxy, arylcarbonyl, carboxyalkyl and amide groups; the group G is selected from the group consisting of: 1) -O-; 2) -N ( ^R30 ) -; and 3) N (R ³⁰ R ³¹ ) -; R ²⁷ , R ²⁸ , R ³⁰ and R ³¹ are substituted or unsubstituted groups independently selected from the group consisting of H, oxygen, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, alkylene, heterocyclic compound, alkoxy, arylcarbonyl, carboxyalkyl and amide groups; any of the groups R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , R ³⁰ and R ³¹ may be associated with any other group R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , R ³⁰ and R ³¹ to form part of a common cycle ; any of the geminal groups R ²⁷ -R ²⁸ may combine with each other to form carbonyl; any of the vicinal R ²⁷ -R ³¹ groups may combine to form a double bond; and at the same time any of the groups R ²⁷ -R ³¹ may combine with each other to form a substituted or unsubstituted fused unsaturated group; (c) modified amines of formulas [XV] and [XVI]: [XV1] · wherein m is 1 to 3 when G is present, and m is 1 to 4 if G is not present; n is an integer from 0 to 4; R ³⁴ is a group selected from the group consisting of substituted or unsubstituted saturated or unsaturated hydroxy, hydroperoxy, alkoxy, peralkoxy, carboxy, percarboxy, sulfo, and persulfo; any of R ³⁵ is independently selected from substituted or unsubstituted groups; H, alkyl, cycloalkyl, aryl, fused ring aromatic, heterocyclic ring, fused ring heterocycle, nitro, halogen, cyano, sulfo, alkoxy, keto, carboxy, and carboalkoxy, vicino, and any R 2, and any R 2, and any R 2, and any ³⁵ may combine with each other to form a fused ring aromatic compound, a fused ring carbocyclic compound, or a fused ring heterocyclic compound; R ³² may be a substituted or unsubstituted group selected from the group consisting of H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, heterocyclic compound residue, silyl, nitro, halo, cyano, sulfo, alkoxy, keto, carboxy, and carboxy; R ³³ may be a substituted or unsubstituted saturated or unsaturated group selected from the group consisting of H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, heterocyclic compound moiety, and also includes a group of the formula: where Z _p- is covalently bonded to To, and is selected from the group consisting of -C 0 ₂ "-S0 ₃ -0S0 ₃ ', -S0 ₂ -0S0 _2' and p is either 1, 2 or 3; the group T _o is selected from the group of groups consisting of: (C) q R ³⁸ wherein q is a natural number of 1 to 8; R ³⁸ is independently selected from substituted or unsubstituted groups selected from the group consisting of straight or branched H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, alkylene, heterocyclic compound moiety, alkoxy, arylcarbonyl, carboxyalkyl, and amide groups; the group G is selected from the group consisting of: 1) -O-; 2) -N (R ³⁹ ) -; and 3). N (R ³⁹ R ⁴⁰ ) -; R ³⁶ , R ³⁷ , R ³⁹ and R ⁴⁰ are substituted or unsubstituted groups independently selected from the group consisting of H, oxygen, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, alkylenes, heterocyclic compound, alkoxy, arylcarbonyl, carboxyalkyl, and amide groups; each R ^32, R ^33, R ^34, R ^35, R ^36, R ^37, R ³⁹ and R ⁴⁰ may be joined together with any other of R ^32, R ^33, R ^34, R ³ 5 R ³⁶ R ³⁷ , R ³⁹ and R ⁴⁰ to form part of a common cycle; any geminal groups R ³⁶ -R ³⁷ may combine with each other to form carbonyl; any of the vicinal groups R ³⁶ , R ³⁷ , R ³⁹ and R ⁴⁰ may combine to form a double bond; and at the same time any of R ³⁶ , R ³⁷ , R ³⁹ and R ⁴⁰ can combine with each other to form a substituted or unsubstituted fused unsaturated group; (d) modified amine oxides of formulas [XVII] to [XX]: wherein m is 1 to 3 when G is present, and m is 1 to 4 when G is absent; n is an integer from 0 to 0 4; R ³⁴ is a group selected from the group consisting of substituted or • 129 unsubstituted saturated or unsaturated hydroxy, hydroperoxy, alkoxy, peralkoxy, carboxy, percarboxy, sulfo and persulfo groups; any of R ³⁵ is independently selected from substituted or unsubstituted groups selected from the group consisting of H, alkyl, cycloalkyl, aryl, fused ring aromatic, heterocyclic ring, fused ring heterocycle, nitro, halo, cyano , sulfo, alkoxy, keto, carboxy, and carboalkoxy, and any two R ³⁵ vicinal substituents may combine to form a fused-ring aromatic compound, a fused-ring carbocyclic compound, or a fused-ring heterocyclic compound; R ³² may be a substituted or unsubstituted group selected from the group consisting of H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, heterocyclic compound residue, silyl, nitro, halo, cyano, sulfo, alkoxy, keto, carboxy, and carboxy; R ³³ may be a substituted or unsubstituted saturated or unsaturated group selected from the group consisting of H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, heterocyclic compound moiety, and also includes a group of the formula: wherein Z ^_ _p is covalently bonded to T _o, and is selected from the group consisting of -CO2-, "-SO 3, -OSO 3 ·, -SO2 'and -OSO2- and p is either 1, 2 or 3; the group T _o is selected from the group of groups consisting of: - 130 • R ³⁸ I - (C) q - R ³⁸ wherein q is a natural number of 1 to 8; R ³⁸ is independently selected from substituted or unsubstituted groups selected from the group consisting of straight or branched H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, alkylene, heterocyclic compound, alkoxy, arylcarbonyl, carboxyalkyl and amide groups; the group G is selected from the group consisting of: 1) -O-; 2) -N (R ³⁹ ) -; and 3) -N (R ³⁹ R ⁴⁰ ) -; R ³⁶ , R ³⁷ , R ³⁹ and R ⁴⁰ are substituted or unsubstituted groups independently selected from the group consisting of H, oxygen, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, alkylene, heterocyclic compound, alkoxy, arylcarbonyl, carboxyalkyl, and amide groups; any of R ³² , R ³³ , R ³⁴ , R ³⁵ , R ³⁶ , R ³⁷ , R ^39, and R ⁴⁰ may be associated with any other R ³² , R ³³ , R ³⁴ , R ³⁵ , R ³⁶ -, R ^{36 37} , R ³⁹ and R ⁴⁰ to form part of a common cycle; any geminal groups R ³⁶ R ³⁷ may combine with each other to form carbonyl; any of the vicinal groups R ³⁶ , R ³⁷ , R ³⁹ and R ⁴⁰ may combine to form a double bond; and at the same time any of the groups R ³ , R ³⁷ , R ³⁹ and R ⁴⁰ can combine with each other to form a substituted or unsubstituted fused unsaturated group; (e) sulfonimines [XXVIIIa], phosphonimines [XXVIIIb], N-acylimines [XXIX] of the general formulas: [XXVIIIa] [XXVIIIb] [XXIX] β Wherein any one of R ⁴⁶ is independently selected from substituted or unsubstituted groups selected from the group consisting of H, alkyl, cycloalkyl, aryl, condensed ring aromatic compound, heterocyclic compound, a fused-ring heterocyclic compound, nitro, halogen, cyano, sulfo, alkoxy, keto, carboxy, and carboalkoxy groups, and any two R ⁴⁶ vicinal substituents can combine to form a fused-ring aromatic compound, a carbocyclic ring residue, or a carbocyclic ring residue fused-ring heterocyclic compounds; R ⁴⁵ may be a substituted or unsubstituted group selected from the group consisting of H, alkyl, cycloalkyl, alkaryl, aryl, aralkyls, heterocyclic compound residue, silyl, nitro, halo, cyano, sulfo, alkoxy, keto, carboxy, and carboxy; the group G, if present, is selected from the group consisting of: 1) -O-; 2) -N (R ⁴⁷ ) -; and 3) -N (R ⁴⁷ R ⁴⁸ ) -; R ⁴⁷ -R ⁴⁸ are substituted or unsubstituted groups independently selected from the group consisting of H, oxygen, straight or branched C 1 -C 12 alkyls, alkylenes, alkoxy, aryl, alkaryl, aralkyl, cycloalkyl and heterocyclic radicals (f) oxaziridinium cations and polyions having a charge in the range of +3 to -3, having the general formula [XIII]: [X111] t9 total * 132 wherein m is 1 to 3 when G is present, and m is 1 to 4 when G is absent; n is an integer from 0 to 4; any of R ²⁰ 'is independently selected from substituted or unsubstituted groups selected from the group consisting of H, alkyl, cycloalkyl, aryl, a fused-ring aromatic compound, a heterocyclic ring, a fused-ring heterocyclic ring, nitro, halogen, cyano, sulfo, alkoxy, keto, carboxy, and carboalkoxy groups, and any two vicinal R ²⁰ 'substituents can combine to form a fused ring aromatic compound, a fused ring carbocyclic compound, or a fused ring heterocyclic compound; R ¹⁸ 'may be a substituted or unsubstituted group selected from the group consisting of H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, the heterocyclic compound residue, silyl, nitro, halo, cyano, sulfo, alkoxy, keto, carboxy, carboxy; R ¹⁹ 'may be a substituted or unsubstituted saturated or unsaturated group selected from the group consisting of H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl and the remainder of the heterocyclic compound. the group G is selected from the group consisting of: 1) -O-; 2) -N (R ²³ ') -; and 3) -N (R ²³ 'R ²⁴ ') -; R ²¹ '-R ²⁴ ' are substituted or unsubstituted groups independently selected from the group consisting of H, oxygen, straight or branched C 1 -C 12 alkyls, alkylenes, alkoxy, aryl, alkaryl, aralkyl, cycloalkyl and heterocyclic radicals; provided that any one of R ¹⁸ 'R ¹⁹ ', R ²¹ ', R ²⁴ ' can be linked to any other R ¹⁸ ', R ¹⁹ ', R ²¹ '-R ²⁴ ' to form part of a common cycle; any geminal groups R ²¹ '-R ²² ' may be combined with each other to form carbonyl; any of the vicinal groups R ²¹ '-R ²⁴ ' may be joined to form a double bond; and at the same time any of the groups R ² '' -R ²⁴ 'can combine with each other. To form a substituted or unsubstituted fused unsaturated group; and at the same time any of the groups R ²¹ '-R ²⁴ ' can combine with each other to form a substituted or unsubstituted fused unsaturated group; X ”is a suitable charge-compensating counterion; and v is a natural number of 1 to 3; (g) oxaziridinium zwitterions having a charge in the range of +3 to -3 having the general formula [XIV]: wherein m is 1 to 3 when G is present, and m is 1 to 4 when G is absent; n is an integer from 0 to 4; any of R ²⁶ 'is independently selected from substituted or unsubstituted groups selected from the group consisting of H, alkyl, cycloalkyl, aryl, aromatic ring compound, heterocyclic ring compound, cyclic ring heterocycle compound, nitro, halogen, cyano, sulfo, alkoxy, keto, carboxy, and carboalkoxy, and any two vicinal substituents R ²⁶ 'may combine to form the remainder of the condensed ring aromatic compound, the fused-ring carbocyclic compound, or the fused-ring heterocyclic compound; R ²⁵ 'may be a substituted or unsubstituted group selected from the group consisting of H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, heterocyclic compound residue, silyl, nitro, halo, cyano, sulfo, alkoxy, keto, carboxy and carboxy; represented by the general formula: wherein the group Z ' _p ' is covalently bonded to the group T ' _o , and is selected from the group consisting of -CO ₂ -SO ₃ , -OSO ₃ ', -SO ₂ , and OSO ₂ " , and p is either 1 or 2; the group T ' _o is selected from the group of groups consisting of: 134 —Γ _ο —ζ-ρθ I - (C) q— R ²⁹ 'wherein q is a natural number of 1 to 8; R ²⁹ 'is independently selected from substituted or unsubstituted groups selected from the group consisting of unbranched or branched H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, alkylene, heterocyclic compound residue, alkoxy, arylcarbonyl, carboxyalkyl and amide groups; the group G is selected from the group consisting of: 1) -O-; 2) -N ( ^R30 ') -; and 3) N (R ³⁰ 'R ³¹ ') -; R ²⁷ ', R ²⁸ ', R ³⁰ 'and R ³¹ ' are substituted or unsubstituted groups independently selected from the group consisting of H, oxygen, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, alkylenes, heterocyclic compound, alkoxy, arylcarbonyl groups, carboxyalkyl and amide groups; any of R ²⁵ ', R ²⁶ ', R ²⁷ ', R ²⁸ ', R ³⁰ 'and R ³¹ ' may be associated with any other R ²⁵ ', R ²⁶ ', R ²⁷ ', R, R and R to form part of a common cycle; any geminal groups R ²⁷ '-R ²⁸ ' may be combined with each other to form carbonyl; any of the vicinal groups R ²⁷ '-R ³¹ ' may be joined to form a double bond; and wherein any of the substituents R ²⁷ '-R ³¹ ' may combine with each other to form a substituted or unsubstituted fused unsaturated group; • 99 · - 135 · 9 a · «« • a · · · · 9 100 99 «ca * 9 9 9 9 »» a (h) oxaziridine sulfonimines [XXXIa], phosphonimines [XXXIb], Nacylimines [XXXII] of the general formulas: [XXX1a] [XXXIb] [ΧΧΧΠ] wherein any one of R ⁴⁶ 'is independently selected from substituted or unsubstituted groups selected from the group consisting of H, alkyl, cycloalkyl, aryl, fused ring aromatic, heterocyclic ring, heterocycle heterocyclic compounds with fused cycles, nitro, halogen, cyano, sulfo, alkoxy, keto, carboxy and carboalkoxy groups, and any two vicinal R ⁴⁶ 'substituents may combine to form a fused ring aromatic compound, a carbocyclic ring residue or a carbocyclic ring residue fused-ring heterocyclic compounds; R ⁴⁵ 'may be a substituted or unsubstituted group selected from the group consisting of H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, heterocyclic compound residue, silyl, nitro, halo, cyano, sulfo, alkoxy, keto and carboxy; the group G, if present, is selected from the group consisting of: 1) -O-; 2) -N (R ⁴⁷ ') -; and 3) -N (R ⁴⁷ 'R ⁴⁸ ') -; R ⁴⁷ '- R ⁴⁸ ' are substituted or unsubstituted groups independently selected from the group consisting of H, oxygen, straight or branched C 1 -C 12 alkyls, alkylenes, alkoxy, aryl, alkaryl, aralkyl, cycloalkyl and heterocyclic radicals; a • fe fefeU · # · · # fe fe fe fe fe fe fe fe fe fe fe fe fe fe fe fe fe fe fe fe fe fe fe fe · Fe · fe · fe · fe · fe fe - 136 (i) mixtures of these substances. 4. The method of claim 1 wherein said fabric is a stain. 5. A bleaching composition comprising (a) a source of peroxygen; and b) an organic catalyst; characterized in that the organic catalyst is released in a controlled manner in the wash solution containing said bleaching agent. 6. A bleaching composition according to claim 5 wherein said peroxygen source is selected from the group consisting of: (i) peroxyacid precursors selected from the group consisting of peroxycarboxylic acids and salts thereof, peroxyacid acid and salts thereof, peroxyacid imides and salts thereof, peroxosulfuric acid and salts thereof, and mixtures thereof; and (ii) a hydrogen peroxide source selected from the group consisting of peroxyborate compounds , percarbonate compounds, peroxyphosphate compounds and mixtures thereof, and a bleach activator. 7. A bleaching composition according to claim 6 wherein said peroxygen source is a hydrogen peroxide source selected from the group consisting of perborate, percarbonate, peroxyphosphate, and mixtures thereof, and a bleach activator. 8. A bleaching composition according to claim 7 wherein said bleach activator is selected from the group consisting of hydrophobic bleach activators. Bleaching composition according to claim 7, characterized in that said bleach activator is selected from the group consisting of tetraacetylethylenediamine (TAED), benzoylcapro-137 lactam (BzCL), 4-nitrobenzoylcaprolactam, 3chlorobenzoylcaprolactam (N) benzoyloxybenzene sulphonate (benzoyloxybenzenesulfonate) , phenylbenzoate (PhBz), decanoyloxybenzenesulfonate (C10-OBS), benzoylvalerolactam (BZVL), octanoyloxybenzenesulfonate (Ca-OBS), perhydrolyzable esters, sodium salt of 4- [N- (nonanoyl) -aminohexanoyloxy] N-benzenesulfonate (N-benzenesulfonate), or Cx ₂ -OBS), 10-decenoyloxybenzenesulfonate (UDOBS or Cn-OBS with a double bond at the 10-position), decanoyloxybenzoic acid (DOBA) and mixtures thereof. 10. A bleaching composition according to claim 5, wherein said organic catalyst is selected from the group consisting of: (a) aryliminium cations and aryliminium polyions having a charge in the range of +3 to -3 and having the general formula [I]: [1] wherein R ¹ -R ² are independently selected from substituted or unsubstituted groups selected from the group consisting of H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, heterocyclic compound residue, silyl, nitro, halo, cyano, sulfo, alkoxy , keto, carboxy, and carboalkoxy; R ¹ and R ⁴ are selected from substituted or unsubstituted saturated or unsaturated groups selected from the group consisting of H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, heterocyclic compound residue, silyl, nitro, halo, cyano, alkoxy, keto, and keto groups ; and X 'is a suitable charge-compensating counterion; and v is a natural number of 1 to 3; • · · · · · · · · · · · · · · · 138 (b) Aryliminium zwitterions having a charge in the range of +3 to -3 having the general formula [II]: [11] wherein R ⁵ -R ⁷ are independently selected from substituted or unsubstituted groups selected from the group consisting of H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, heterocyclic compound residue, silyl, nitro, halo, cyano, sulfo, alkoxy , keto, carboxy, and carboalkoxy; they also include a group of the general formula: where Z _p is covalently bonded to T _o, and is selected from the group consisting of -C 0 -S0 ₂ ~ ₃ -0S0 _3, -S0 ₂ ", -0S0 ₂ and p is either 1, 2 or 3; the group To is selected from the group consisting of substituted or unsubstituted saturated or unsaturated alkyl, cycloalkyl, aryl, alkaryl, aralkyl, and the rest of the heterocyclic compound; (c) modified amines having a charge in the range of -3 to +3, of formulas [V] and [VI]: [VI] [VI] Wherein R ⁹ -R ¹⁰ are independently selected from substituted or unsubstituted groups selected from the group consisting of H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, heterocyclic moiety compounds, silyl, nitro, halogen, cyano, sulfo, alkoxy, keto, carboxy, and carboalkoxy groups and positive or negative charge groups; R ⁸ and R ¹¹ , if present, are selected from the group consisting of substituted or unsubstituted saturated or unsaturated H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, heterocyclic compound residue, silyl, nitro, halo, cyano, sulfo , alkoxy, keto, carboxy and carboalkoxy groups and positive or negative charge groups; R ¹² is a leaving group whose protonated form has a pK _{and a} value (in aqueous medium) between 37> pK _and >-2; wherein, when R ⁹ -R ¹² groups are present, they may combine with each other to form a fused ring aromatic compound, a fused ring carbocyclic compound, or a fused ring heterocyclic compound; and a group of the formula: where Z _p is covalently bonded to To, selected from the group consisting of -C 0 ₂ "-S0 _3", -OSO 3, -SO ₂ ', -0S0 ₂ and p is either 1, 2 or 3; , T _o is selected from the group consisting of substituted or unsubstituted, saturated or unsaturated alkyl, cycloalkyl, aryl, alkaryl, aralkyl, and heterocyclic ring; (d) modified amine oxides having a charge in the range of -3 to +3, of the general formulas [VII] to [X]: - 140 [ix] [X] wherein R ⁹ -R ¹⁰ are independently selected from substituted or unsubstituted groups selected from the group consisting of H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, heterocyclic radical, silyl, nitro, halo, cyano, sulfo, alkoxy, keto, carboxy and carboalkoxy groups and positive or negative charge groups; R ⁸ and R ¹¹ are groups selected from the group consisting of substituted or unsubstituted saturated or unsaturated H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, heterocyclic compound, silyl, nitro, halo, cyano, alkoxy, keto, and carboalkoxy carrying a positive or negative charge; R ¹² is a leaving group whose protonated form has a pK _{and a} value (in aqueous medium) between 37> pK _and >-2; provided that when R ⁸ -R ¹² groups are present, they may combine with each other to form a fused-ring aromatic compound, a fused-ring carbocyclic compound, or 141 a fused-ring heterocyclic compound residue; they also include a group of the general formula: ₀ -t ^ -Z where Z _p is covalently bonded to T _o, and is selected from the group consisting of -CO2- "-S03 ~ -0S0 ₃ ', -SO _2', and _AP-2 -0S0 either 1, 2 or 3; , T _o is selected from the group consisting of substituted or unsubstituted, saturated or unsaturated alkyl, cycloalkyl, aryl, alkaryl, aralkyl, and heterocyclic ring; (e) sulfonimines, phosphonimines, N-acylimines and thiodiazole dioxides of the general formulas [XXIa], [XXIb], [XXII] and [XXIII]: [XX1a] [XXIb] [XXII] wherein R ⁴¹ -R ⁴⁴ , if present, are independently selected from substituted or unsubstituted saturated or unsaturated groups selected from the group consisting of H, alkyl, cycloalkyl; aryl, alkaryl, aralkyl, heterocyclic compound, silyl, nitro, halo, cyano, sulfo, alkoxy, keto, carboxy, and carboalkoxy; provided that any one of the R ⁴¹ -R ⁴⁴ groups may be linked to any other R ⁴¹ -R ^{44 group} to form part of a common cycle, including the remainder of the aromatic compound with fused cycles, the remainder of the carbocyclic compound with fused cycles or 142 cycles; (f) oxaziridinium cations and polyions having a charge in the range of +3 to -3, having the general formula [III]: Wherein R ² '-R ³ ' are independently selected from substituted or unsubstituted groups selected from the group consisting of H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, heterocyclic compound residue, silyl, nitro, halo, cyano , sulfo, alkoxy, keto, carboxy, and carboalkoxy; R ¹ 'and R ⁴ ' are groups selected from the group consisting of substituted or unsubstituted saturated or unsaturated, H, alkyl, cycloalkyl, aryl, alkyl, aralkyl, heterocyclic compound residue, silyl, nitro, halo, cyano, alkoxy groups , keto and carboalkoxy groups; X 'is a suitable charge-compensating counterion; and v is a natural number of 1 to 3; (g) oxaziridinium zwitterions having a charge in the range of +3 to -3 having the general formula [IV]: [1V] wherein R ⁵ '-R ⁷ ' are independently selected from substituted or unsubstituted groups selected from the group consisting of H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, heterocyclic compound residue, silyl, nitro, halo, cyanose ··· * * · · · · · · · · · · · · · · · 143 groups, sulfo, alkoxy, keto, carboxy and carboalkoxy groups; they also include a group of the general formula: -T where Z _p is covalently bonded to T ' _o, and is selected from the group consisting of -CO2- "-SO3" -0S0 _3, -S0 ₂ and -OSO2- and p is either 1, 2 or 3; , T _o is selected from the group consisting of substituted or unsubstituted, saturated or unsaturated alkyl, cycloalkyl, aryl, alkaryl, aralkyl, and heterocyclic ring; (h) oxaziridines, sulfonimines [XXIVa], phosphonimines [XXIVb], Nacylimines [XXV] and thiodiazole dioxides [XXVI] and [XXVII], of the following general formulas: 42 ' O. O. 43 '^ so ₂ y 44 ' 42 'NL 44. ^ SO ₂ R 43 '[XXV] [XXIVb] [XXIVa] [XXVI] wherein R ⁴¹ ' -R ⁴⁴ ', if present, are independently selected from substituted or unsubstituted groups selected from the group consisting of H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, heterocyclic compound, silyl, nitro, halo, cyano, sulfo, alkoxy, ketos144, carboxy, carboalkoxy, any of the R ⁴¹ '-R ⁴⁴ ' groups may be associated with any other R ⁴¹ 'R ^44' to form part of a common cycle, including a fused ring aromatic compound, a fused ring carbocyclic compound, or a fused ring heterocyclic compound; (i) mixtures of these substances. 11. A bleaching composition according to claim 10 wherein the organic catalyst is selected from the group consisting of: (a) aryliminium cations and aryliminium polyions having a charge in the range of +3 to -3 and having the general formula [XI]: wherein m is 1 to 3 when G is present, and m is 1 to 4 when G is absent; n is an integer from 0 to 4; any of R ²⁰ is independently selected from substituted or unsubstituted groups selected from the group consisting of H, alkyl, cycloalkyl, aryl, fused ring aromatic, heterocyclic ring, fused ring heterocycle, nitro, halo, cyano , sulfo, alkoxy, keto, carboxy, and carboalkoxy, and the combination of any two R ²⁰ vicinal substituents may form a fused ring aromatic compound, a fused ring carbocyclic compound, or a fused ring heterocyclic residue; R ¹⁸ may be substituted or 145 is an unsubstituted group selected from the group consisting of H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, heterocyclic compound residue, silyl, nitro, halo, cyano, sulfo, alkoxy, keto, carboxy; carboalkoxy; R ¹⁹ is a group selected from substituted or unsubstituted, saturated or unsaturated groups which are H, alkyl, cycloalkyl, alkaryl, aralkyl, and the heterocyclic compound residue; the group G is selected from the group consisting of: 1) -O-; 2) -N (R ²³⁾ -; and 3) -N (R ²³ R ²⁴ ) -; R ²¹ -R ²⁴ are substituted or unsubstituted groups independently selected from the group consisting of H, oxygen, straight or branched C 1 -C 12 alkyls, alkylenes, alkoxy, aryl, alkaryl, aralkyl, cycloalkyl and heterocyclic radicals; wherein any one of R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ -R ²⁴ may be linked to any other R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ -R ²⁴ to form part of a common cycle; any geminal groups R ²¹ -R ²² may combine with each other to form carbonyl; any of the vicinal groups R ²¹ -R ²⁴ may combine to form a double bond; and at the same time any of the groups R ²¹ -R ²⁴ may combine with each other to form a substituted or unsubstituted fused unsaturated group; X is a suitable charge-compensating counterion; and v is a natural number of 1 to 3; (b) Aryliminium zwitterions having a charge in the range of +3 to -3 and having the general formula [XII]: wherein m is 1 to 3 when G is present and m is 1 to 4 when G is not present; n is an integer from 0 to 4; any of the groups «· • · 146 pin R ²⁶ is independently selected from substituted or unsubstituted groups selected from the group consisting of H, alkyl, cycloalkyl, aryl, aromatic compound of fused-ring aromatic, heterocyclic compound, fused-ring heterocyclic, nitro, halogen, cyano, sulfo, alkoxy, keto, carboxy, and carboalkoxy groups, and any two R ²⁶ vicinal substituents may combine to form the remainder of the fused-ring aromatic compound, the fused-ring carbocyclic compound, or the fused-ring heterocyclic compound; R ²⁵ may be a substituted or unsubstituted group selected from the group consisting of H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, heterocyclic radical, silyl, nitro, halo, cyano, sulfo, alkoxy, keto, carboxy, and carboxy; they also include a group of the general formula: wherein a group, _Z 'is covalently bonded to To, and is selected from the group consisting of -C 0 ₂ "-S0 ₃ -0S0 _3', -S0 ₂ -0S0 ₂ and p is either 1, 2 or 3; _the group T is selected from the group of substances of the formula R ^J where q is a natural number 1 to Q; R ²⁹ is independently selected from substituted or unsubstituted groups selected from the group consisting of unbranched or branched · ♦ · »Μ 147 alkyl, cycloalkyl, alkaryl, aryl, aralkyl, alkylene, heterocyclic compound, alkoxy, arylcarbonyl, carboxyalkyl and amide groups; the group G is selected from the group consisting of: 1) -O-; 2) -N ( ^R30 ) -; and 3) N (R ³⁰ R ³¹ ) -; R ²⁷ , R ²⁸ R ³⁰ and R ³¹ are substituted or unsubstituted groups independently selected from the group consisting of H, oxygen, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, alkylenes, heterocyclic compound, alkoxy, arylcarbonyl, carboxyalkyl and amide groups groups; any of the groups R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , R ³⁰ and R ³¹ may be associated with any other group R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , R ³⁰ and R ³¹ to form part of a common cycle ; any geminal groups R ²⁷ -R ²⁸ may combine with each other to form carbonyl; any of the vicinal R ²⁷ -R ³¹ groups may join to form a double bond; and at the same time any of R ²⁷ -R ³¹ may combine to form a substituted or unsubstituted fused unsaturated group; (c) modified amines of formulas [XV] and [XVI]: [XV] [XVI] of? wherein m is 1 to 3 when G is present, and m is 1 to 4 when G is absent; n is an integer from 0 to 4; R ³⁴ is a group selected from the group consisting of substituted or unsubstituted saturated or unsaturated hydroxy, hydroperoxy, alkoxy, peralkoxy, carboxy, percarboxy, sulfo, and persulfo; any of R ³⁵ is independently selected from substituted or unsubstituted groups selected from the group consisting of H, alkyl, cycloalkyl, aryl, fused ring aromatic, heterocyclic ring, 148 heterocyclic compounds with fused cycles, nitro, halogen, cyano, sulfo, alkoxy, keto, carboxy and carboalkoxy groups, and any two R ³⁵ vicinal substituents can combine to form a fused-ring aromatic compound, a carbocyclic ring, or a carbocyclic ring residue fused-ring heterocyclic compounds; R ³² may be a substituted or unsubstituted group selected from the group consisting of H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, heterocyclic compound residue, silyl, nitro, halo, cyano, sulfo, alkoxy, keto, carboxy, and carboxy; R ³³ may be a substituted or unsubstituted saturated or unsaturated group selected from the group consisting of H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, heterocyclic compound moiety, and also includes a group of the formula: where Z _p is covalently bonded to T _o, and is selected from the group consisting of -CO2-, "-SO 3, -OSO 3 ', -S0 ₂ -0S0 _2', and p is either 1, 2 or 3; the group T _o is selected from the group of groups consisting of: I - (C) q— R38 wherein q is a natural number of 1 to 8; R ³⁸ is independently selected from substituted or unsubstituted groups selected from the group consisting of unbranched or branched H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, alkyl; 149 nu, heterocyclic compound, alkoxy, arylcarbonyl, carboxyalkyl, and amide groups; the group G is selected from the group consisting of: 1) -O-; 2) -N (R ³⁹ ) -; and 3) N (R ³⁹ R ⁴⁰ ) -; R ³⁶ , R ³⁷ , R ³⁹ and R ⁴⁰ are substituted or unsubstituted groups independently selected from the group consisting of H, oxygen, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, alkylenes, heterocyclic compound, alkoxy, arylcarbonyl, carboxyalkyl and amide groups; any of R ³² , R ³³ , R ³⁴ , R ³⁵ , R ³⁶ , R ³⁷ , R ³⁹ and R ⁴⁰ may be associated with any other R ³² , R ³³ , R ³⁴ , R ³⁵ , R ³⁶ , R ³⁷ , R ³⁹ and R ⁴⁰ to form part of a common cycle; any geminal groups R ³⁶ -R ³⁷ may combine with each other to form carbonyl; any of the vicinal groups R ³⁶ , R ³⁷ , R ³⁹ and R ⁴⁰ may combine to form a double bond; and at the same time any of R ³⁶ , R ³⁷ , R ³⁹ and R ⁴⁰ can combine with each other to form a substituted or unsubstituted fused unsaturated group; (d) modified amine oxides of formulas [XVII] to [XX]: wherein m is 1 to 3 when G is present, and m is 1 to 4 when G is absent; n is an integer from 0 to 4; R ³⁴ is a group selected by «·» • · * * • · · 150 is selected from the group consisting of substituted or unsubstituted saturated or unsaturated hydroxy, hydroperoxy, alkoxy, peralkoxy, carboxy, percarboxy, sulfo, and persulfo; any of R ³⁵ is independently selected from substituted or unsubstituted groups selected from the group consisting of H, alkyl, cycloalkyl, aryl, fused ring aromatic, heterocyclic ring, fused ring heterocycle, nitro, halo, cyano , sulfo, alkoxy, keto, carboxy, and carboalkoxy, and any two R ³⁵ vicinal substituents may combine to form a fused-ring aromatic compound, a fused-ring carbocyclic compound, or a fused-ring heterocyclic compound; R ³² may be a substituted or unsubstituted group selected from the group consisting of H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, heterocyclic radical, silyl, nitro, halo, cyano, sulfo, alkoxy, keto, carboxy, and carboxy; R ³³ may be a substituted or unsubstituted saturated or unsaturated group selected from the group consisting of H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, heterocyclic compound moiety, and also includes a group of the formula: To - 2 - wherein the group Z _p is covalently bonded to the group T _o and is selected from the group consisting of -CO ₂ -SO ₃ , -OSO ₃ , -SO ₂ - and -OSO ₂ ', and _p is either 1, 2 or 3; group T _o is selected from the group of groups consisting of: I · * φ φ «* • φ · 151 «Φ · ΦΦ4« * ^r 7 · Φ · · ΦΦ · «Φ R38 Φ · Φ Φ · Φ> * ΦΦ ΦΦΦ ΦΦΦΦ - (C) q - R ³⁸ where q is a natural number 1 to 8; R ³⁸ is independently selected from substituted or unsubstituted groups selected from the group consisting of unbranched or branched H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, alkylene, heterocyclic compound residue, alkoxy, arylcarbonyl, carboxyalkyl and amide groups; the group G is selected from the group consisting of: 1) -O-; 2) -N (R ³⁹ ) -; and 3) -N (R ³⁹ R ⁴⁰ ) -; R ³⁶ , R ³⁷ , R ³⁹ and R ⁴⁰ are substituted or unsubstituted groups independently selected from the group consisting of H, oxygen, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, alkylenes, heterocyclic compound, alkoxy, arylcarbonyl, carboxyalkyl, and amide groups; any of R ³² , R ³³ , R ³⁴ , R ³⁵ , R ³⁶ , R ³⁷ , R ³⁹ and R ⁴⁰ may be associated with any other R ³² , R ³³ , R ³⁴ , R ³⁵ , R ³⁶ , R ³⁷ , R ³⁹ and R ⁴⁰ to form part of a common cycle; any geminal groups R ³⁶ R ³⁷ may combine with each other to form carbonyl; any of the vicinal groups R ³⁶ , R ³⁷ , R ³⁹ and R ⁴⁰ may combine to form a double bond; and at the same time any of R ³⁶ , R ³⁷ , R ³⁹ and R ⁴⁰ can combine with each other to form a substituted or unsubstituted fused unsaturated group; (e) sulfonimines [XXVIIIa], phosphonimines [XXVIIIb], N-acylimines [XXIX] of the general formulas: [XXVIIIa] 152 w w w w w w w w w w w w w «« Wherein any one of R ⁴⁶ is independently selected from substituted or unsubstituted groups selected from the group consisting of H, alkyl, cycloalkyl, aryl, a condensed ring aromatic compound, a heterocyclic compound residue , fused-ring heterocyclic compound, nitro, halogen, cyano, sulfo, alkoxy, keto, carboxy, and carboalkoxy, and any two R ⁴⁶ substituents may combine to form a fused-ring aromatic compound, carbocyclic ring, or carbocyclic ring residue; a fused-ring heterocyclic compound residue; R ⁴⁵ may be a substituted or unsubstituted group selected from the group consisting of H, alkyl, cycloalkyl, alkaryl, aryl, aralkyls, heterocyclic compound residue, silyl, nitro, halo, cyano, sulfo, alkoxy, keto, carboxy, and carboxy; the group G, if present, is selected from the group consisting of: 1) -O-; 2) -N (R ⁴⁷ ) -; and 3) -N (R ⁴⁷ R ⁴⁸ ) -; R ⁴⁷ R ⁴⁸ are substituted or unsubstituted groups independently selected from the group consisting of H, oxygen, straight or branched C 1 -C 12 alkyls, alkylenes, alkoxy, aryl, alkaryl, aralkyl, cycloalkyl and heterocyclic radicals; and n is an integer from 0 to 4; (f) oxaziridinium cations and polyions having a charge in the range of +3 to -3, having the general formula [XIII]: [X111] t t t X X X X X X X X X * 153 wherein m is 1 to 3 when G is present, and m is 1 to 4 when G is not present; n is an integer from 0 to 4; any of R ²⁰ 'is independently selected from substituted or unsubstituted groups selected from the group consisting of H, alkyl, cycloalkyl, aryl, aromatic compound of fused-ring aromatic, heterocyclic compound, fused-ring heterocyclic compound, nitro, halogen, cyano, sulfo, alkoxy, keto, carboxy, and carboalkoxy, and any two R ²⁰ 'vicinal substituents may combine to form a fused ring aromatic, fused ring carbocyclic or heterocyclic ring; R ¹⁸ 'may be a substituted or unsubstituted group selected from the group consisting of H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, heterocyclic compound residue, silyl, nitro, halo, cyano, sulfo, alkoxy, keto, carboxy, and carboxy; R ¹⁹ 'may be a substituted or unsubstituted saturated or unsaturated group selected from the group consisting of H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, and the heterocyclic compound moiety, G is selected from the group consisting of: 1) -O-; 2) -N (R ²³ ') -; and 3) -N (R ^23Z R ²⁴⁾ R ²¹ '-R ^24' are substituted or unsubstituted radicals independently selected from the group consisting of H, oxygen, linear or branched C1-C12 alkyls, alkylenes, alkoxys, aryls, alkaryls , aralkyls, cycloalkyls and heterocyclic radicals; wherein any of R ¹⁸ ', R ¹⁹ ', R 10 '-R ²⁴ ' may be joined to any other R ¹⁸ ', R ¹⁹ ', R ²⁰ '-R ²⁴ ' to form part of a common cycle; any geminal groups R ²¹ '-R ²² ' may be combined with each other to form carbonyl; any of the vicinal groups R ²¹ '-R ²⁴ ' may be joined to form a double bond; and at the same time any of the groups R ²¹ -R ²⁴ 'can combine with each other to form a substituted or unsubstituted fused unsaturated moiety154 · · · · · · · ft · ft · ··· · «ny; X 'is a suitable charge-compensating counterion; and v is a natural number of 1 to 3; (g) oxaziridinium zwitterions having a charge in the range of +3 to -3 having the general formula [XIV]: wherein m is 1 to 3 when G is present and m is 1 to 4 when G is not present; n is an integer from 0 to 4; any of R ²⁶ 'is independently selected from substituted or unsubstituted groups selected from the group consisting of H, alkyl, cycloalkyl, aryl, aromatic ring compound, heterocyclic ring compound, cyclic ring heterocycle compound, nitro, halogen, cyano, sulfo, alkoxy, keto, carboxy, and carboalkoxy groups, and any two vicinal R ²⁶ 'substituents may combine to form a fused ring aromatic compound, a fused ring carbocyclic compound, or a fused ring heterocyclic residue; R ²⁵ 'may be a substituted or unsubstituted group selected from the group consisting of H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, heterocyclic compound residue, silyl, nitro, halo, cyano, sulfo, alkoxy, keto, carboxy and carboxy; groups of general formula: —T _o —zf ³ Wherein Ζ'ρ 155 is covalently bonded to T ' _o is selected from the group consisting of -S0 ₂ -C 0 -C _3, -OSO _3, -S0 ₂ -0S0 ₂ and a is either 1 or 2; the group T ' _o is selected from the group of groups consisting of: R29 ’- (C) q— ^{29 29} 'where q is a natural number from 1 to 8; R ²⁹ 'is independently selected from substituted or unsubstituted groups selected from the group consisting of straight or branched H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, alkylene, heterocyclic compound residue, alkoxy, arylcarbonyl, carboxyalkyl and amide groups; the group G is selected from the group consisting of: 1) -O-; 2) -N ( ^R30 ') -; a3) N (R ³⁰ 'R ³¹ ') -; R ²⁷ '. R ²⁸ '. R ³⁰ 'and R ³¹ ' are substituted or unsubstituted groups independently selected from the group consisting of H, oxygen, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, alkylenes, heterocyclic compound residue, alkoxy, arylcarbonyl groups, carboxyalkyl groups and amide groups; any of R ²⁵ ', R ²⁶ ', R ²⁷ ', R ²⁸ ', R ³⁰ 'and R ³¹ ' may be associated with any other R ²⁵ ', R ²⁶ ', R ²⁷ ', R ²⁸ ', R ³⁰ 'and R ³¹ ' to form part of a common cycle; any geminal groups R ²⁷ '-R ²⁸ ' may be combined with each other to form carbonyl; any of the vicinal groups R ²⁷ '-R ³¹ ' may be joined to form a double bond; and at the same time any of the groups R ²⁷ '-R ³¹ ' may combine with each other to form a substituted or unsubstituted fused unsaturated group; (h) oxaziridine sulfonimines [XXXIa], phosphonimines [XXXIb], Nacylimines [XXXII] of the general formulas: 156 [XXXIa] [XXXIb] [XXXII] where any of the R groups ⁴⁶ 'is independently selected from substituted or unsubstituted groups selected from the group consisting of H, alkyl, cycloalkyl, aryl, fused ring aromatic compound, heterocyclic ring compound, fused ring heterocycle compound, nitro, halogen, cyano, sulfo, alkoxy, keto, carboxy, and carboalkoxy groups, and any two R ⁴⁶ 'vicinal substituents can combine to form a fused ring aromatic compound, a carbocyclic ring compound, or a fused ring heterocycle compound; R ⁴⁵ 'can be a substituted or unsubstituted group selected from the group consisting of H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, heterocyclic compound residue, silyl, nitro, halo, cyano, sulfo, alkoxy, keto, carboxy, and carboxy; the group G, if present, is selected from the group consisting of: 1) -O-; 2) -N (R ⁴⁷ ') -; and 3) N (R ⁴⁷ 'R ⁴⁸ ') -; R ⁴⁷ '-R ⁴⁸ ' are substituted or unsubstituted groups independently selected from the group consisting of H, oxygen, straight or branched C 1 -C 12 alkyls, alkylenes, alkoxy, aryl, alkaryl, aralkyl, cycloalkyl and heterocyclic radicals; and n is an integer from 0 to 4; and (i) mixtures of these substances. 12. A bleaching composition according to claim 5, wherein said bleaching composition further comprises one bleaching composition. 157 or more detergent ingredients selected from the group consisting of: surfactants, solvents, buffers, enzymes, soil release agents, clay soil removal agents, dispersants, brighteners, foam suppressors, fabric softeners, organic foaming catalysts, enzyme stabilizers , extenders, chelating agents, other bleaching agents including metal catalysts, other organic catalysts, dyes, dye transfer inhibiting agents, fragrances and mixtures thereof. 13. An article comprising an organic catalyst, including instructions for use of said compound for cleaning soiled fabric, comprising the step of contacting said fabric with a laundry solution containing said article, wherein said organic catalyst is released in a controlled manner into said article. washing solution. The article of claim 13, which is a laundry detergent. The article of claim 13, which is a laundry adjuvant, 16. A modified amine selected from the group consisting of modified amine oxides of formulas [VII] to [X]: [1X] [X] • 158 wherein R ⁸ -R ¹⁰ are independently selected from substituted or unsubstituted groups selected from the group consisting of H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, heterocyclic compound, silyl, nitro, halo, cyano, alkoxy, keto, carboalkoxy and groups carrying positive or negative charges; R ¹¹ , if present, is selected from the group consisting of substituted or unsubstituted saturated or unsaturated H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, heterocyclic compound residue, silyl, nitro, halo, cyano, alkoxy, ketos , carboalkoxy and groups carrying positive or negative charges; R ¹² is a leaving group whose protonated form has a pK _{and a} value (in aqueous medium) between 37> pK _and >-2; wherein, when R ⁸ -R ¹² groups are present, they can combine with each other to form a fused-ring aromatic compound, a fused-ring carbocyclic compound, or a fused-ring heterocyclic compound. A modified amine according to claim 16, wherein R ¹¹ is a group of the formula: wherein Zp 'is covalently bonded to T _o, selected from the group consisting of -S0 ₂ -C 0 -C _3', -0S0 _3, -S0 ₂ ~ -0S0 ₂ and p is either 1, 2 or 3; , T _o is selected from the group consisting of substituted or unsubstituted, saturated or unsaturated alkyl, cycloalkyl, aryl, alkaryl, aralkyl, and heterocyclic ring. The modified amine of claim 17, wherein the pK _and R ¹² are greater than 3 and less than 23. 159 • fcfcfcfc ► · · · · · · The modified amine of claim 17, wherein the pK _and R ¹² are greater than 9 and less than 21. The modified amine of claim 18, wherein the pK _and R ¹² are greater than 11 and less than 17. 21. The modified amine compound according to claim 16, characterized in that the group R ¹² is selected from the group consisting of substituted or unsubstituted, saturated or unsaturated hydroxy, perhydroxy, an alkoxy and peralkoxy radicals. The modified amine of claim 21, wherein said R ¹² is selected from the group consisting of hydroxy or hydroperoxy groups. 23. The modified amine of claim 16, wherein the modified amine is one of compounds of formulas [XVII] to [XX]. wherein m is 1 to 3 when G is present, and m is 1 to 4 when G is absent; n is an integer from 0 to 4; R ³⁴ is a leaving group whose protonated form has a pK _{and a} value (in aqueous medium) between 37> pK _and >-2; any of R ³⁵ is 160 is independently selected from substituted or unsubstituted groups selected from the group consisting of H, alkyl, cycloalkyl, aryl, fused ring aromatic, heterocyclic ring, fused ring heterocycle, nitro, halo, cyano, sulfo, alkoxy, keto, carboxy, and carboalkoxy groups, and any two R ³⁵ vicinal substituents can combine to form a fused ring aromatic compound, a fused ring carbocyclic compound, or a fused ring heterocyclic compound; R ³² may be a substituted or unsubstituted group selected from the group consisting of H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, heterocyclic compound residue, silyl, nitro, halo, cyano, sulfo, alkoxy, keto, carboxy and carboxy; R ³³ may be a substituted or unsubstituted saturated or unsaturated group selected from the group consisting of H _of alkyl, cycloalkyl, alkaryl, aryl, aralkyl, the heterocyclic compound moiety, including anionic and / or charged cationic groups. 24th modified amine compound according to claim 23, characterized in that the group R ³³ has the formula: - T _o —zf wherein Z _p 'is a group covalently bonded to a To group selected from the group consisting of -CO 2 - -SO 3 ", -OSO 3, -SO ₂ " and -OSO ₂ "and _p is either 1, 2 or 3; group This is selected from a group of groups consisting of _r 38 I - (C) q— R ³⁸ - 161 wherein q is a natural number of 1 to 8; R ³⁸ is independently selected from substituted or unsubstituted groups selected from the group consisting of unbranched or branched H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, alkylene, heterocyclic compound residue, alkoxy, arylcarbonyl, carboxyalkyl and amide groups; the group G is selected from the group consisting of: 1) -O-; 2) -N (R ³⁹ ) -; and 3) -N (R ³⁹ R ⁴⁰ ) -; R36, P37, _{R 39} ares 4o j _sou substituted or unsubstituted radicals 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 R ³² , R ³³ , R ³⁴ , R ³⁵ , R ³⁶ , R ³⁷ , R ³⁹ and R ⁴⁰ may be associated with any other R ³² , R ³³ , R ³⁴ , R ³⁵ , R ³⁶ , R ³⁷ , R ³⁹ and R ⁴⁰ to form part of a common cycle; any geminal groups R ³⁶ R ³⁷ may combine with each other to form carbonyl; any of the vicinal groups R ³⁶ , R ³⁷ , R ³⁹ and R ⁴⁰ may combine to form a double bond; and at the same time any of R ³⁶ , R ³⁷ , R ³⁹ and R ⁴⁰ may combine with each other to form a substituted or unsubstituted fused unsaturated group. 25. The modified amine of claim 23, wherein the pK _and the R &lt; ³⁴ &gt; 23. 26. The modified amine of claim 25, wherein the pK _and the R &lt; ³⁴ &gt; value are greater than 11 and less than 17. 27th modified amine compound according to claim 23, characterized in that the group R ³⁴ is selected from the group consisting of substituted or unsubstituted, saturated or unsaturated hydroxy, perhydroxy, alkoxy and peralkoxy radicals. A modified amine according to claim 27, characterized in that 162, wherein R ³⁴ is selected from the group consisting of hydroxy or hydroperoxy. 29. The modified amine of claim 16, wherein the modified amine is one of compounds of formulas [XV] and [XVI]. [XV] [xvi] wherein m is 1 to 3 when G is present, and m is 1 to 4 when G is not present; n is an integer from 0 to 4; R ³⁴ is a leaving group whose protonated form has a p-β value (in aqueous medium) between 20> pK _and >10; any of R ³⁵ is independently selected from the group consisting of H, alkyl, cycloalkyl, aryl, fused ring aromatic compound, heterocyclic ring compound, fused ring heterocycle compound, nitro, halo, cyano, sulfo, alkoxy, keto, , carboxy and carboalkoxy groups, and any two R ³⁵ vicinal substituents may combine to form a fused ring aromatic compound, a fused ring carbocyclic compound, or a fused ring heterocyclic residue; R ³² is a group selected from the group consisting of H or Me; R ³³ is a substituted or unsubstituted saturated or unsaturated group selected from the group consisting of C 3 -C 18 alkyl, C 3 -C 18 cycloalkyl, and groups bearing a negative or positive charge. Modified amine according to claim 29, characterized in that the group R ³³ has the general formula: · Z · Z To Z To To To To To To To To To To To To To To To To To To _p - group is covalently bonded to T _o, which is selected from the group consisting of -CO2-, "-SO 3, -OSO3-, -SO2- and -OSO2- and p ~ is either 1, 2 or 3; the group T _o is selected from the group of groups consisting of: 163 R38 - (C) q— Wherein q is a natural number from 1 to 8; R ³⁸ is independently selected from substituted or unsubstituted groups selected from the group consisting of unbranched or branched H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, alkylene, heterocyclic compound moiety, alkoxy, arylcarbonyl, carboxyalkyl and amide groups; the group G is selected from the group consisting of: 1) -O-; 2) -N (R ³⁹ ) -; and 3) -N (R ³⁹ R ⁴⁰ ) -; R ³⁶ , R ³⁷ , R ³⁹ and R ⁴⁰ are substituted or unsubstituted groups independently selected from the group consisting of H, oxygen, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, alkylene, heterocyclic compound, alkoxy, arylcarbonyl, carboxyalkyl, and amide groups; any of R ³² , R ³³ , R ³⁴ , R ³⁵ , R ³⁶ , R ³⁷ , R ³⁹ and R ⁴⁰ may be associated with any other R ³² , R ³³ , R ³⁴ , R ³⁵ , R ³⁶ , R ³⁷ , R ³⁹ and R ⁴⁰ to form part of a common cycle; if G is present, any geminal groups R ³⁶ -R ³⁷ may combine with each other to form carbonyl; any of the vicinal groups R ³⁶ , R ³⁷ , R ^39, and R ⁴⁰ may combine to form a double bond; and at the same time any of the groups R ³ , R ³⁷ , R ³⁹ and R ⁴⁰ may combine with each other to form a substituted or unsubstituted fused unsaturated group, 31. The modified amine of claim 29, wherein the amine is modified 164 wherein R ³⁴ is selected from the group consisting of hydroxy or hydroperoxy. 32. A bleaching composition comprising a modified amine in conjunction with or without a peroxygen source, characterized in that the modified amine is selected from the group consisting of modified amines of general formula [V] and / or of general formula [VI]; amine oxides of the formulas [VII] to [X] and mixtures thereof: [V11] [VIII] [IX] [X] wherein R ⁸ -R ¹⁰ are independently selected from substituted or unsubstituted groups selected from the group consisting of H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, heterocyclic compound residue, silyl, nitro, halo, cyano, alkoxy, keto, carboalkoxy and positive or negative charge groups; a group R ¹¹ , if present, is a group selected from the group consisting of a group consisting of: 165 substituted or unsubstituted saturated or unsaturated H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, heterocyclic compound residue, silyl, nitro, halo, cyano, alkoxy, keto, carboalkoxy, and positive or negative groups; R ¹² is a leaving group whose protonated form has a pK _{and a value} (in aqueous medium) between 37> pK _and >-2; wherein, when R ⁸ -R ¹² groups are present, they may combine with each other to form a fused ring aromatic compound, a fused ring carbocyclic compound, or a fused ring heterocyclic residue. A bleaching composition according to claim 32, wherein the group R ¹¹ has the general formula: wherein Zp is a group covalently bonded to a To group selected from the group consisting of -CO 2 -SO 3 ', -OSO 3 ·, -SO 2 "and -OSO 2", p is either 1, 2 or 3; , T _o is selected from the group consisting of substituted or unsubstituted, saturated or unsaturated alkyl, cycloalkyl, aryl, alkaryl, aralkyl and heterocyclic ring. A bleaching composition according to claim 32, wherein the pK _and R ¹² are greater than 3 and less than 23. 35. A bleaching composition according to claim 34, characterized in that the pKa value of R ¹² is greater than 9 and lower than the 21st 36. A bleaching composition according to claim 35, characterized in that the pKa value _and the groups R ¹² is greater than 11 and less than 17. 166 The bleaching composition of claim 32, wherein R ¹² is selected from the group consisting of substituted or unsubstituted saturated or unsaturated hydroxy, hydroperoxy, alkoxy, and peralkoxy. 38. A bleaching composition according to claim 37, characterized in that R ¹² is selected from the group consisting of hydroxy smb or perhydroxy. 39. The bleaching composition of claim 32, wherein said modified amine is from about 0.001 to about 10% by weight of said composition, and wherein said peroxygen source, if present, is from about 0.01 to about 60% by weight of said bleaching agent. preparation. 40. The bleaching composition of claim 32, wherein said peroxygen source, if present, is selected from the group consisting of: (a) peroxyacid precursors selected from the group consisting of percarboxylic acids and their salts, peroxyimides and their salts, peroxosulfuric acid and its salts, and mixtures thereof; (b) hydrogen peroxide sources selected from the group consisting of perborate compounds, percarbonate compounds, perphosphate compounds, and mixtures thereof; and a bleach activator. A bleaching composition comprising any of the modified amines of formulas [XV] to [XX]. [XV] 167 • c ···· · · · · · Wherein m is 1 to 3 when G is present, and m is 1 to 4 when G is absent; n is an integer from 0 to 4; R ³⁴ is a leaving group whose protonated form has a pK _and an (aqueous) value of 37> pK _and >-2; any of R ³⁵ is independently selected from substituted or unsubstituted groups selected from the group consisting of H, alkyl, cycloalkyl, aryl, fused ring aromatic, heterocyclic ring, fused ring heterocycle, nitro, halo, cyano , sulfo, alkoxy, keto, carboxy, and carboalkoxy, and any two R ³⁵ vicinal substituents may combine to form a fused-ring aromatic compound, a fused-ring carbocyclic compound, or a fused-ring heterocyclic compound; R ³² may be a substituted or unsubstituted group selected from the group consisting of H, alkyl, cycloalkyl, alkaryl, aryl, aralkyls, heterocyclic compound residue, silyl, nitro, halo, cyano, sulfo, alkoxy, keto, carboxyalkoxy and carboxyalkoxy groups ; R ³³ may be a substituted or unsubstituted saturated or unsaturated group selected from the group consisting of H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, heterocyclic compound moiety, including negative or positive charge groups. 42. A bleaching composition according to claim 41, wherein the group R ³³ has the general formula: where Z _p is covalently bonded to To, which is selected from the group consisting of -C 0 -C ₂ -SO ₃ '-0S0 _3, -SO 2' and -0S0 ₂ and p is either 1, 2 or 3; the group T _o is selected from the group of groups consisting of: R ³⁸ I - (C) q— R ³⁸ wherein q is a natural number of 1 to 8; R ³⁸ is independently selected from substituted or unsubstituted groups selected from the group consisting of straight or branched H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, alkylene, heterocyclic compound, alkoxy, arylcarbonyl, carboxyalkyl and amide groups; the group G is selected from the group consisting of: 1) -0; 2) -N (R ³⁹ ) -; and 3) -N (R ³⁹ R ⁴⁰ ) -; R ³⁶ , R ³⁷ , R ³⁹ and R ⁴⁰ are substituted or unsubstituted groups independently selected from the group consisting of H, oxygen, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, alkylenes, heterocyclic compound, alkoxy, arylcarbonyl, carboxyalkyl, and amide groups; any of R ³² , R ³³ , R ³⁴ , R ³⁵ , R ³⁶ , R ³⁷ , R ³⁹ and R ⁴⁰ may be associated with any other R ³² , R ³³ , R ³⁴ , R ³⁵ , R ³⁶ , R ³⁷ , R ³⁹ and R ⁴⁰ for part of a common cycle; any geminal groups R ³⁶ -R ³⁷ may combine with each other to form carbonyl; any of the vicinal groups R ³⁶ , R ³⁷ , R ³⁹ and R ⁴⁰ may combine to form a double bond; and at the same time any of R ³⁶ , R ³⁷ , R ³⁹ and R ⁴⁰ may combine with each other to form a substituted or unsubstituted fused unsaturated group. A bleaching composition according to claim 41, wherein the pK _and the R ³⁴ value are greater than 3 and less than 23. A bleaching composition according to claim 43, wherein the pK _and the R ³⁴ value are greater than 11 and less than 17. 45. A bleaching composition according to claim 41, characterized in that R ³⁴ is selected from the group consisting of substituted or unsubstituted, saturated or unsaturated hydroxy, perhydroxy, alkoxy and peralkoxy radicals. The bleaching composition of claim 45, wherein the R ^{34 group} is selected from the group consisting of hydroxy and hydroperoxy. 47. The bleaching composition of claim 32, further comprising one or more detergent ingredients selected from the group consisting of: surfactants, solvents, buffers, enzymes, soil release agents, clay soil removal agents, dispersants, brighteners, foam reducing agents, fabric softeners, organic foaming catalysts, enzyme stabilizers, extenders, chelating agents, other bleaching agents including metal catalysts, other organic catalysts, dyes, dye transfer inhibiting agents, fragrances and mixtures thereof. 48. The bleaching composition of claim 47, further comprising a surfactant. A bleaching composition according to claim 48, characterized in that the bleaching agent is a bleaching agent. 170, wherein said surfactant is a branched surfactant. 50. The bleaching composition of claim 49, wherein said surfactant is a medium molecular weight surfactant. 51. The bleaching composition of claim 48, wherein said surfactant is an anionic surfactant. 52. The bleaching composition of claim 41, wherein said surfactant further comprises a chelating agent. 53. The bleaching composition of claim 41, wherein said surfactant further comprises other bleaching agents selected from the group consisting of perborates, percarbonates, peroxyphosphates, and mixtures thereof. 54. The bleaching composition of claim 53, wherein said surfactant further comprises a bleach activator. 55. The bleaching composition of claim 54, wherein said activator is selected from the group consisting of hydrophobic bleach activators. 56. The bleaching composition of claim 55 wherein said bleach activators are selected from the group consisting of tetraacetylethylenediamine (TAED), benzoylcaprolactam (BzCL), 4-nitrobenzoylcaprolactam, 3-chlorobenzoylcaprolactam, benzoyloxybenzenesulfonate (BOBS), nonanoyloxybenzenesulfonate (NOBS), phenylbenzoate (PhBz), decanoyloxybenzenesulfonate (C10-OBS); ) amino-hexanoyloxy] -benzene sulfonate (NACAOBS), lauryl-oxybenzenesulfonate (LOBS or C12-OBS), 10 171 fcfc fcfcfcfc fcfcfcfc fcfc fcfcfcfc undecenoyloxybenzenesulfonate (UDOBS or Cu-OBS double bonded) 10), decanoyloxybenzoic acid (DOBA) and mixtures thereof. 57. The bleaching composition of claim 41, further comprising an enzyme. 58. The bleaching composition of claim 57, wherein the enzyme is an enzyme selected from the group consisting of cellulase, lipase, amylase, phospholipase, protease, peroxidase, and mixtures thereof. 59. A method of laundering soiled fabrics comprising contacting said fabrics with a laundry solution comprising a bleaching composition according to claim 32. 60. A laundry detergent containing a modified amine selected from the group consisting of modified amines of formulas [V] to [X] and mixtures thereof: R ⁸ o 1 _r 8 R ² T '- [IN] [VI] R ¹² _{Rf &gt}; rf ₂ w-y [VII] [VIII] R, 4 ^ 0® R ^{, o} 't t ² ? R ² [ix] [X] • » Wherein R ⁸ -R ¹⁰ are independently selected from substituted or unsubstituted groups selected from the group consisting of H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, heterocyclic compound residue, silyl, nitro group , halo, cyano, alkoxy, keto, carboalkoxy and positive or negative charge groups; if present, R ^11, it is a group selected from the group consisting of substituted or unsubstituted, saturated or unsaturated H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, heterocyclic ring, silyl, nitro, halo, cyano, alkoxy, keto, carboalkoxy and positively or negatively charged groups; R ¹² is a leaving group whose protonated form has a pK _and an (aqueous) value of 37> pK _and >-2; wherein, when R ⁸ -R ¹² groups are present, they may combine with each other to form a fused-ring aromatic compound, a fused-ring carbocyclic compound, or a fused-ring heterocyclic compound. 61. The laundry additive product according to claim 60, characterized in that the group R ¹¹ has the formula: • £ To- wherein Zp 'is covalently bonded to T _o, which is selected from the group consisting of -CO 2 -SO _3, -OSO _3', and -SO2-OSO2 'and p is either 1, 2 or 3; the group To is selected from the group consisting of substituted or unsubstituted saturated or unsaturated alkyl, cycloalkyl, aryl, alkaryl, aralkyl, and the rest of the heterocyclic compound. 62. The laundry detergent composition of claim 60, wherein the laundry detergent composition is packaged in the form of capsules, tablets, gel pads, or other packs. - 173 containing single doses. 63. The laundry detergent composition of claim 60, further comprising a suitable carrier.