ES2252054T3 - COMPONENTS OF STABLE FORMULATIONS, COMPOSITIONS AND CLOTHING WASHING METHODS USED BY THE SAME. - Google Patents

Abstract

A bleaching composition comprising an organic catalyst compound together with or without a peroxygen source, wherein said organic catalyst compound has a shelf life of the organic catalyst greater than or equal to 30 minutes and is a cationic organic catalyst compound having the following formula: wherein and where R50-R54 are independently selected from a substituted or unsubstituted radical selected from the group consisting of H, alkyl, cycloalkyl, alkylaryl, aryl, aralkyl, heterocyclic ring, silyl, nitro, halo radicals, linear or branched cyano, alkoxy, keto and carboalkoxy, provided that any R50-R54 can be attached to any other R50-R54 to form part of a common ring; and when R54 is H, R50- R51 does not combine with any R53-R53 to form an aromatic ring, X- is a suitable charge-balancing counterion, and v is an integer from 1 to 3, which is characterized by at least one of R50-R51 is not H.

Description

Components of stable formulations, compositions and methods of washing clothes using same.

Field of the Invention

The present invention relates to components for formulations such as organic catalyst compounds that have greater stability and to compositions and methods of washing clothes that use these organic catalyst compounds. Plus especially, this invention relates to catalyst compounds organic such as bleach reinforcing compounds of type quaternary imine, oxaciridinium type bleaching species quaternary, modified amines and amine oxides, and to compositions and laundry methods that use these compounds organic catalysts

Background of the invention

Launching bleaching agents lately of oxygen are becoming increasingly popular in Household and personal grooming products for facilitating the stain and dirt removal. The bleachers are especially desirable for its elimination properties of stains, thick tissue cleaning, bleaching and sanitation. Oxygen bleaching agents have special acceptance in laundry products such as detergents, in dishwasher products and in cleaners of hard surfaces. The bleaching agents releasing Oxygen, however, have somewhat limited efficacy. Between the most frequently encountered inconveniences include your lack of security for the color of the tissues and their tendency to Extremely depend on the temperature. So, the colder it is the solution in which they are used, the less effective is the action of bleaching. Temperatures above 60ºC are typically necessary to ensure the effectiveness of a bleaching agent oxygen releasing solution.

To solve the problem of dependence on the aforementioned temperature has developed a kind of compounds known as "bleach activators". The bleach activators, typically acyl compounds perhydrolysable having a leaving group such as oxybenzenesulfonate, react with the active oxygen group, of typical form hydrogen peroxide or its anion, to form a peroxyacid oxidant more effective. It is the peroxyacid compound that then oxidize the dirty or stained substrate material. Without However, bleach activators also depend on some temperature measurement. Bleach activators are more effective at temperate water temperatures between approximately 40 ° C and approximately 60 ° C. At water temperatures below approximately 40 ° C, the peroxyacid compound loses part of its whitening efficiency

Unsuccessful attempts have been made, as described in patents US-5,360,568, US 5,360,569 and US 5,370,826, granted to Madison et al., to develop a system bleach comprising organic catalysts, more in in particular, organic catalysts based on iminium, whatever effective at lower water temperatures and safe for colors. However, the cationic salts of quaternary imine, the Organic catalysts described in these applications do not result totally satisfactory for bleaching applications in laundry In particular, quaternary imine salts when they combine with peroxygenated compounds damage unacceptably The colors of the fabric. In addition, quaternary imine salts are less stable at higher wash temperatures, which may cause a loss of efficiency.

US Patents 5,576,282 and US 5,817,614, both granted to Miracle et al., describe another attempt to develop a bleaching system that understand effective organic catalysts in lower conditions Water temperature and be safe for colors. Although the bleaching system described in this patent provides greater color security with respect to bleaching systems with traditional organic catalyst in conditions of lower water temperatures, it is also preferred to achieve this bleaching at higher washing temperature.

Many imines and dihydroisoquinoliniums and bleaching quaternary oxaciridinium species formed from of them illustrated in the art have a shelf life of organic catalyst less than 30 min at 20 ° C, determined according to Test protocol described below. Older temperatures, such as 40 ° C, the life of the organic catalyst It would be less than 3 min. At even higher wash temperatures,  such as 60 ° C, the life of the organic catalyst would be shorter to 20 seconds This instability at wash temperatures more Hot can lead to a dramatic loss of effectiveness.

In view of the above, researchers have been looking for bleaching systems with organic catalyst effective that provide effective bleaching at water temperatures lower (cold) and higher (warm or hot) and provide better stability against unwanted decomposition of organic catalyst

Therefore, it is clear that the need to have a bleaching system with catalyst organic that provides greater stability against a unwanted decomposition of the organic catalyst and that provide effective bleaching not only in lower conditions water temperature but also more effective bleaching at higher water temperature with respect to the bleaching system described in The state of the art.

Summary of the invention

The present invention covers the needs discussed above. The present invention provides components for formulations such as catalyst compounds organic as defined in claim 1 with a shelf life of the organic catalyst greater than 30 minutes, determined according to Test protocol described below. These compounds organic catalysts are effective not only for another period prolonged under conditions of lower water temperature, such as the temperature of 20ºC indicated in the Protocol, and at temperatures lower such as 5 ° C, but also have a longer life catalyst useful under higher temperature conditions of water, such as above 40 ° C and up to about 60 ° C or even higher temperatures, leading to higher stability of the organic catalyst compared to the organic catalyst for state bleaching systems technique.

For example, an organic catalyst compound with an organic catalyst (OCL) shelf life of only 20 minutes at 20 ° C, determined according to the Test Protocol described more forward, you will have an OCL of only about 2 minutes at 40 ° C, while an organic catalyst compound with an OCL of 10 hours at 20 ° C, determined according to the Test Protocol that described below, you will have an OCL of approximately 1 hour at 40 ° C Similarly, an organic catalyst compound with an OCL 40 minutes at 20 ° C, determined according to the Test Protocol that described below, you will have an OCL of approximately 4 minutes at 40 ° C. The performance advantage of a lifetime of 1 hour at 40 ° C against a useful life of 2 minutes at 40 ° C it is evident. For a 10 minute wash cycle, for example, the performance of a organic catalyst compound with a shelf life of 4 minutes at 40 ° C, compared with a shelf life of 2 minutes at 40 ° C, also it can be much larger, especially if the stained tissue that requires to be washed is added to the wash solution after that the OCL of the organic catalyst of the state of the technique (that is, after 2 minutes). Organic catalyst of the state of the art will present a reduced or no bleaching (shelf life expired), while the organic catalyst provided by the present invention (which has 2 minutes left OCL) will continue to show effective bleaching.

Non-limiting examples of the advantages provided by the components of the formulation, in particular Organic catalyst compounds, include greater efficacy bleaching, such as stain removal, bleaching, etc., to higher and lower water temperatures, the possibility of different ways of addition, a minimum presence of products from unwanted decomposition of the organic catalyst and the resulting minimum loss of oxygen available from peracid due to bleach decomposition products, greater efficiency of the organic catalyst (i.e. use of less catalyst organic and therefore a reduction in the costs of bleaching compositions, less environmental impact and less formula space).

In one aspect of the present invention, provides a bleaching composition comprising a compound organic catalyst with or without a peroxygen source, where said organic catalyst compound has a shelf life of organic catalyst greater than or equal to 30 minutes and is a compound cationic organic catalyst having the following formula:

one

in where

2

and where R 50 -R 54 are independently selected each other, from a substituted or unsubstituted radical selected from group consisting of H, alkyl, cycloalkyl radicals, alkylaryl, aryl, aralkyl, heterocyclic ring, silyl, nitro, linear or branched halo, cyano, alkoxy, keto and carboalkoxy, provided that any R 50 -R 54 can join any other R 50 -R 54 to be part of a common ring; and when R 54 is H, R 50 -R 51 does not bind to any R 53 -R 53 to form an aromatic ring, X- is a suitable load balancer counterion and v is a number integer from 1 to 3, which is characterized because at least one of R 50 -R 51 is not H.

Therefore, an object of the present invention is provide: a component of the formulation, preferably a organic catalyst compound, which has improved performance at higher and lower temperatures of the water solution of washed; a bleaching composition comprising one or more of the formulation components described herein; a method of washing a tissue using one or more bleaching compositions described herein; and a laundry additive product comprising one or more formulation components described herein.

These and other objects, features and advantages of the present invention will be recognized by the expert in the technique in view of the following description and of the attached claims.

All percentages, ratios and proportions they are expressed herein by weight, unless indicated contrary.

Detailed description of the invention

The present invention describes components of the very useful formulation, such as catalyst compounds organic ("bleach reinforcing compounds", "bleaching species", "modified amines", "oxides of modified amines "and mixtures thereof), compositions and methods that use the components of the formulation.

The components of the formulation, especially the organic catalyst compounds of the present invention as defined in claim 1, they provide greater efficiency bleaching, such as stain removal, bleaching, etc., to lower and higher water temperatures, allow different Ways of addition, minimize the unwanted presence of products of decomposition of the organic catalyst and the resulting loss of available peroxide oxygen (AvO) due to bleaching of decomposition products, allow greater efficiency of organic catalyst (i.e. allow the use of less catalyst organic with the consequent cost reduction of bleaching compositions, less environmental impact and less formula space) when compared to systems conventional organic catalyst bleach.

The components of the formulation of the present invention act together with or without, preferably with, sources of conventional peroxygen bleach to provide the greatest stability of the aforementioned organic catalyst and the highest bleaching efficiency as described above.

Definitions

The expression "source of peroxygen" in the This report means materials that generate compounds peroxygenated and may include the compounds themselves peroxygenated Examples include, but are not limited to,  bleach activators, peracids, percarbonates, perborates, hydrogen peroxide, bleach reinforcing compounds and / or bleaching species (i.e. oxaciridiniums).

The expression "peroxygenated compounds" in This report includes peracids and peroxides (i.e. hydrogen peroxide, alkyl hydroperoxides, etc.).

The expression "peracid" in the present memory means a peroxy acid such as peroxycarboxylic acid  and / or peroximonosulfuric acid (trade name OXONE) and its you go out.

Organic catalyst compounds

Examples of catalyst compounds organic, such as bleach reinforcing compounds and bleaching species are described in the patents US 5,041,232, US 5,045,223, US 5,047,163, US 5,310,925, US 5,413,733, US 5,360,568, US-5,482,515, US-5,550,256, US 5,360,569, US 5,478,357, US 5,370,826, US 5,442,066, US-5,576,282, US-5,760,222, US-5,753,599, US-5,652,207 and US-5,817,614, PCT WO 98/23602, WO 95/13352, WO 95/13353, WO 95/13351, WO 97/06147 and WO 98/23717 and EP 728 182.

The organic catalyst compounds of the present invention as defined in claim 1 present a shelf life of the organic catalyst exceeding 30 minutes, determined according to the Test Protocol described to continuation.

Bleach reinforcing compounds : in cationic organic catalyst compounds we have surprisingly discovered that the substitution or branching in R19 provides greater stability when the substitution or branching is in the alpha (?) Position as a double substitution geminal as shown in the following formula:

3

where R 19 has the formula:

4

where R 50 -R 54 can be selected, independently of each other, from a radical substituted or not substituted selected from the group consisting of H, radicals alkyl, cycloalkyl, alkylaryl, aryl, aralkyl, ring heterocyclic, silyl, nitro, halo, cyano, alkoxy, keto and linear or branched carboalkoxy, provided that any R 50 -R 54 can be attached to any other R 50 -R 54 to be part of a ring common; and provided that when R 54 is H, R 50 -R 51 does not join each other R 52 -R 53 to form an aromatic moiety. X - is a suitable charge balancer counterion and v is a integer from 1 to 3. At least one, more preferably two, of R 50 -R 51 is not H. Even more preferably, R 50 -R 51 are selected, independently of each other, from the group consisting of radicals alkyl and cycloalkyl; most preferably R 50 -R 51 are independently selected each other, of a methyl radical or ethyl.

Suitable examples of X -, a counterion anionic, including, but not limited to: BF_ {4} -, OTS - and other anionic counterions described in the documents WO 97/06147, WO 95/13352, WO 95/13353, WO 95/13351, WO 98/23717, US Patents 5,360,568, US 5,360,569, US 5,482,515, US-5,550,256, US-5,478,357, US 5,370,826, US 5,442,066, EP 728 182 B1 and UK 1 215 656. Preferably, the anionic counterion is compatible with bleach.

In structures that do not carry a net charge There are no counterions associated with the compound.

In structures that carry a negative charge net, suitable examples of X +, a cationic counterion, include, but are not limited to Na +, K +, H +.

In structures that carry a multiple load net, suitable examples of anionic and cationic counterions include, but not limited to, those described previously.

Other organic catalyst compounds : in addition to the bleach reinforcing compounds, the bleaching species and the modified amines and the amine oxides described above, the organic catalyst compounds can be any compound known in the art that is capable of reacting with a peracid to form an oxygen transfer agent (a bleach).

Concentration of organic catalyst compounds : the organic catalyst compounds of the present invention can be added to a wash solution at a level of about 0.00001% (0.0001 ppm) to about 10% (100 ppm) by weight of the composition, preferably from about 0.0001% (0.001 ppm) to about 2% (20 ppm) by weight of the composition, more preferably from about 0.005% (0.05 ppm) to about 0.5% (5 ppm), even more preferably from about 0.01% (0.1 ppm) to about 0.2% (2 ppm) and most preferably from about 0.02% (0.2 ppm) to about 0.1% (1 ppm).

Preferably, the bleaching compositions of the present invention comprise an amount of compound organic catalyst such that the resulting concentration of bleach reinforcing compound in a wash solution from about 0.001 ppm to about 5 ppm.

In addition, preferably the compositions bleaching agents of the present invention comprise an amount of peroxygenated compound, if present, and an amount of organic catalyst compound so that the molar ratio resulting between said peroxygenated compound and said compound organic catalyst in a wash solution is preferably greater than 1: 1, more preferably greater than 10: 1, even more preferably greater than 50: 1. The intervals of the relationship Preferred molar between peroxygenated compound and compound cationic organic catalyst are approximately 30,000: 1 a about 10: 1, even more preferably of about 10,000: 1 to about 50: 1, even more preferably from about 5,000: 1 to about 100: 1 and even more preferably about 3,500: 1 a approximately 150: 1.

Conversion values (in ppm) are presented at illustrative title based on a product concentration during its use of 1,000 ppm. A wash solution of 1,000 ppm of a product containing 0.2% of an organic catalyst compound in weight gives an organic catalyst compound concentration of 2 ppm. Similarly, a 3,500 ppm wash solution of a product containing 0.2% organic catalyst compound in weight gives an organic catalyst compound concentration of 6.5 ppm.

The method of supplying compounds Organic catalysts of the present invention and the method for supply bleaching compositions (products) containing these organic catalyst compounds especially useful in the method of the present invention are the catalyst compounds organic and the compositions that contain them so that satisfy the preferred method of bleaching a stained substrate in an aqueous medium with a source of peroxygen and with a compound organic catalyst whose structures are defined herein memory and wherein said medium contains active oxygen from of the peroxygenated compound of about 0.05 a about 250 ppm per liter of medium, and said compound organic catalyst from 0.001 ppm to about 5 ppm, preferably from about 0.01 ppm to about 3 ppm, more preferably about 0.1 ppm at about 2 ppm, and most preferably about 0.2 ppm to about 1 ppm.

This preferred method of bleaching a substrate stained in an aqueous medium with a source of peroxygen and with a Organic catalyst compound is of particular value for those applications where the security for the substrate color staining that you want to clean is a problem. In these applications the preferred embodiment (ie 0.01 ppm at approximately 3 ppm) is of particular importance to achieve Acceptable safety for fabric colors. In others applications in which the security for the substrate color staining that you want to clean is a lower priority, they can higher concentrations of use are preferred.

Decomposition of organic catalysts

Organic catalysts, in particular the bleach reinforcing compounds of the present invention, can be decomposed by different routes including, but not limited to, aromatization. The aromatization (decomposition) reaction of 6-member ring enhancers is well known in the art, as illustrated, without claiming to impose any theory, in Hanquet et al., Tetrahedron 1993 , 49 , p. 423-438. Other means of decomposition include, but are not limited to, attack by nucleophiles to the bleach reinforcing compound and / or to bleaching species, including but not limited to, attack by hydroxide anion, perhydroxide anion, carboxylate anion, percarboxylate anion and others nucleophiles present in the washing conditions. The decomposition reaction of a 6-membered oxaciridinium ring whose general process can reduce bleaching efficiency is included below for illustrative purposes and without imposing any theory:

5

Methods for delayed (controlled) addition of compounds organic catalysts

In organic catalyst compounds of limited shelf life it has been surprisingly found that the addition of organic catalyst compounds through a delivery medium to a wash solution after adding a fabric to a wash solution, provides improved bleaching compared to the addition of this organic catalyst compound to the wash solution before adding a tissue to the wash solution. It is believed, without attempting to impose any theory, that the organic catalyst compound undergoes a breakdown in the wash solution before introducing the tissue load. One method of improving the performance of organic catalyst compounds is to delay the addition of the organic catalyst compounds of the present invention to the wash solution. Another method to improve the performance of organic catalyst compounds is to use an organic catalyst compound with greater stability in the washing conditions. The present invention is directed to this latter method, although additional advantages can be achieved using the first and second methods. The methods for a delayed (controlled) addition of organic catalyst compounds are described in more detail in the provisional co-owned and co-owned US patent application entitled "Controlled Availability of Formulation Components, Compositions and Laundry Methods Employing Same" filed on 27 August 1999 (P&G Attorney Docket No. 7749P).

Bleaching compositions comprising compounds organic catalysts

In addition to using the catalyst compounds organic discussed above, you can also use the organic catalyst compounds of the present invention together with a source of peroxygen in other bleaching compositions, regardless of its shape. For example, the compounds Organic catalysts can be used in an additive product for washing clothes.

In the bleaching compositions herein invention, the peroxygen source may be present at levels from about 0.1% (1 ppm) to about 60% (600 ppm) in composition weight, and preferably about 1% (10 ppm) at about 40% (400 ppm) by weight of the composition, and organic catalyst compounds may be present in approximately 0.00001% (0.0001 ppm) to approximately 10% (100 ppm) by weight of the composition, preferably about 0.0001% (0.001 ppm) to approximately 1% (10 ppm) by weight of the composition, more preferably about 0.001% (0.01 ppm) at about 0.5% (5 ppm), even more preferably of approximately 0.004% (0.04 ppm) to approximately 0.25% (2.5 ppm) and most preferably about 0.01% (0.1 ppm) at approximately 0.1% (1 ppm). The catalyst compounds organic and bleaching compositions comprising the Organic catalyst compounds of the present invention may be used advantageously in laundry applications, hard surface cleaning, dishwasher applications, bleaching applications associated with wood pulp and / or textiles, applications with antimicrobial agents and / or disinfectants as well as cosmetic applications such as for dentures, teeth, hair and skin. However, due to the unique advantages of greater efficiency in cold water solutions and possibly tempered thanks to possible greater stability, the Organic catalyst compounds of the present invention result ideally suitable for laundry applications such such as bleaching tissues by using detergents that They contain bleach or bleaching additives for laundry. In addition, the bleach reinforcing compounds of the present invention can be used in granule-shaped compositions, powder, tablet, paste, foam, gel or liquid.

Therefore, the bleaching compositions of the present invention may include different additional ingredients  desirable in laundry applications. These ingredients include detersive surfactants, bleaching catalysts, detergency builders, chelating agents, enzymes, polymeric agents to release dirt, brighteners and other ingredients Compositions that include any of these different additional ingredients preferably have a pH from about 6 to about 12 and preferably from about 8 to about 10.5, in a 1% solution of the bleaching composition. Bleaching compositions preferably they include at least one detersive surfactant, at less a chelating agent, at least one detersive enzyme and preferably they have a pH of about 6 to about 12, preferably from about 8 to about 10.5, in a 1% solution of the bleaching composition.

In another embodiment of the present invention It provides a method to wash a fabric that needs to be washed. The preferred method comprises contacting the tissue with a laundry solution. The tissue can comprise any fabric capable of being washed under normal conditions of use by of the consumer The laundry solution comprises a bleaching composition, as described in detail herein memory. Water temperatures preferably are about 0 ° C to about 50 ° C or higher. The water: tissue ratio is preferably about 1: 1 to approximately 15: 1. The laundry solution can also include at least one additional ingredient selected from the group consisting of detersive surfactants, chelating agents, enzymes detersives and mixtures thereof. Preferably, the solution for washing clothes has a pH of approximately 6 to about 12, preferably about 8 to approximately 10.5, in a 1% solution of the composition bleaching

In accordance with another aspect of the present invention, an additive product for washing clothes is provided. The laundry additive product comprises an organic catalyst compound, as described in detail above. This laundry additive product would ideally be suitable for inclusion in a washing process when additional bleaching efficiency is desired. These cases may include, but are not limited to, laundry applications with low temperature and intermediate temperature solution.
day.

It is desirable that the additive product for washing of clothing also include a source of peroxygen, as has been described in detail above. The additive product for washing of clothing may also include liquid or powder compositions that contain a source of hydrogen peroxide or a source of peroxygen as defined in detail above.

In addition, if the additive product for washing of clothing includes a source of hydrogen peroxide, it is desirable that the laundry additive product also includes an activator of bleach, as described in detail above.

Preferably, the additive product for washing of clothing is packaged in unit doses for addition to a laundry process in which a source of peroxygen and greater bleaching efficiency is desired. This form Unit dose can comprise a pill, pill, capsule gelatin or other unit dose such as powders or liquids premeditated If desired, a loading material or vehicle to increase the volume of the composition. The materials of cargo or suitable vehicles can be selected, although not in a limited way, of different salts of sulfate, carbonate and silicate as well as talc, clay and the like. The materials of cargo or vehicles for liquid compositions can be water or primary and secondary low molecular weight alcohols, including polyols and diols. Examples include methanol, ethanol, propanol and isopropanol. Monohydric alcohols can also be used. The compositions may contain from about 5% to approximately 90% of these materials. Loads can be used acids to reduce pH.

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A preferred bleaching composition is a bleaching composition comprising:

(to)

a peroxygen source; Y

(b)

one or more organic catalyst compounds;

where the organic catalyst compounds become active in a wash solution containing said bleaching composition a some time after said peroxygen source becomes active The source of peroxygen, as discussed above, it is preferably selected from the group consisting in:

(i)

preformed peracid compounds selected from the group that consists of acids and percarboxylic salts, acids and salts percarbonics, acids and perimide salts, acids and salts peroximonosulfuric, and mixtures thereof, and

(ii)

sources of hydrogen peroxide selected from the group consisting of perborate compounds, percarbonate compounds, perfosphate compounds and mixtures of the same, and a bleach activator.

Preferably, the peroxygen source is select from hydrogen peroxide sources selected from group consisting of perborate compounds, compounds of percarbonate, perfosphate compounds and mixtures thereof, and a bleach activator.

More preferably, the bleach activator is selected from the group consisting of bleach activators hydrophobic as described herein.

The period between the moment in the that the peracid becomes active in a wash solution and the moment in which the organic catalyst compounds become assets can be in the range of about 1 second to approximately 24 hours Alternatively, since the Organic catalyst compounds are relatively stable in the wash solution, the peracid can become active in the solution  wash after the organic catalyst compounds are become active or available.

The end of a delayed addition of the composition bleach (which may or may not be used in this invention) is allow the peracid to reach a maximum bleaching capacity in a tissue to be cleaned, such as a stained fabric, in a wash solution before introducing the catalyst compound organic. In other words, a bleaching composition that it comprises an organic catalyst compound that becomes active in a wash solution after adding a desired fabric Clean the wash solution. Alternatively, since the organic catalyst compounds may have a higher stability, a bleaching composition can be used that comprise an organic catalyst compound that becomes active in a wash solution before adding a desired fabric Clean in the wash solution.

The bleaching compositions of the present invention also comprise, in addition to one or more of the organic catalysts described above, one or more cleaning adjuvant materials preferably compatible with the organic catalyst (s) and / or with any enzyme present in the bleaching composition. The "compatible" expression, herein, means that the materials of the bleaching composition do not reduce the action of bleaching of the organic catalyst and / or any enzymatic action of any enzyme present in the bleaching composition up to a point at which the organic catalyst and / or the enzyme stops be effective in the desired way in normal use situations. The expression "cleaning adjuvant materials", herein memory, means any liquid, solid or gaseous material selected for the particular type of bleaching composition desired and the shape of the product (i.e. liquid, granule, powder, tablet, paste, powdered, compressed, gel, composition foamy), these materials being also preferably compatible with the protease enzyme (s) and the bleaching agent (s) used (s) in the composition. Granulated compositions they can also be in "compact" form and the compositions Liquids may also be in "concentrated" form.

The specific selection of materials cleaning adjuvants is easily done considering the surface, article or fabric to be cleaned and the shape Desired composition under clean conditions during use (i.e. use to add detergent during washing). Examples of suitable cleaning adjuvant materials include, although not limited to surfactants, reinforcing additives of detergency, bleach, bleach activators, bleach catalysts, other enzymes, systems enzyme stabilizers, chelators, optical brighteners, polymers for dirt release agents transfer of dyes, dispersants, suppressors of soaps, dyes, perfumes, dyes, loading salts, hydrotropes, photoactivators, fluorescent agents, tissue conditioners, hydrolysable surfactants, preservatives, antioxidants, anti-shrinking agents, agents anti-wrinkles, germicides, fungicides, colored spots, agents for the care of silver, anti-slip and / or anti-corrosion sources of alkalinity, solubilizing agents, vehicles, improvers process, pigments and pH regulators as described in the US-5,705,464, US-5,710,115, US-5,698,504, US-5,695,679, US 5,686,014 and US 5,646,101. Some Specific materials of bleaching composition are illustrated in detail below.

If cleaning adjuvant materials are not compatible with the protease variant (s) in the bleaching compositions, then methods can be used suitable for keeping adjuvant materials separate cleaners and the protease variant (s) (so that are not in contact with each other) until deemed appropriate Combine the two components. Suitable methods can be any method known in the art, such as capsules of jelly, encapsulation, pills, physical separation, etc.

These bleaching compositions include detergent compositions for cleaning hard surfaces in a unlimited range of forms (i.e. liquid, granulate, paste, foam, spray, etc.); cleaning detergent compositions fabrics, in an unlimited range of forms (i.e. formulations for granules, liquids, tablets, etc.); washing compositions of dinnerware (in an unlimited range of shapes and including granulated and liquid dishwashing compositions); oral bleaching compositions, in an unlimited range of forms (i.e. formulations for toothpaste, toothpaste and mouthwash); and bleaching compositions for dentures, in an unlimited range of forms (i.e. liquid, tablet).

The bleaching compositions for tissues of the present invention are primarily intended to be used in the washing cycle of a clothes washer; without However, other uses such as products of pretreatment for heavily stained tissues or soaking products; the use is not necessarily limited to the context of the washing machine clothing and the compositions of the present invention can be used alone or with compatible compositions for hand washing.

Bleaching compositions may include about 1% to about 99.9% by weight of the composition of cleaning adjuvant materials.

Here, the expression "bleaching compositions for nonwovens" includes whitening compositions for hard surfaces, compositions for dishwashing, oral bleaching compositions, bleaching compositions for dentures and compositions personal cleaning cleaners.

When the bleaching compositions of the present invention are formulated as suitable compositions For use in a method of machine washing clothes, compositions of the present invention preferably contain a surfactant and a detergent builder additive compound and in addition one or more cleaning adjuvant materials preferably selected from organic polymeric compounds, agents bleaches, additional enzymes, suds suppressants, dispersants, limestone soap dispersants, suspending agents of dirt, anti-redeposition agents and inhibitors of corrosion. The laundry compositions can also contain softeners as cleaning adjuvant materials additional.

The compositions of the present invention they can also be used as detergent additive products in solid or liquid form. These additives are intended for complement or improve the performance of the compositions conventional detergents and can be added at any stage of the cleaning process.

When formulated as compositions for use in manual dishwashing methods, the compositions of the invention preferably contain a surfactant and preferably other cleaning adjuvant materials selected from organic polymeric compounds, boosters of soaps, group II metal ions, solvents, Hydrotropes and additional enzymes.

If necessary, the density of the laundry detergent compositions herein invention is 400 to 1,200 g / liter, preferably 500 to 950 g / liter, of the composition measured at 20 ° C.

The "compact" form of the compositions bleaching agents of the present invention are optimally reflected in density and, in terms of composition, in the amount of salts inorganic fillers; inorganic filler salts are conventional ingredients of detergent compositions in powder form; in conventional detergent compositions the charge salts are present in significant amounts, so typical of 17-35% by weight of the total composition. In compact compositions, the loading salt is present in amounts not exceeding 15% of the total composition, preferably not exceeding 10% and most preferably that they do not exceed 5%, by weight of the composition. Loading salts inorganic, such as those of the compositions herein invention, are selected from alkali metal salts and alkaline earth sulfates and chlorides. A preferred loading salt It is sodium sulfate.

The bleaching liquid compositions according to the The present invention may also be in "concentrated form",  in which case the bleaching liquid compositions according to the The present invention will contain a smaller amount of water than conventional liquid detergents. Typically the content of water of the concentrated liquid bleaching composition is preferably less than 40%, more preferably less than 30%  and most preferably less than 20%, by weight of the composition bleaching

Adjuvant cleaning materials

Although they are not essential for the purposes of present invention, various cleaning adjuvant materials Conventional, illustrated below, are suitable for use in the bleaching compositions of the present invention and can be desirably incorporated in the preferred embodiment of the invention, for example to favor or improve capacity cleaner, to treat the substrate to be cleaned or to modify the aesthetics of the bleaching composition, for example with perfumes, dyes, dyes or the like. The concrete nature of these additional components and the amounts in which they incorporate will depend on the physical state of the composition and the type of cleaning operation for which it will be used. Unless I know indicate otherwise, the bleaching compositions of the invention they can, for example, be formulated as granulated washing agents or in the form of universal type powder or "intensive cleaning", especially laundry detergents; agents of washing liquids, in the form of gel or universal paste, especially the so-called liquid types of intensive cleaning; detergents liquids for delicate fabrics; agents for manual washing of dishes or agents for washing mild cleaning dishes, especially the very sparkling type; washing agents Automatic tableware, including different types of tablets, granulated, liquid and rinse aid for domestic use and for institutional use; liquid cleaning agents and disinfectants including hand wash types antibacterials, laundry tablets, mouthwashes, denture cleaners, car shampoos or carpets, bathroom cleaners; hair shampoos and products for the hair lightening; shower gels, foam baths and cleaners of metals; as well as auxiliary cleaning substances such as bleaching additives and types "stain remover bar" or pretreatment

Bleaching System : In addition to the organic catalyst of the present invention, the bleaching compositions of the present invention preferably comprise a bleaching system. Bleaching systems typically comprise a peroxygen source. The peroxygen sources are well known in the art and the peroxygen source used in the present invention may comprise any of these well known sources, including peroxygenated compounds as well as compounds that under conditions of consumer use provide an effective amount of peroxygen in situ . The peroxygen source may include a source of hydrogen peroxide, the in situ formation of a peracid anion by the reaction of a source of hydrogen peroxide with a bleach activator, preformed peracid compounds or mixtures of suitable peroxygen sources. Logically, one skilled in the art will recognize that other sources of peroxygen can be used without thereby abandoning the scope of the invention. Preferably, the peroxygen source is selected from the group consisting of:

(i)

preformed peracid compounds selected from the group consisting of salts and acids percarboxylic acids and percarbonic salts, acids and salts perimides, acids and peroxymonosulfuric salts, and mixtures of themselves, and

(ii)

sources of hydrogen peroxide selected from the group consisting of perborate compounds, percarbonate compounds, perfosphate compounds and mixtures of the same, and a bleach activator.

If present, the sources of peroxygen (sources of peracids and / or hydrogen peroxide) will be of typically at levels of about 1%, preferably of about 5% to about 30%, preferably at approximately 20%, by weight of the composition. If present, the bleach activator will typically be in an amount of about 0.1%, preferably about 0.5% at about 60%, preferably about 40%, by weight of the bleaching composition comprising the bleaching agent plus bleach activator.

to. Preformed peracids: The preformed peracid compound in the present invention is any suitable compound that is stable and that under conditions of use by the consumer provides an effective amount of peracid anion. The organic catalyst compounds of the present invention can logically be used together with a preformed peracid compound selected from the group consisting of percarboxylic acids and salts, percarbonic acids and salts, perimidic acids and salts, peroximonosulfuric acids and salts, and mixtures thereof, Examples of which are described in US Patent 5,576,282 issued to Miracle et al.

A class of organic peroxycarboxylic acids Suitable has the general formula:

\uelm{C}{\uelm{\dpara}{O}}

--- O --- OHY --- R ---

 \ uelm {C} {\ uelm {\ dpara} {O}} 

--- O --- OH

where R is an alkylene group or substituted alkylene containing from 1 to about 22 atoms of carbon or a substituted phenylene or phenylene group, and y is hydrogen, halogen, alkyl, aryl, -C (O) OH or -C (O) OOH.

Organic peroxyacids suitable for use in the present invention they may contain one or two peroxy groups and They can be aliphatic or aromatic. If peroxycarboxylic acid organic is aliphatic, unsubstituted peracid has the formula general:

\uelm{C}{\uelm{\dpara}{O}}

--- O --- OHY --- (CH_2) n ---

 \ uelm {C} {\ uelm {\ dpara} {O}} 

--- O --- OH

       \ newpage
    

where Y can 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. If peroxycarboxylic acid organic is aromatic, unsubstituted peracid has the formula general:

\uelm{C}{\uelm{\dpara}{O}}

--- O --- OHY --- C_ {6} H_ {4} ---

 \ uelm {C} {\ uelm {\ dpara} {O}} 

--- O --- OH

where Y can be, for example, hydrogen, alkyl, alkylhalogen, halogen, C (O) OH or C (O) OOH.

Typical monoperoxy acids useful in Present invention include alkylperoxy acids and arylperoxy acids such as:

(i)

peroxybenzoic acid and ring-substituted peroxybenzoic acid, that is, peroxy-a-naphthoic acid, monoperoxyxtalic acid (magnesium hexahydrate salt) and o- carboxybenzamidoperoxyhexanoic acid (sodium salt);

(ii)

  aliphatic, substituted aliphatic acids and arylalkyl monoperoxy, that is, peroxylauric acid, peroxystearic acid, acid N-nonanoylaminoperoxycaproic acid (NAPCA), acid N, N- (3-octylsuccinoyl) aminoperoxycaproic (SAPA) and N, N-phthaloylaminoperoxicaproic acid (PAP);

(iii)

amidoperoxy acids, that is, acid monononylamide peroxisuccinic (NAPSA) or peroxyandipic acid (NAPAA).

Typical diperoxyacids useful herein invention include alkyldiperoxy acids and aryldiperoxy acids, such as:

(iv)

acid 1,12-diperoxy dodecanedioic;

(v)

acid 1,9-diperoxyazelaic;

(saw)

diperoxybrasilic acid; diperoxisebacic acid and diperoxyisophthalic acid;

(vii)

acid 2-decyldiperoxybutane-1,4-dioic;

(viii)

acid 4,4'-sulfonylbisperoxybenzoic.

These bleaching agents are described in the US Patents 4,483,781, issued to Hartman on 20 November 1984, US-4,634,551, granted to Burns et al., EP-0.133.354, Banks et al., published on 20 February 1985, and US-4,412,934, granted to Chung et al. on November 1, 1983. Sources also include the acid 6-nonylamino-6-oxoperoxicaproproic as described in detail in the patent 4,634,551, issued January 6, 1987 to Burns et al. Persulfate compounds such as, for example, OXONE, commercially manufactured by E.I. DuPont de Nemours de Wilmington, DE, can also be used as an adequate source of peroxymonosulfuric acid.

b. Sources of hydrogen peroxide : The source of hydrogen peroxide can be any suitable source of hydrogen peroxide and present at the levels described in detail in US Pat. No. 5,576,282. For example, the source of hydrogen peroxide can be selected from the group consisting of perborate compounds, percarbonate compounds, perfosphate compounds and mixtures thereof.

Sources of hydrogen peroxide are described. in detail in Kirk's Encyclopedia of Chemical Technology Othmer, 4th ed. (1992, John Wiley & Sons), Vol. 4, p. 271-300, "Bleaching Agents (Survey)" and include different forms of sodium perborate and sodium percarbonate, including different coated and modified forms.

The preferred hydrogen peroxide source of use in the present invention can be any suitable source, including hydrogen peroxide itself. For example, in the present invention can be used perborate, e.g. eg perborate sodium (any hydrate but preferably monohydrates or tetrahydrates), sodium carbonate peroxyhydrate or salts of equivalent percarbonate, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate or sodium peroxide. Also useful are available oxygen sources such as bleach type persulfate (e.g., OXONE, manufactured by DuPont). Perborate sodium monohydrate and sodium percarbonate are particularly preferred. Mixtures from any source can also be used. adequate hydrogen peroxide.

A preferred percarbonate bleach it comprises dry particles with an average particle size in the range from about 500 micrometers to about 1,000 micrometers, where not more than about 10%, by weight of said particles are less than about 200 micrometers and no more than about 10%, by weight of said particles are greater than 1,250 micrometers. Optionally, the percarbonate can be coated with silicate, borate or water-soluble surfactants. Percarbonate is marketed by various companies such as FMC, Solvay or Tokai Denka.

The compositions of the present invention they can also comprise as a bleaching agent a material chlorine bleach. These agents are well known in the art. and include, for example, sodium dichloroisocyanurate ("NaDCC"). However, chlorinated bleaches are less preferred for compositions comprising enzymes.

b. Bleach activators : preferably, the peroxygen source in the composition is formulated with an activator (peracid precursor). The activator is present at levels of about 0.01%, preferably about 0.5%, more preferably from about 1% to about 15%, preferably at about 10%, more preferably at about 8%, by weight of the composition . A bleach activator in the present invention is any compound that when used in conjunction with a source of hydrogen peroxide produces in situ the peracid corresponding to the bleach activator. Different non-limiting examples of activators are described in detail in patents US 5,576,282, US 4,915,854 and US 4,412,934 (see also US 4,634,551 for other typical bleach and activators useful in the present invention) .

Preferred activators are selected from group consisting of tetraacetyl ethylenediamine (TAED), benzoyl caprolactam (BzCL), 4-nitrobenzoylcaprolactam, 3-chlorobenzoylcaprolactam, benzoyloxybenzenesulfonate (BOBS), nonanoyloxybenzenesulfonate (NOBS), phenyl benzoate (PhBz), decanoyloxybenzenesulfonate (C 10 -OBS), benzoylvalerolactam (BZVL), octanoyloxybenzenesulfonate (C 8 -OBS), esters perhydrolysable and mixtures thereof, and most preferably Benzoil Caprolactam and Benzoil Valerolactam. The activators of bleach in the pH range of about 8 to approximately 9.5 particularly preferred are those selected for having an outgoing OBS or VL group.

Hydrophobic bleach activators Preferred include, but not limited to, nonanoyloxybenzenesulfonate (NOBS), sodium salt of 4- [N- (nonanoyl) amino hexanoyloxy] -benzenesulfonate (NACA-OBS) an example of which is described in the US 5,523,434, lauroyloxybenzenesulfonate (LOBS or C 12 -OBS), 10-undecenoyloxybenzenesulfonate (UDOBS or C_ {11} -OBS with unsaturation at position 10) and Decanoyloxybenzoic acid (DOBA).

Preferred bleach activators are those described in US Patents 5,698,504, granted to Christie et al. on December 16, 1997; US 5,695,679, issued to Christie et al. the 9 of December 1997; US 5,686,401, granted to Willey et al. on November 11, 1997; US 5,686,014, granted to Hartshorn et al. on November 11, 1997; 5,405,412, granted to Willey et al. on 11 of April 1995; 5,405,413, granted to Willey and cabbage. on April 11, 1995; US-5,130,045, granted to Mitchel et al. on July 14, 1992; Y US 4,412,934, granted to Chung et al. the 1st of November 1983

The molar ratio between the bleaching compound peroxygenated (as AvO) and the bleach activator in the The present invention is generally at least 1: 1, preferably from about 20: 1, more preferably from about 10: 1 to about 1: 1, preferably at about 3: 1

Substituted quaternary bleach activators may also be included. The present bleaching compositions preferably comprise a substituted quaternary bleach activator (QSBA) or a substituted quaternary peracid (QSP); more preferably, the first. Preferred QSBA structures are also described in US 5,686,015 issued to Willey et al. on November 11, 1997; US 5,654,421, issued to Taylor et al. on August 5, 1997; US 5,460,747, Gosselink et al. on October 24, 1995; US 5,584,888, granted to Miracle et al. on December 17, 1996; and US 5,578,136, granted to Taylor et al. on November 26
nineteen ninety six.

The most preferred bleach activators useful in the present invention are amide-substituted as described in the patents US-5,698,504, US-5,695,679 and US-5,686,014, all cited above in This memory. Preferred examples of these activators Bleach include: (6-octanamidocaproyl) oxybenzenesulfonate, (6-nonanamidocaproyl) oxybenzenesulfonate, (6-decanamido caproyl) oxybenzenesulfonate and mixtures thereof.

Other useful activators, described in the US-5,698,504, US-5,695,679, US-5,686,014, all cited above in this report, and US 4,966,723, granted to Hodge et al. on October 30, 1990, include type activators benzoxazine, such as a C 6 H 4 ring with which it find a remainder fused in position 1.2 -C (O) OC (R1) = N-.

Depending on the activator and the application in issue, good bleaching results can be obtained with bleaching systems with a pH in use of approximately 6 to about 13, preferably about 9.0 to approximately 10.5. Typically they are used, for example, activators with electron capture remains for intervals of Almost neutral or subneutral pH. To guarantee this pH you can use alkalis and buffering agents.

Acyl lactam type activators, as described in patents US-5,698,504, US 5,695,679 and US 5,686,014, cited all of them previously herein, are very useful in the present invention, especially acyl caprolactams (see, for example, WO 94-28102 A) and the acyl valerolactams (see US 5,503,639, granted to Willey et al. the 2 of April 1996).

d. Organic peroxides, especially diacyl peroxides : In addition to the bleaching agents described above, the bleaching compositions of the present invention may optionally include organic peroxides. Organic peroxides are widely illustrated in Kirk Othmer, Encyclopedia of Chemical Technology, Vol. 17, John Wiley and Sons, 1982, p. 27-90 and especially pages. 63-72. If a diacyl peroxide is used, it should preferably be one that exerts a minimal negative impact on the formation of spots or films.

and. Metal-containing bleaching catalysts : bleaching compositions may also optionally include metal-containing bleaching catalysts, preferably bleaching catalysts containing manganese and cobalt.

A type of bleaching catalyst that contains metal is a catalyst system comprising a metal cation of transition with a defined catalytic bleaching activity, such such as cations copper, iron, titanium, ruthenium, tungsten, molybdenum or manganese, a metal auxiliary cation that has little or no catalytic bleaching activity, such as cations of zinc or aluminum, and a chelator that has constants of defined stability for catalytic and metal cations auxiliaries, particularly acid ethylenediamine tetraacetic, ethylenediaminetetra (methylene phosphonic acid) and water soluble salts thereof. These catalysts are described in US 4,430,243, granted to Bragg on February 2, 1982.

i.

Manganese metal complexes : if desired, the compositions of the present invention can be catalyzed by a manganese compound. These compounds and levels of use are well known in the art and include, for example, the manganese-based catalysts described in US 5,576,282, granted to Miracle et al. on November 19, 1996; US 5,246,621, issued to Favre et al. on September 21, 1993; US 5,244,594, issued to Favre et al. on September 14, 1993; US 5,194,416, granted to Jureller et al. on March 16, 1993; US-5,114,606, granted to van Vliet et al. on May 19, 1992; and European patents EP-549,271 A1, EP-549,272 A1, EP-544,440 A2 and EP-544,490 A1. Preferred examples of these catalysts include Mn IV 2 (uO) 3 (1,4,7-trimethyl-1,4,7-triazacyclononane) 2 (PF 6) 2, Mn III 2 (uO) 1 (u-OAc) 2 (1,4,7-trimethyl-1,4,7-triazacyclononane) 2 (ClO 4) 2, Mn IV 4 (uO) 6 (1,4,7-triazacyclononane) 4 (ClO 4) 4 , Mn III Mn IV 4 (uO) 1 (u-OAc) 2 - (1,4,7-trimethyl-1,4,7-triazacyclononane) 2 (ClO 4) 3, Mn IV (1,4,7-trimethyl-1,4,7-triazacyclononane) - (OCH 3) 3 (PF_ {6}), and mixtures thereof. Other metal-based bleaching catalysts include those described in US 4,430,243, included herein by reference, and in US 5,114,611, granted to van Kralingen on May 19, 1992. The use of manganese with different Complex ligands for improving bleaching are also mentioned in the following patents: US-4,728,455, issued to Rerek on March 1, 1988; US 5,284,944, issued to Madison on February 8, 1994; 5,246,612, granted to van Dijk et al. on September 21, 1993; US 5,256,779, granted to Kerschner et al. on October 26, 1993; US 5,280,117, granted to Kerschner et al. on January 18, 1994; US 5,274,147, granted to Kerschner et al. on December 28, 1993; 5,153,161, granted to Kerschner et al. on October 6, 1992; and US 5,227,084, granted to Martens et al. on July 13, 1993.

ii.

Cobalt metal complexes : Cobalt bleach catalysts useful in the present invention are known and are described, for example, in US 5,597,936, issued to Perkins et al. on January 28, 1997; 5,595,967, granted to Miracle et al. on January 21, 1997; US 5,703,030, granted to Perkins et al. on December 30, 1997; and ML Tobe, "Base Hydrolysis of Transition-Metal Complexes", Adv. Inorg Bioinorg Mech ., (1983), 2, pages 1-94. The most preferred cobalt catalyst useful in the present invention are the cobalt pentaamine acetate salts having the formula [Co (NH3) 5 OAc] T y, wherein "OAc" represents a moiety acetate and "T y" is an anion, and especially cobalt pentaamine acetate chloride, [Co (NH 3) 5 OAc] Cl 2; as well as [Co (NH 3) 5 OAc] (OAc) 2; [Co (NH 3) 5 OAc] (PF 6) 2; [Co (NH 3) 5 OAc] (SO 4); [Co (NH 3) 5 OAc] (BF 4) 2 and [Co (NH 3) 5 OAc] (NO 3) 2 ( herein "PAC").

These cobalt catalysts are readily prepared by known methods as described, for example, in US 5,597,936, US 5,595,967, US 5,703,030, cited above, the Tobe article and references cited herein, and in US-4,810,410, granted to Diakun et al. on March 7, 1989, J. Chem. Ed . (1989), 66 (12), 1043-45; The Synthesis and Characterization of Inorganic Compounds, WL Jolly (Prentice-Hall; 1970), p. 461-3; Inorg Chem ., 18 , 1497-1502 (1979); Inorg Chem ., 21 , 2881-2885 (1982); Inorg Chem ., 18 , 2023-2025 (1979); Inorg Synthesis, 173-176 (1960); and Journal of Physical Chemistry , 56 , 22-25 (1952).

iii.

Transition metal complexes of macropolycyclic rigid ligands : the compositions of the present invention may also suitably include as a bleaching catalyst a transition metal complex of a macropolycyclic rigid ligand. The expression "macropolycyclic rigid ligand" is sometimes abbreviated as "MRL" in the discussion below. The amount used is a catalytically effective amount, suitably of about 1 ppb or more, for example up to about 99.9%, more typically of about 0.001 ppm or more, preferably of about 0.05 ppm to about 500 ppm ( where "ppb" means parts per billion by weight and "ppm" means parts per million by weight).

Suitable transition metals, e.g. eg, Mn, are illustrated below. The term "macropolyclic" means that an MRL is a macrocycle and also polycyclic. The term "polycyclic" means at least bicyclic. The term "rigid" herein includes "having a superstructure" and "with a cross bridge." The term "rigid" has been defined as the opposite of flexible: see DH Busch., Chemical Reviews ., (1993), 93 , 847-860, incorporated herein by reference. More especially, "rigid" herein means that the MRL must be determinably stiffer than a macrocycle ("precursor macrocycle") that is otherwise identical (with the same ring size and type and number of atoms in the main ring) but without the superstructure (special junction remains or, preferably cross bridge remains) found in the MRLs. To compare the rigidity of the macrocycles with and without superstructures, the technician will use the free form (not the metal-bound form) of the macrocycles. Stiffness is well known for being a useful parameter for comparing macrocycles; Suitable tools for determining, measuring or comparing stiffness include computer methods (see, for example, Zimmer, Chemical Reviews , (1995), 95 (38), 2629-2648 or Hancock et al., Inorganica Chimica Acta , (1989) , 164, 73-84.

Preferred MRLs in the present invention are a special type of ultra-rigid ligands with cross bridge. A "cross bridge" is illustrated not limiting in 1.11 later in this report. In 1.11, the cross bridge is a remainder -CH_ {CH} {2} - that joins by means of a bridge N 1 with N 8 in the structure of the example. Comparing, a "same-side" bridge, by example if one had to be entered through N1 and N12 in 1.11, would not be enough to constitute a "bridge crossed "and therefore would not be preferred.

Suitable metals in complexes with rigid ligands include Mn (II), Mn (III), Mn (IV), Mn (V), Fe (II), Fe (III), Fe (IV), Co (I), Co (II), Co (III), Ni (I), Ni (II), Ni (III), Cu (I), Cu (II), Cu (III), Cr (II), Cr (III), Cr (IV), Cr (V), Cr (VI), V (III), V (IV), V (V), Mo (IV), Mo (V), Mo (VI), W (IV), W (V), W (VI), Pd (II), Ru (II), Ru (III), and Ru (IV). The preferred transition metals in the bleaching catalysts of transition metal of the present invention include manganese, iron and chrome

More generally, MRLs (and corresponding transition metal catalysts) of the The present invention suitably comprises:

(to)

to the less a macrocyclic main ring comprising four or more heteroatoms; Y

(b)

a non-metallic superstructure joined by covalent bond capable of increase the rigidity of the macrocycle, preferably selected from

(i)

 a bridge-bound superstructure, such as a rest of Union;

(ii)

a cross-bridge superstructure, such as a junction rest of cross bridge; Y

(iii)

combinations of same.

The expression "superstructure" is used in this report according to the definition in the Busch bibliography et al. (See, for example, Busch's articles in "Chemical Reviews ").

Preferred superstructures herein invention not only improve the rigidity of the precursor macrocycle, but which also favor the folding of the macrocycle so that coordinate a metal in a gap. The right superstructures they can be considerably simple, for example, can be used a junction moiety as any of those illustrated in Fig. 1 and Fig. 2 below.

6

where n is an integer, for example 2 to 8, preferably less than 6, typically 2 to 4, or

7

where m and n are integers from about 1 to 8, more preferably from 1 to 3; Z is N or CH; and T is a compatible substituent, for example H, alkyl, trialkylammonium, halogen, nitro, sulfonate, or the like. The ring aromatic of 1.10 can be replaced by a ring saturated in where the Z atom that binds to the ring can contain N, O, S or C.

Suitable MRLs are illustrated in more detail than non-limiting form by the following compound:

8

This is an MRL according to the invention which is a cyclam derivative, with cross bridge, methyl-substituted (all nitrogen atoms are tertiary) very preferred. From the formal point of view, this ligand is called 5,12-dimethyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane according to Baeyer's expanded system. See "A Guide to IUPAC Nomenclature of Organic Compounds: Recommendations 1993 ", R. Panico, W.H. Powell and J-C Richer (Eds.), Blackwell Scientific Publications, Boston, 1993; see especially the section R-2.4.2.1.

The metal bleaching catalysts of transition of rigid macrocyclic ligands that are suitable for use in the compositions of the invention may, in general, include known compounds according to the definition in the present memory, as well as, more preferably, any of a large number of new compounds expressly designed for laundry or cleaning uses of the present invention and illustrated in a non-limiting manner by any of the following:

Dichloro-5,12-dimethyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane manganese (II)

Diaquo-5,12-dimethyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane manganese (II)

Hexafluorophosphate

Aquo-hydroxy-5,12-dimethyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane manganese (III)

Hexafluorophosphate

Diaquo-5,12-dimethyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane manganese (II)

Tetrafluoroborate

Dichloro-5,12-dimethyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane manganese (III)

Hexafluorophosphate

Dichloro-5,12-di-n-butyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane manganese (II)

Dichloro-5,12-dibenzyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane manganese (II)

Dichloro-5-n-butyl-12-methyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane manganese (II)

Dichloro-5-n-octyl-12-methyl-1,5,8,12-tetraaza-bicyclo [6.6.2] hexadecane manganese (II)

Dichloro-5-n-butyl-12-methyl-1,5,8,12-tetraaza-bicyclo [6.6.2] hexadecane of manganese (II).

On a practical level, and not as a limitation, the compositions and cleaning processes of the present invention can be adjusted to provide on the order of at least one part per hundred million of the active bleaching catalyst in the middle of aqueous wash and will preferably provide approximately 0.01 ppm to about 25 ppm, more preferably of approximately 0.05 ppm to approximately 10 ppm and with maximum preference of about 0.1 ppm to about 5 ppm, of bleaching catalyst in the wash solution. To get these levels in the washing solution of a washing process automatic, typical compositions of the present invention they will comprise from about 0.0005% to about 0.2%, plus preferably from about 0.004% to about 0.08%, of the bleaching catalyst, especially catalysts of manganese or cobalt, by weight of the cleaning composition.

Preferably, the peroxygen source is select from hydrogen peroxide sources selected from group consisting of perborate compounds, compounds of percarbonate, perfosphate compounds and mixtures thereof, and a bleach activator.

Preferably, the bleach activator is select from the group consisting of bleach activators hydrophobic as described herein.

The purpose of this bleaching composition is to reduce unwanted decomposition of the organic catalyst and allow that the peracid develops its bleaching capacity in a tissue that it is desired to clean, such as stained fabric, in a solution of washed before the organic catalyst is found available.

Surfactant system : the detersive surfactants included in the fully formulated bleaching compositions of the present invention comprise at least 0.01%, preferably at least about 0.1%, more preferably at least about 0.5%, most preferably at least about 1% to about 60%, more preferably to about 35%, most preferably to about 30%, by weight of the bleaching composition depending on the surfactant used and the desired effects.

The detersive surfactant may be nonionic, anionic, ampholytic, hybrid ion, cationic, non-ionic semipolar, and mixtures thereof, non-limiting examples of which are described in US Patents 5,707,950 and 5,576,282. Detergent compositions and Preferred bleaches comprise detersive surfactants anionics or mixtures of anionic surfactants with others surfactants, especially non-ionic surfactants.

Anionic surfactants are very preferred. for use with the organic catalyst and compositions bleaching agents of the present invention.

Non-limiting examples of useful surfactants in the present invention include the alkyl C 11 -C 18 benzenesulfonates and primary, secondary and random alkyl sulfates, alkylalkoxy C 10 -C 18 sulfates, the C 10 -C 18 poly (alkyl glycosides) and their corresponding sulfated polyglycosides, acid esters C 12 -C 18 fatty alpha-sulphonates, alkyl and alkylphenol C 12 -C 18 alkoxylates (especially mixed ethoxylated and ethoxy / propoxy), betaines and sulfobetains C_ {12} -C_ {18} ("sultanas"), amine oxides  C 10 -C 18 conventional, and the like. Other useful conventional surfactants are described in the standard texts.

The surfactant is preferably formulated to be compatible with the enzymatic components present in the composition. In liquid or gel compositions, the surfactant is formulates most preferably so that it improves, or at least not reduce the stability of the enzymes present in these compositions

Non-ionic surfactants : polyethylene oxide, polypropylene and polybutylene oxide condensates of alkylphenols are suitable for use as the non-ionic surfactant of the surfactant systems of the present invention, with poly (ethylene oxide) condensates being preferred. Commercial non-ionic surfactants of this type include Igepal? CO-630, marketed by GAF Corporation; and Triton ™ X-45, X-114, X-100 and X-102, all sold by Rohm & Haas Company. These surfactants are generically referred to as alkoxylated alkylphenols (for example ethoxylated alkylphenols).

The condensation products of alcohols primary and secondary aliphatics with about 1 to approximately 25 moles of ethylene oxide are suitable as nonionic surfactants of nonionic surfactant systems according to the present invention. Examples of nonionic surfactants Commercials of this type include Tergitol? 15-S-9 (the condensation product of the linear C 11 -C 15 alcohol with 9 moles of ethylene oxide), Tergitol? 24-L-6 NMW (the product of condensation of primary C 12 -C 14 alcohol with 6 moles of ethylene oxide with a narrow distribution of molecular weight), both marketed by Union Carbide Corporation; Neodol ™ 45-9 (the product of condensation of linear C 14 -C 15 alcohol with 9 moles of ethylene oxide), Neodol ™ 23-3 (the condensation product of alcohol C 12 -C 13 linear with 3.0 moles of oxide ethylene), Neodol ™ 45-7 (the product of condensation of linear C 14 -C 15 alcohol with 7 moles of ethylene oxide), Neodol ™ 45-5 (the condensation product of alcohol C 14 -C 15 linear with 5 moles of oxide ethylene) marketed by Shell Chemical Company, Kyro? EOB (the condensation product of alcohol C 13 -C 15 with 9 moles of ethylene oxide), marketed by The Procter & Gamble Company, and Genapol LA O3O or O5O (the condensation product of alcohol C 12 -C 14 with 3 or 5 moles of oxide ethylene) marketed by Hoechst. The preferred HLB interval in these products it is 8-11 and with maximum 8-10 preference.

Also useful as the non-ionic surfactant of The surfactant systems of the present invention are the alkylpolysaccharides described in the patent US 4,565,647.

Preferred alkyl polyglycosides have the formula: R 2 O (C n H 2 O) t (glycosyl) x wherein R2 is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures of the same where the alkyl groups contain about 10 to about 18, preferably about 12 to about 14 carbon atoms; n is 2 or 3, preferably 2; t is from 0 to about 10, preferably 0; and x is from about 1.3 to about 10, preferably of about 1.3 to about 3 and most preferably about 1.3 to about 2.7.

The condensation products of ethylene oxide with a hydrophobic base formed by the condensation of the oxide of Propylene with propylene glycol are also suitable to be used as additional non-ionic surfactant systems according to the present invention. Examples of compounds of this type include some of Plurafac? commercial surfactants LF404 and Pluronic ™, marketed by BASF.

They are also suitable as the surfactant Non-ionic non-ionic surfactant system according to the present invention the condensation products of ethylene oxide with the product of the reaction between propylene oxide and the ethylenediamine Examples of this type of non-ionic surfactant include some commercial Tetronic ™ compounds, marketed by BASF.

For use as a non-ionic surfactant of Surfactant systems according to the present invention are preferred polyethylene oxide condensates of alkylphenols, products of condensation of primary and secondary aliphatic alcohols with from about 1 to about 25 moles of ethylene oxide, alkylpolysaccharides and mixtures thereof. The most preferred are C 8 -C 14 alkyl ethoxylated phenols that they have 3 to 15 ethoxy groups and alcohols C 8 -C 18 ethoxylated (preferably C 10 on average) having 2 to 10 ethoxy groups, and mixtures of the same.

The most preferred nonionic surfactants are the polyhydroxy fatty acid type surfactants of the formula: R 2 -C (O) -N (R 1) - Z wherein R 1 is H, or R 1 is hydrocarbyl C 1-4, 2-hydroxyethyl, 2-hydroxy propyl or a mixture thereof, R 2 is C 5-31 hydrocarbyl, and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly attached to the chain, or a derivative alkoxylated thereof. Preferably, R1 is methyl, R 2 is a C 11-15 alkyl or alkyl chain or linear C 16-18 alkenyl such as coconut alkyl or mixtures thereof and Z comes from a reducing sugar as glucose, fructose, maltose or lactose in a reaction of reductive amination

Anionic surfactants : The anionic surfactants suitable for use in the present invention are linear alkylbenzenesulfonate and alkyl ester sulfonate surfactants including linear esters of C 8 -C 20 carboxylic acids (i.e., fatty acids) that are sulfonated with SO 3 gas according to "The Journal of the American Oil Chemists Society", 52 (1975), p. 323-329. Suitable starting materials would include natural fatty substances such as those derived from tallow, palm oil, etc.

Alkylsulfonate ester surfactants preferred, especially for laundry applications, they comprise alkyl sulphonate ester surfactants of the formula structural:

\melm{\delm{\para}{SO _{3} M}}{C}{\uelm{\para}{H}}

---

\uelm{C}{\uelm{\dpara}{O}}

--- OR^{4}R3 ---

 \ melm {\ delm {\ para} {SO3 M}} {C} {\ uelm {\ para} {H}} 

---

 \ uelm {C} {\ uelm {\ dpara} {O}} 

--- OR 4

where R 3 is a hydrocarbyl C 8 -C 20, preferably an alkyl, or combinations thereof, R 4 is a hydrocarbyl C 1 -C 6, preferably an alkyl, or combinations thereof, and M is a cation that forms a salt Water soluble with the alkyl sulfonate ester. The training cations Suitable salts include metals such as sodium, potassium and lithium and substituted and unsubstituted ammonium cations, such as monoethanolamine, diethanolamine and triethanolamine. Preferably, R 3 is C 10 -C 16 alkyl and R 4 is methyl, ethyl or isopropyl. Especially preferred are esters. methylsulfonate, wherein R 3 is alkyl C_ {10} -C_ {16}.

Other suitable anionic surfactants include alkyl sulfate surfactants that are salts or acids water-soluble formula ROSO 3 M where R is preferably a C 10 -C 24 hydrocarbyl, preferably an alkyl or hydroxyalkyl having an alkyl component C 10 -C 20, more preferably an alkyl or C 12 -C 18 hydroxyalkyl and M is H or a cation. Typically, alkyl chains are preferred C 12 -C 16 for wash temperatures more low (e.g., below 50 ° C) and chains C 16-18 alkyl for wash temperatures higher (eg, above 50 ° C).

Other anionic surfactants useful for purposes Detersives include soap salts, alkane C 8 -C 22 primary sulfonates or secondary, C 8 -C 24 olefin sulfonates, sulfonated polycarboxylic acids prepared by sulfonation of pyrolized product of alkaline earth metal citrates, is say, as described in GB-1,082,179, C 8 -C 24 alkyl polyglycol ethersulfates (which contain up to 10 moles of ethylene oxide); alkyl glycerol sulfonates, acyl glycerol fatty sulfonates, oleyl glycerol sulfates  fatty, alkylphenol ether sulfates of ethylene oxide, sulphonates paraffin, alkyl phosphates, isethionates such as acyl isethionates, N-acyl taurates, alkylsuccinamates and sulfosuccinates, sulphosuccinate monoesters (especially C 12 -C 18 saturated monoesters e unsaturated) and sulphosuccinate diesters (especially C 6 -C 12 saturated and unsaturated diesters), acylsarcosinates, alkylpolysaccharide sulfates such as alkyl polyglycoside sulfates (non-ionic compounds not sulfates are described below), primary alkyl sulfates branched and alkyl polyethoxy carboxylates such as those of formula RO (CH 2 CH 2 O) k -CH 2 COO-M +  where R is a C 8 -C 22 alkyl, k is a integer from 1 to 10, and M is a salt-forming cation soluble. Also suitable are resin acids and hydrogenated resin acids such as rosin, rosin hydrogenated and hydrogenated resin acids present in the oil of conifers or derivatives thereof.

Other examples are described in "Surface Active Agents and Detergents "(Vol. I and II, by Schwartz, Perry and Berch).  Some of said surfactants are also described in a manner General in US Patent 3,929,678, issued on 30 December 1975 to Laughlin et al., from column 23, line 58, to column 29, line 23.

Anionic surfactants especially Preferred in the present invention include surfactants of the type alkoxylated alkyl sulfate in the form of salts or water-soluble acids of formula RO (A) m SO3M, where R is a group C 10 -C 24 alkyl or hydroxyalkyl no substituted with an alkyl component C 10 -C 24, preferably an alkyl or C 12 -C 20 hydroxyalkyl, more preferably an alkyl or hydroxyalkyl C 12 -C 18, A is an ethoxy or propoxy unit, m is greater than zero, typically about 0.5 to about 6, more preferably about 0.5 to about 3, and M is H or a cation that can be, for example, a metal cation (for example sodium, potassium, lithium, calcium, magnesium, etc.), or an ammonium or substituted ammonium cation. In the The present invention contemplates both ethoxylated alkyl sulfates as propoxylated alkyl sulfates. Specific examples of cations of substituted ammonium include methylammonium cations, dimethylammonium and trimethylammonium and quaternary ammonium cations such as tetramethylammonium cations and dimethylpiperidinium as well as alkylamine derivatives such as ethylamine, diethylamine, triethylamine, mixtures thereof and Similar. Examples of surfactants are alkyl C 12 -C 18 polyethoxylated sulfate (1.0) (C 12 -C 18 E (1.0) M), the alkyl C 12 -C 18 polyethoxylated sulfate (2.25) (C 12 -C 18 E (2.25) M), the alkyl C 12 -C 18 polyethoxylated sulfate (3.0) (C 12 -C 18 E (3.0) M) and the C 12 -C 18 alkyl polyethoxylated sulfate (4.0) (C 12-C 18 E (4.0) M), where M Sodium and potassium are conveniently selected.

If included, the compositions bleaching agents of the present invention typically comprise of about 1%, preferably about 3% at about 40%, preferably about 20%, by weight of these anionic surfactants.

Cationic Surfactants : Cationic detersive surfactants suitable for use in the bleaching compositions of the present invention are those having a long chain hydrocarbyl group. Examples of cationic surfactants of this type include ammonium type surfactants such as, for example, alkyltrimethylammonium halides and surfactants with the formula: [R 2 (OR 3) y] [R 4 (OR 3) y] 2 R 5 N + X- wherein R 2 is an alkyl or alkyl benzyl group having from about 8 to about 18 atoms of carbon in the alkyl chain, each R 3 is selected from the group consisting of -CH 2 CH 2 -, -CH 2 CH (CH 3) -, -CH 2 CH (CH 2 OH) -, -CH 2 CH 2 CH 2 -, and mixtures thereof; each R 4 is selected from the group consisting of C 1 -C 4 alkyl, C 1 -C 4 hydroxyalkyl, benzyl ring structures formed by the union of the two R R groups 4, -CH 2 CHOH-CHOHCOR 6 CHOHCH 2 OH wherein R 6 is any hexose or hexose polymer with a molecular weight of less than about 1,000, and hydrogen when and is not 0 ; R 5 is equal to R 4 or is an alkyl chain in which the total number of carbon atoms of R 2 plus R 5 is not more than about 18; each y is from 0 to about 10 and the sum of the values of y is from 0 to about 15; and X is any compatible anion.

Very preferred cationic surfactants are the water-soluble quaternary ammonium compounds useful in the present composition of formula (i): R 1 R 2 R 3 R 4 N + X - where R 1 is C 8 -C 16 alkyl, each R 2, R 3 and R 4 is, independently of each other, C 1 -C 4 alkyl, C_ hydroxyalkyl {1} -C 4, benzyl and - (C 2 H 40) x H where x has a value of 2 to 5, and X is an anion. No more than one R 2, R 3 or R 4 must be benzyl. The preferred alkyl chain length for R 1 is C 12 -C 15, particularly when the alkyl group is a mixture of chain lengths derived from coconut or palm kernel oil or is derived by synthesis by accumulation of olefins or synthesis of OXO alcohols. Preferred groups for R 2, R 3 and R 4 are methyl and hydroxyethyl groups and the X anion can be selected from halide, methosulfate, acetate and
phosphate.

\delm{C}{\delm{\dpara}{O}}

-- C_{12-14} alquilo y R_{2}R_{3}R_{4} son metilo); y di-alquilimidazolinas [(i)].Examples of suitable quaternary ammonium compounds of the formulas (i) for use in the present invention include, but are not limited to: trimethyl ammonium coconut chloride or bromide; coconut methyl dihydroxyethyl ammonium chloride or bromide; decyl triethylammonium chloride; decyl dimethyl hydroxyethyl ammonium chloride or bromide; C 12-15 dimethyl hydroxyethyl ammonium chloride or bromide; coconut dimethyl hydroxyethyl ammonium chloride or bromide; myristyl trimethyl ammonium methylsulfate; lauryl dimethyl benzyl ammonium chloride or bromide; lauryl dimethyl (ethenoxy) 4 ammonium chloride or bromide; choline esters (compounds of formula (i) wherein R 1 is CH 2 - CH 2 - O -

 \ delm {C} {\ delm {\ dpara} {O}} 

- C 12-14 alkyl and R 2 R 3 R 4 are methyl); and di-alkylimidazolines [(i)].

In US Patent 4,228,044, granted to Cambre on October 14, 1980, and in the request for European patent EP 000.224 also describes other cationic surfactants useful in the present invention.

If included, the compositions bleaching agents of the present invention typically comprise of about 0.2%, preferably about 1% at about 25%, preferably about 8%, by weight of these cationic surfactants.

Ampholytic Surfactants : Ampholytic surfactants, examples of which are described in US Patent 3,929,678, are also suitable for use in the bleaching compositions of the present invention.

If included, the compositions bleaching agents of the present invention typically comprise of about 0.2%, preferably about 1% at about 15%, preferably about 10%, by weight of these ampholytic surfactants.

Hybrid ion surfactants: Hybrid ion surfactants, examples of which are described in US Patent 3,929,678, are also suitable for use in bleaching compositions.

If included, the compositions bleaching agents of the present invention typically comprise of about 0.2%, preferably about 1% at about 15%, preferably about 10%, by weight of these hybrid ion surfactants.

Semi-polar non-ionic surfactants : semi-polar non-ionic surfactants are a special category of non-ionic surfactants that include water-soluble amine oxides having the formula:

\melm{ \oplus }{N}{\uelm{\para}{O ^{\ominus} }}

--- (R^{5})_{2}R 3 --- (OR 4) x ---

 \ melm {\ oplus} {N} {\ uelm {\ para} {O ^ {\ ominus}}} 

--- (R 5) 2

where R 3 is a group alkyl, hydroxyalkyl or alkylphenyl or mixtures thereof that it contains from about 8 to about 22 atoms of carbon; R 4 is an alkyl or hydroxyalkyl group containing from about 2 to about 3 carbon atoms or mixtures thereof; x is 0 to about 3; and each R5 is a alkyl or hydroxyalkyl group containing from about 1 to about 3 carbon atoms or a poly (oxide group of ethylene) containing from about 1 to about 3 ethylene oxide groups (R 5 groups may be attached each other, that is, through an oxygen or nitrogen atom, to form a ring structure); phosphine oxides water-soluble containing an alkyl moiety of about 10 at about 18 carbon atoms and 2 moieties selected from group consisting of alkyl groups and hydroxyalkyl groups that they contain from about 1 to about 3 atoms of carbon; and water-soluble sulfoxides containing an alkyl moiety from about 10 to about 18 carbon atoms and a remainder selected from the group consisting of alkyl moieties and hydroxyalkyl of about 1 to about 3 atoms of carbon.

The amine oxide type surfactants in Particularly include alkyl dimethyl oxides C 10 -C 18 amine and alkoxyethyl oxides dihydroxyethyl C 8 -C 12 amine.

If included, cleaning compositions of the present invention typically comprise of about 0.2%, preferably about 1% at about 15%, preferably about 10%, by weight of these semi-polar nonionic surfactants.

Auxiliary Surfactants : The bleaching compositions of the present invention may also comprise an auxiliary surfactant selected from the group of primary or tertiary amines. The primary amines suitable for use in the present invention include amines according to the formula R1 NH2 where R1 is a C6-C12 alkyl chain, preferably C6 - C 10 or R 4 X (CH 2) n, X is -O-, -C (O) NH- or -NH-, R 4 is a C 6 -C_ alkyl chain {12}, n is from 1 to 5 and preferably 3. The alkyl chains R1 may be linear or branched and may be interrupted by up to 12, preferably less than 5, ethylene oxide moieties.

Proteolytic enzymes, if present, will be incorporate into the cleaning compositions herein invention at a level of 0.0001% to 2%, preferably 0.001% to 0.2%, more preferably from 0.005% to 0.1%, of pure enzyme by weight of the composition.

Amylases (α and / or β) may be included to remove carbohydrate stains. In the document WO94 / 02597 describes cleaning compositions that incorporate mutant amylases (see also WO95 / 10603). Other amylases Known for use in cleaning compositions include α- and β-amylases. The α-amylases are known in the art and include those described in US-5,003,257; EP 252,666; WO / 91/00353; FR 2,676,456; EP 285,123; EP 525,610; EP 368,341 and GB-1,296,839 (Novo). Other suitable amylases are the improved stability amylases described in the documents WO94 / 18314 and WO96 / 05295, Genencor, and variants of amylases that have an additional modification in the immediate precursor marketed by Novo Nordisk A / S, described in WO 95/10603. Also suitable are the amylases described in EP 277 216.

Examples of commercial α-amylase products are Purafect Ox Am® from Genencor and Termamyl®, Ban®,
Fungamyl® and Duramyl®, all sold by Novo Nordisk A / S Denmark. In document WO95 /
26397 other suitable amylases are described: α-amylases are characterized by having a specific action at least 25% higher than the specific action of Termamyl® in a temperature range of 25 ° C to 55 ° C and a pH in the range of 8 to 10 , measured by the Phadebas® α-amylase activity assay. Variants of the above enzymes, described in WO96 / 23873 (Novo Nordisk) are suitable. Other amylolytic enzymes with improved properties in terms of activity level and with a combination of thermostability and higher activity level are described in WO95 / 35382.

These amylolytic enzymes, if present, are incorporated into the cleaning compositions herein invention at a level of 0.0001% to 2%, preferably 0.00018% to 0.06%, more preferably from 0.00024% to 0.048%, of pure enzyme in composition weight.

The enzymes listed above may have any suitable origin, such as vegetable, animal, Bacterial, fungal or yeast. The origin can also be mesophilic or extremophilic (psychrophilic, psychotropic, thermophilic, barophilic, alkalophilic, acidophilic, halophilic, etc.). Can be used purified or unpurified forms of these enzymes. Currently It is a common practice to modify wild-type enzymes by protein or gene engineering techniques to optimize your performance efficiency in detergent compositions for laundry and / or fabric care of the invention. By For example, variants can be designed to increase the Enzyme compatibility with respect to the ingredients of use common in these compositions. Alternatively, the variant can be designed to optimally adapt pH, stability of the bleach or chelator, the catalytic action and the like of the Enzyme variant to a certain cleaning application.

In particular, special attention should be given to oxidation sensitive amino acids for the stability of bleaching and in the case of surface charges for surfactant compatibility. The point can be modified. isoelectric of these enzymes replacing some amino acids loaded so that, p. eg, an increase in isoelectric point helps to improve compatibility with anionic surfactants. Too the stability of enzymes can be improved by creating, e.g. eg additional salt bridges and making the binding sites of the Calcium increase chelator stability.

These optional detersive enzymes, if you are present, they are normally incorporated into the cleaning composition a 0.0001% to 2% levels of pure enzyme by weight of the composition cleaner. Enzymes can be added as unique ingredients separated (pellets, granules, stabilized liquids, etc., which contain an enzyme) or as mixtures of two or more enzymes (e.g., cogranulates).

Other suitable detergent ingredients that They can be added are enzyme oxidation inactivators. Examples of these enzyme oxidation inactivators are the tetraethylene ethoxylated polyamines.

A series of enzymatic materials and means for its incorporation into synthetic detergent compositions is also described in WO 9307263 and WO 9307260, a Genencor International, WO 8908694, and US-3,553,139, granted on January 5, 1971 to McCarty et al. Enzymes too are described in US 4,101,457 and in US 4,507,219. Enzymatic materials useful for liquid detergent formulations and their incorporation into these Formulations are described in US 4,261,868.

Enzyme stabilizers : The enzymes used in detergents can be stabilized by different techniques. Enzyme stabilization techniques are described and illustrated in US-3,600,319, EP 199,405 and EP 200,586. Enzyme stabilization systems are also described, for example, in US 3,519,570. A Bacillus, sp. Useful AC13 providing proteases, xylanases and cellulases is described in WO 9401532. The enzymes used in the present invention can be stabilized thanks to the presence of water-soluble sources of calcium and / or magnesium ions in the finished compositions that provide these ions to the enzymes Enzyme stabilizers and appropriate levels of use are described in US-5,705,464, US-5,710,115 and US-5,576,282.

Detergency builder additives : the detergent and bleach compositions described herein preferably comprise one or more detergency builder additives or detergent builder additive systems. If present, the compositions will typically comprise at least about 1% of the detergent builder additive, preferably from about 5%, more preferably from about 10% to about 80%, preferably at about 50%, more preferably at about 30 % by weight, of detergency reinforcing additive. However, this does not mean that lower or higher levels of detergent builder additive are excluded.

Additives strengthening detergency preferred for use in detergent compositions and bleaches, especially the compositions for washing tableware, described herein include, but not limiting form, water-soluble compounds of reinforcing additive of the detergency (for example polycarboxylates) as described in US Patents 5,695,679, US-5,705,464 and US-5,710,115. Others Suitable polycarboxylates are described in the patents US 4,144,226, US 3,308,067 and 3,723,322. Preferred polycarboxylates are hydroxycarboxylates containing up to three carboxy groups per molecule, more especially titrates.

Additives strengthening detergency inorganic or containing P include, but not limiting, alkali metal, ammonium and alkanolammonium salts of polyphosphates (illustrated by tripolyphosphates, pyrophosphates and vitreous polymeric metaphosphates), phosphonates (see, for example, US Patents 3,159,581; US 3,213,030;  US 3,422,021; US-3,400,148 and US 3,422,137), phytic acid, silicates, carbonates (including bicarbonates and sesquicarbonates), sulfates and aluminosilicates.

       \ newpage
    

However, in certain cases they are required Phosphate-free detergency builders. It should be noted that the present compositions act surprisingly well even in the presence of the so-called reinforcing additives of the "weak" detergency (compared to phosphates), such such as citrate, or in the so-called situation "of infrastructure "that may occur when used zeolite or silicate detergency builder additives laminate.

Suitable silicates include silicates of water-soluble sodium with a SiO2: Na2O ratio of approximately 1.0 to 2.8, with the ratios of approximately 1.6 to 2.4 and the ratio of approximately 2.0. The silicates can be in salt form anhydrous or hydrated salt. Sodium silicate with a ratio SiO2: Na2O of 2.0 is the most preferred. Silicates, yes are present, are preferably present in the detergent and bleaching compositions described herein memory at a level of about 5% to about 50% in composition weight, more preferably about 10% at about 40% by weight.

The additive reinforcing compounds of the partially soluble or insoluble detergency suitable for use in detergent and bleaching compositions, especially in granulated detergent compositions, include, but not limiting form, crystalline laminar silicates, preferably crystalline laminar sodium silicates (partially water soluble) as described in the patent US 4,664,839, and sodium aluminosilicates (insoluble in water). If they are present in the compositions detergents and bleaches, these additives reinforcing the detergency are typically present at a level of about 1% to 80% by weight, preferably of approximately 10% to 70% by weight and most preferably approximately 20% to 60% by weight of the composition.

They can be used in the compositions described crystalline lamellar sodium silicates herein which have the general formula NaMSi_ {x} O_ {2x + 1} \ cdotyH_ {2} where M is sodium or hydrogen, x is a number of approximately 1.9 to about 4, preferably about 2 to approximately 4, most preferably 2, e y is a number of about 0 to about 20, preferably 0. Silicates  sodium crystalline laminar of this type are described in EP-A-0164514 and the methods for its preparation are described in DE-A-3417649 and DE-A-3742043. The most material preferred is delta-Na2 SiO5, marketed  by Hoechst AG as NaSKS-6 (usually abbreviated herein as "SKS-6"). Unlike the detergent-enhancing additives of type zeolite, the silicate type detergency builder Na SKS-6 does not contain aluminum. He NaSKS-6 presents the morphology delta-Na2 SiO5 laminar silicate. He SKS-6 is a very preferred laminar silicate for its use in the compositions described herein, although can be used in the compositions described herein memory other layered silicates such as those with the formula general NaMSi_ {O} {2x + 1} \ cdotyH_ {2} where M is sodium or hydrogen, x is a number from 1.9 to 4, preferably 2, e y is a number from 0 to 20, preferably 0. Other layered silicates of Hoechst include NaSKS-5, NaSKS-7 and NaSKS-11, such as alpha, beta and gamma forms. How indicated above, the form delta-Na2 {SiO5 {(NaSKS-6) is most preferred for use in the present invention. Others silicates can also be useful as, for example, silicate magnesium, which can serve as a potentiating agent for friability in granulated formulations, as agent stabilizer for oxygen releasing bleaches and as component of the regulating systems of the soaps.

Laminate Sodium Silicate Material crystalline is preferably present in the compositions granular particulate detergents mixed intimately with a solid, water-soluble ionizable material. Solid material, Water soluble ionizable is preferably selected from acids organic, salts of organic and inorganic acids and mixtures of same.

Additives strengthening detergency aluminosilicate type are of great importance in most granular intensive cleaning detergent compositions currently marketed and can also be an ingredient significant detergency builder additive for liquid detergent formulations. The reinforcing additives of the aluminosilicate type detergency have the empirical formula:

[M_ {z} (AlO2) y} \ cdot \ xH_ {2} O

where z and y are whole numbers of at least 6, the molar ratio between z and y is 1.0 to about 0.5, and x is an integer of about 15 to about 264. Preferably, the reinforcing additive of the aluminosilicate type detergency is a zeolite type aluminosilicate having the cell formula unity:

Na_ {z} [(AlO2) z (SiO2) y] \ \ cdot \ xH_ {2} O

where z and y are at least 6; the molar ratio z: y is 1.0 to 0.5 and x is at least 5, preferably from 7.5 to 276 and more preferably from 10 to 264. The aluminosilicate type detergency builder additives are preferably in hydrated form, are preferably crystalline and contain from about 10% to about 28%, more preferably from about 18% to about 22% water hydration.

These ion exchangers materials of aluminosilicate can have a crystalline or amorphous structure and they can be natural or synthetic aluminosilicates. A method for manufacture aluminosilicate ion exchange materials se described in US 3,985,669. The materials synthetic crystalline aluminosilicate ion exchangers Preferred useful in the present invention are marketed with the names zeolite A, zeolite B, zeolite P, zeolite X, zeolite MAP and zeolite HS and mixtures thereof. In one embodiment especially  preferred, the aluminosilicate ion exchange material Crystalline has the formula:

Na 12 [(AlO 2) 12 (SiO 2) 12] \ \ cdot \ xH_ {2} O

where x is about 20 to about 30, especially about 27. This material is known as Zeolite A. They can also be used in the present invention dehydrated zeolites (x = 0-10). Preferably, the aluminosilicate has a particle size of approximately 0.1 to 10 micrometers in diameter. Zeolite X has the formula:

Na_86 [(AlO2) 86 (SiO2) 106] \ \ cdot \ 276H2 O

Additives strengthening detergency citrate type, for example, citric acid and soluble salts thereof (particularly sodium salt) are reinforcing additives of the polycarboxylate type detergency of particular importance for liquid detergent formulations for intensive cleaning for its availability from renewable resources and its biodegradability Citrates can also be used in granulated compositions, especially together with additives Zeolite and / or laminar silicate detergency builders. Oxydisuccinates are also especially useful in this type of Compositions and combinations

Also suitable in the compositions detergents described herein are the 3,3-dicarboxy-4-oxa-1,6-hexanedioates  and related compounds described in US 4,566,984. The reinforcing additives of the Useful succinic acid type detergency include acids C 5 -C 20 alkyl and alkenyl succinic and the You leave them. A particularly preferred compound of this type is dodecenylsuccinic acid. Specific examples of Succinate-type detergency builder additives include: lauryl succinate, myristyl succinate, palmityl succinate, 2-dodecenylsuccinate (preferred), 2-pentadecenylsuccinate and the like. The lauryl succinates are detergency builders preferred from this group and are described in the patent EP-6200690.5 / 0.200.263, published on November 5 of 1986.

They can also be incorporated into the compositions fatty acids, for example, monocarboxylic acids C_ {12} -C_ {18}, alone or together with the above detergency builders, especially additives detergent builders of citrate and / or succinate type, for obtain an additional detergency reinforcing action. Saying use of fatty acids will generally produce a decrease in soaps, which should be taken into account by the formulator

Dispersants : in the cleaning compositions of the present invention one or more suitable polyalkyleneimine dispersants may be incorporated. Examples of these suitable dispersants can be found in EP-111,965, EP-111,984 and EP-112,592; US 4,597,898, US 4,548,744 and US 5,565,145. However, in the laundry compositions of the present invention any dirt or clay stain dispersant or suitable redeposition inhibitor can be used.

In addition, polymeric dispersing agents that include polycarboxylates and polymeric polyethylene glycols are suitable for use in the present invention. Acids unsaturated monomers that can be polymerized to form Suitable polymeric polycarboxylates include acrylic acid, maleic acid (or maleic anhydride), fumaric acid, acid itaconic acid, aconitic acid, mesaconic acid, citraconic acid and methylenemalonic acid Polymeric Polycarboxylates particularly suitable can be derived from acrylic acid. The Acrylic acid based polymers of this type that are useful in This invention is the water-soluble salts of acrylic acid polymerized The average molecular weight of the polymers of this type in the acid form preferably ranges from about 2,000 to 10,000, more preferably about 4,000 to 7,000 and, most preferably, from about 4,000 to 5,000. The Water-soluble salts of acrylic acid polymers of this type may include, for example, alkali metal salts, ammonium and substituted ammonium. Soluble polymers of this type are known materials The use of polyacrylates of this type in detergent compositions have been described, for example, in 3,308,067.

As a preferred component of the agent dispersant / antiredeposition copolymers can also be used  based on acrylic acid / maleic acid. Materials of this type include the water-soluble salts of acrylic acid copolymers and maleic acid The average molecular weight of copolymers of this type in the acid form preferably ranges from about 2,000 to 100,000, preferably from about 5,000 to 75,000 and most preferably about 7,000 to 65,000. The relationship between acrylate and maleate segments in Copolymers of this type will generally range from about 30: 1 and about 1: 1, more preferably about 10: 1 to 2: 1. Water soluble salts of acid copolymers acrylic / maleic acid of this type may include, for example, alkali metal, ammonium and substituted ammonium salts. The soluble acrylate / maleate copolymers of this type are materials known that are described in EP-66915, published on December 15, 1982, as well as in EP 193.360, published on September 3, 1986, which also describes polymers of this type comprising hydroxypropyl acrylate. Other useful dispersing agents include terpolymers of Maleic / acrylic / vinyl alcohol. Materials of this type are also described in EP 193,360, including, for example, the 45/45/10 acrylic / maleic / vinyl alcohol terpolymer.

Other polymeric material that can be included It is polyethylene glycol (PEG). The PEG may submit a dispersant agent behavior and also act as a stain removal agent clay-antiredeposition. Weight ranges typical molecular for these purposes range from about 500 to about 100,000, preferably about 1,000 to about 50,000 and more preferably about 1,500 to about 10,000.

Dispersing agents can also be used. of polyaspartate and polyglutamate, especially together with additives Zeolite type detergency builders. The agents dispersants such as polyaspartate preferably have a molecular weight (average) of approximately 10,000.

Agents for releasing dirt : the compositions according to the present invention may optionally comprise one or more agents for releasing dirt. If used, the soil release agents will generally comprise from about 0.01%, preferably from about 0.1%, more preferably from about 0.2% to about 10%, preferably to about 5%, more preferably to about 3%, by weight of the composition. Non-limiting examples of suitable soil release polymers are described in US Patents 5,728,671; US 5,691,298; US 5,599,782; US 5,415,807; US 5,182,043; US 4,956,447; US 4,976,879; US 4,968,451; US 4,925,577; US 4,861,512; US 4,877,896; US 4,771,730; US 4,711,730; US 4,721,580; US 4,000,093; US 3,959,230; and US 3,893,929; and EP-0 219 048.

Other suitable dirt release agents They are described in US Patents 4,201,824; US 4,240,918; US 4,525,524; US 4,579,681; US 4,220,918; Y US 4,787,989; EP 279,134 A; EP 457,205 A; and of 2,335,044.

Chelating agents : the compositions of the present invention may also optionally contain a chelating agent that serves to chelate metal ions and metal impurities that would otherwise tend to deactivate the bleaching agent (s). Useful chelating agents may include aminocarboxylates, phosphonates, amino phosphonates, polyfunctionally substituted aromatic chelating agents and mixtures thereof. Other examples of suitable chelating agents and levels of use are described in US-5,705,464, US-5,710,115, US-5,728,671 and US-5,576,282.

The compositions of the present invention they can also contain water-soluble salts (or acid form) of the methyl glycine di-acetic acid (MGDA) as a chelator or detergency builder co-additive useful with, for example, insoluble detergency builder additives such as zeolites, laminar silicates and the like.

If used, these chelating agents generally will comprise from about 0.1% to about 15%, more preferably from about 0.1% to about 3.0%, by weight of the detergent composition herein invention.

Soap suppressant : Another optional ingredient is a suds suppressant, illustrated by silicones and silica-silicone blends. Examples of suitable suds suppressants are described in US Patent 5,0707,950 and US 5,728,671. These suds suppressors are normally used at levels of 0.001% to 2% by weight of the composition, preferably 0.01% to 1% by weight.

Softeners : Fabric softeners can also be incorporated into laundry detergent compositions according to the present invention. Examples of inorganic softeners are smectite clays described in GB-A-1 400 898 and in US 5,019,292. Organic softeners include water insoluble tertiary amines as described in GB-A-1 514 276 and EP-B-011 340 and combinations thereof with C12-C14 mono quaternary ammonium salts as described in EP-B-026 527 and EP-B-026 528 and long double chain amides as described in EP-B-0 242 919. Other useful organic ingredients of fabric softener systems include high molecular weight poly (ethylene oxide) materials as described in EP-A-0 299 575 and 0 313 146.

Especially suitable fabric softeners are described in patents US-5,707,950 and US 5,728,673.

Smectite clay levels are normally from 2% to 20%, more preferably from 5% to 15% in weight, adding the product as a dry mixed component to the rest of the formulation Organic fabric softeners such as materials based on non-water-soluble tertiary amines or amides Long double chain are incorporated at levels of 0.5% to 5% in weight, usually 1% to 3% by weight, while the materials of high molecular weight polyethylene oxide and materials Water-soluble cationics are added in amounts of 0.1% to 2%, usually from 0.15% to 1.5% by weight. These materials are added normally to the spray dried portion of the composition, although in some cases it may be more convenient to add them in form of dry mixed particles or spray them in the form of molten liquid on the solid components of the composition.

Quaternary Ammonium Compounds biodegradable as described in EP-A-040 562 and EP-A-239 910 have been presented as alternatives to ammonium chlorides with double alkyl chains long and traditionally used methyl sulfates.

Non-limiting examples of compatible anions with the softener for quaternary ammonium compounds and Amine precursors include chloride or methylsulfate.

Inhibition of dye transfer : the detergent compositions of the present invention may also include compounds to inhibit the transfer from one tissue to another of dissolved and suspended dyes present during tissue washing and conditioning operations when colored fabrics are used.

Dye transfer inhibiting agents polymeric

Detergent compositions according to the present invention may also comprise from 0.001% to 10%, preferably  from 0.01% to 2%, more preferably from 0.05% to 1%, by weight of agents that inhibit the transfer of polymeric dyes. Such dye transfer inhibitors Polymers are normally incorporated in the compositions detergents to inhibit the transfer of dyes from colored fabrics to other fabrics washed with them. These polymers have the property of adsorbing or complexing with fugitive dyes from colored tissues before that these can be fixed on other washed products.

The transfer inhibiting agents of Especially suitable polymeric dyes are the polymers of Polyamine N-oxide, the copolymers of N-vinyl pyrrolidone and N-vinylimidazole, the polymers of polyvinylpyrrolidone, polyvinyloxazolidones and polyvinylimidazoles or mixtures thereof. Examples of these dye transfer inhibiting agents are described in patents US-5,707,950 and 5,707,951.

Other transfer inhibiting agents Suitable colorants include, but are not limited to, the crosslinked polymers. Crosslinked polymers are polymers whose Main chains are interconnected to a certain degree. These links can be chemical or physical in nature, possibly with active groups in the main chain or in the ramifications. Crosslinked polymers have been described in Journal of Polymer Science, volume 22, p. 1035-1039.

In one embodiment, crosslinked polymers they are so that they form a rigid three-dimensional structure that can trap dyes in the pores of its structure three-dimensional In another embodiment, crosslinked polymers they catch dyes due to swelling. These crosslinked polymers are described in the patent application European codependent 94870213.9.

The addition of these polymers also improves the Enzyme yield according to the invention.

PH modification and buffering : Many of the detergent and bleaching compositions described herein are buffered, that is, they are relatively resistant to a pH drop in the presence of acid stains. However, other compositions of the present invention may have an exceptionally low buffering capacity or may be basically unbuffered. Techniques for controlling or varying the pH at recommended levels of use include more generally the use not only of buffers but also of alkalis, acids, systems to increase pH, containers with double compartments, etc. and are well known to those skilled in the art.

Preferred ADD compositions herein invention comprise a pH regulator component selected from water-soluble alkaline inorganic salts and reinforcing additives of organic or inorganic water-soluble detergency as described in patents US-5,705,464 and US 5,710,115.

Materials Care Agents : Preferred ADD compositions may contain one or more materials care agents that are effective as corrosion inhibitors and / or anti-tarnishing adjuvants as described in US Pat. Nos. 5,705,464 , US-5,710,115 and US-5,646,101.

When present, such materials protectors are preferably incorporated at low levels, by example, from about 0.01% to about 5% of the ADD composition.

Other materials : the detersive ingredients or adjuvants optionally included in the compositions of the invention may include one or more materials to strengthen or improve the cleaning capacity, treat the substrate to be cleaned or improve the aesthetics of the compositions. Adjuvants that may also be included in the compositions of the present invention, at their conventional levels of use established by the art (generally, adjuvant materials comprise, in total, from about 30% to about 99.9%, preferably from about 70% to about 95%, by weight of the composition), include other active ingredients such as phosphate-free detergency builders, color spots, silver care agents, anti-tarnish and / or anti-corrosion agents , dyes, fillers, germicides, sources of alkalinity, hydrotropes, antioxidants, perfumes, solubilizing agents, vehicles, process improvers, pigments and pH regulators as described in patents US-5,705,464, US-5,710,115, US -5,698,504, US-5,695,679, US-5,686,014 and US-5,646,101.

Cleaning methods : In addition to the methods for cleaning tissues, dishes and other hard surfaces and parts of the body by personal cleansing, described herein, the present invention also encompasses a pretreatment process for washing fabrics that are stained or soiled comprising the steps of directly contacting said stains and / or dirt with a very concentrated form of the bleaching composition mentioned above and then washing this fabric with conventional aqueous wash solutions. Preferably, the bleaching composition remains in contact with the dirt / stain for a period of approximately 30 seconds to 24 hours before proceeding to wash the stained or dirty substrate pretreated in a conventional manner. More preferably, the pretreatment times will be approximately 1 to 180 minutes.

Organic catalyst product

The organic catalyst compound and / or the bleaching compositions of the present invention may be used in different products for use in the process of washed.

In a preferred embodiment a product comprising the organic catalyst compound and / or the bleaching compositions of the present invention. The product also includes instructions for using the compound organic catalyst and / or bleaching composition to clean a tissue to be cleaned, preferably a stained fabric. The instructions include the steps, preferably sequential, from:

(i)

contact the tissue with a wash solution, preferably containing a peracid; Y

(ii)

supply the catalyst compound organic and / or the bleaching composition by means of supply to the wash solution.

The supply stage of stage (ii) can be performed with different means of supply as discussed in This memory.

The result of following these instructions is that the organic catalyst compound and / or the compositions Bleaches are added to the wash solution after adding the fabric to wash solution.

More advantages can be achieved by adding the organic catalyst compound or bleaching compositions of Longer duration to the wash solution after adding the fabric to the wash solution, although the greater stability of the longer-lasting organic catalysts downplay the order of addition.

Determination of the longest lasting organic catalyst : to facilitate the determination of those organic catalysts that are included within the scope of the present invention, a test protocol, Test Protocol I, is presented below.

Test Protocol I

General / Parameters: all solutions are kept at 20 ° C. PH adjustments can be made if necessary using sodium carbonate or sulfuric acid, as appropriate. All the solutions are continuously stirred at 52.4 rad / s (500 rpm), except small aliquots (1-5 ml) of the solution dye bleach (DBS) that is removed to measure the absorbency. Absorbance values are measured in the λ max of the dye reference solution (RDS). He peracetic acid, 32% solution by weight in dilute acetic acid, is acquired from Aldrich (# 26,933-6).

OC is the organic catalyst

The SCO is the catalyst containing solution organic prepared by dissolving 0.010 mmol (typically approximately 2-3 mg, depending on weight molecular) of an organic catalyst (OC) at 20 ° C in 5 ml of water deionized immediately before (less than a minute) of adding the OCS to the base solution. If the organic catalyst is not soluble in 5 ml of deionized water, another 5 ml of a solvent are added 5 ml organic deionized water to facilitate dissolution of the organic catalyst. The organic solvents used are methanol, ethanol, dimethylformamide or acetonitrile. If the catalyst Organic is not soluble in a 1: 1 mixture of deionized water and organic solvent, the organic catalyst is dissolved in 100% of organic solvent If the organic catalyst is insoluble in The above dissolution media, the organic catalyst is add to the base solution in pure form.

The BS is the base solution to which the SCO is added. The base solution is prepared by mixing 1.0 l of deionized water with 10 mg (10 ppm) of a chelator (capable of sequestering transition metal ions to prevent the decomposition of peracetic acid and / or bleaching species) and an amount enough of sodium carbonate so that by adding 76 mg (76 ppm, 1.0 mmol) of peracetic acid (based on 100% activity), the pH of the solution is 10.0 (between 9.9 and 10, one). After one minute of stirring, the preparation of
BS.

OCBS is the base solution that contains organic catalyst that is prepared by adding the OCS to 1 l of the BS freshly prepared After adding the OCS to the BS, it is terminated OCBS preparation. OCBS must now have a pH of 10.0 (between 9.9 and 10.1). If the pH is not within this range, the OCBS preparation should be repeated so that the addition from the SCO to the BS be done together with the addition of carbonate sodium or sulfuric acid to obtain an OCBS with a pH of 10.0 (between 9.9 and 10.1).

CDS is the concentrated dye solution defined as a 90 ppm solution of Tropeoline O dye (Aldrich 19,968-0) in deionized water.

DBS is the dye bleach solution formed by the addition of a 100 ml aliquot of OCBS to 10 ml of CDS. The DBS should have an initial pH of 10.0. Yes (in the case unlikely) that the pH of the DBS falls below 9.6 in the time = t_ {D} (defined below), the pH must be controlled so that during the interval t_ {D} it remains between 9.8 and 10.1

w_ {OC} is a parameter in the protocol of final test that is used to describe the weight of the catalyst organic (OC), based on 100% purity, used to Prepare the solution with organic catalyst (OCS). The value for Default parameter is 0.010 mmol, added to 1.0 L of BS.

Determination of A_ {max}. 100 ml of water deionized at pH 10 are added to 10 ml of CDS. The absorbency of the resulting homogeneous dye reference solution (RDS) determined by UV spectroscopy visible at λ max (approximately 518 nm) is A max.

d_ {dec} is a parameter in the protocol of essay that describes the time that passes between the formation of the OCBS and the formation of the dye bleaching solution (DBS) after adding the OCBS to the CDS. This value is the duration of the decomposition of the organic catalyst in the OCBS before its addition to the CDS. The default value of parameter d_ {dec} (is that is, d_ {dec} = 45 min) is defined in the set of claims. The value of the d_ {dec} parameter is defined as equal to the value of the parameter d_ {ref}.

d_ {ref} is a parameter in the protocol of essay that describes the time that passes between the end of the BS preparation and bleaching solution formation dyes (DBS) by adding the BS to the CDS. This value is the reference duration of the peracid in the BS before the addition to the CDS. The default value of parameter d_ {ref} (is that is, d_ {ref} = 45 min) is defined in the set of claims. The value of the d_ {ref} parameter is defined as equal to the value of the parameter d_ {dec}.

d_ {bleach} is a parameter in the protocol test describing the time that passes between the formation of the dye bleaching solution (DBS) and collecting data. This value is the duration of bleaching of the DBS formed at from the addition of the BS or OCBS to the CDS. The value for Default parameter d_ {bleach} is 5 min.

Test protocol (Part I)

The initial stage is the preparation of the BS as It has been described. The time of completion of the preparation of the BS is set as t = 0. A 100 ml aliquot of the BS is removed to d_ {ref} and added once to 10.0 ml of CDS. An aliquot of 1-5 ml, R, of the resulting DBS is removed immediately before determining absorbency (collection of data). The absorbency of R is measured at λ max at the end d_ {bleach}.

The moment at which absorbency is measured (data collection) of the aliquot R is defined as t_ {R}. Therefore, it is necessary that t_ {R} = d_ {ref} + d_ {bleach}. The absorbency value measured at t_R is defined as A_ {t (R)}. The symbol \ deltaA_ {t (R)} is defined as A_ {max} - A_ {t (R)}.

Test protocol (Part II)

The initial stage is the preparation of the OCBS as described The time of preparation completion OCBS is set at t = 0. A 100 ml aliquot of the OCBS is removed to d_ {dec} and added once to 10.0 ml of CDS. An aliquot of 1-5 ml, D, of the resulting DBS is removed immediately before determining absorbency (collection of data). The absorbency of D is measured at λ max at the end d_ {bleach}.

The moment at which absorbency is measured (data collection) of aliquot D is defined as t_ {D}. Therefore, it is necessary that t_ {D} = d_ {dec} + d_ {bleach}. The absorbency value measured at t_ {D} is defined as A_ {t (D)}. The symbol \ deltaA_ {t (D)} is defined as A_ {max} - A_ {t (D)}.

The shelf life of the organic catalyst (OCL) is defined as the value d_ {dec} (or the time that the OC spends in the OCBS) so that the value \ deltaA_ {t (D)} = 3 x \ deltaA_ {t (R)}.

There are two cases, depending on the values \ deltaA_ {t (D)} compared to the value of \ deltaA_ {t (R)}.

Case A: if the value of \ deltaA_ {t (D)} \ geq m_ {f} x \ deltaA_ {t (R)}, where m_ {f} is 3, then a long-lasting organic catalyst is indicated and The OC is within the limits of this invention.

Case B: if the value of \ deltaA_ {t (D)} <m_ {f} x \ deltaA_ {t (R)}, where m_ {f} (the final multiplier) is 3, then a catalyst is not indicated Organic long-lasting and the OC is not within the limits of this invention.

Finally, if the value of the final multiplier determined (m_ {f}), which relates the value of \ deltaA_ {t (D)} with the value of δA_ {t (R)}, remains constant for a period of 30 min and if the determined value from m_ {f} to d_ {dec} = 2 min is 1.5 times higher than the value of m_ {f} that has remained constant over the 30 min interval, then the OCL is defined as the d_ {dec} at which the value of m_ {f} remains for the first constant time.

The following examples are included to illustrate the compositions of the present invention although not necessarily  limit or otherwise define the scope of the invention. Some of the organic catalyst compounds synthesized in the following examples (i.e. structure 6) have centers stereogenic so that it is possible to synthesize more than one isomeric organic catalyst compound depending on the choice of the isomeric starting materials. Therefore, it is obvious to the skilled in the art that organic catalyst compounds with different isomeric configuration may present different properties, including the shelf life of the organic catalyst.

Illustrative examples Example I Tetraphenylborate preparation N- (1-cyclohexylethyl) -3,4-dihydroisoquinolinium (one)

9

The typical procedure for the synthesis of dihydroisoquinolinium salts is as described in the art, as in Page, P. C B. et al. J. Org. Chem. 1998 , 63 , 2774. The precursor amine used in this reaction was 1-cyclohexylethylamine.

Example II Preparation of N- tert -butyl-3,4-dihydroisoquinolinium tetraphenylborate (2)

10

The typical procedure for the synthesis of dihydroisoquinolinium salts is as described in the art, as in Page, P. C B. et al. J. Org. Chem. 1998 , 63 , 2774. The precursor amine used in this reaction was cyclohexanomethylamine.

Example III Preparation of 2-sulfate 3- (3,4-dihydroisoquinolinium) -butane (6)

Stage one

The preparation of 3,4-dihydroisoquinoline (2) is as described in 5,576,282.

Stage 2

Preparation of cyclic 2,3-butanediol sulfate (5)

eleven

A 500 ml round bottom flask of three necks, equipped with mechanical stirrer, addition funnel with pressure equalization and reflux condenser with a tube dried full with Drierite®, loaded with 2,3-butanediol (4.51 g, 50.0 mmol) and 50 ml of carbon tetrachloride. Once dissolved the 2,3-butanediol, is added dropwise chloride of thionyl (5.5 ml, 75 mmol) at room temperature and the reaction is heats to approximately 60 ° C. After two hours, the reaction cool slowly to about 0 ° C. Water is added deionized (50 ml) and acetonitrile (75 ml). Chloride is added hydrated ruthenium (0.13 g, 0.50 mmol) and sodium periodate (21.4 g, 100 mmol) and the reaction mixture is stirred at room temperature for 1 h. The mixture is extracted with diethyl ether (4 x 175 ml), the organic residue is washed with deionized water (5 x 100 ml), saturated sodium bicarbonate solution (3 x 100 ml) and brine (2 x 100 ml) and then filtered through celite / silica gel. He filtered is dried over magnesium sulfate, filtered and concentrated by rotary evaporation until an oil is obtained transparent.

Stage 3

Preparation of 2-sulfate 3- (3,4-dihydroisoquinolinium) -butane (6)

12

A 100 ml round bottom flask equipped with magnetic stirrer is charged with 3,4-dihydroisoquinoline (2.02 g, 15.4 mmol) and acetonitrile (15.2 ml). To the mixture is added once sulfate 2,3-cyclic butanediol (2.43 g, 16.0 mmol). One time thickened the reaction mixture, an additional amount of acetonitrile (60 ml) and the mixture is stirred overnight. Be collect the precipitate, wash five times with acetone and leave air dry

Example IV

(Not included in the scope of claim one)

Preparation of 1-sulfate 3- (3,4-dihydroisoquinolinium) -propane (8)

13

A 100 ml round bottom flask equipped with magnetic stirrer is charged with 3,4-dihydroisoquinoline (2.02 g, 15.4 mmol) and acetonitrile (15.2 ml). To the mixture is added once sulfate 1,3-cyclic propanediol (2.21 g, 16.0 mmol). A once the reaction mixture has thickened, an additional amount is added of acetonitrile (60 ml) and the mixture is stirred overnight. Be collect the precipitate, wash five times with acetone and leave air dry

The following examples are included to illustrate the compositions of the present invention although they do not limit or otherwise necessarily define the scope of the invention.

In the following examples some are used abbreviations known to the person skilled in the art, according with the description of this report.

Example V Granulated dishwasher composition

Component TO B C Acid citric 15.0 - - Citrate 4.0 29.0 15.0 Copolymer from acrylate / methacrylate 6.0 - 6.0 Copolymer Acrylic Acid / Acid maleic - 3.7 - Carbonate for addition in dry 9.0 - 20.0 Silicate metal alkaline 8.5 17.0 9.0 Paraffin - 0.5 - Benzotriazole - 0.3 - Amylase 1.6 1.6 1.6 Protease 0.2 0.1 0.06 Percarbonate (AvO) 1.5 - - Perborate monohydrate - 0.3 1.5 Perborate tetrahydrate - 0.9 - NOBS - - 2.40 TAED 3.8 4.4 - Catalyst organic 0.2 one 0.005 Acid diethylenetriamine-pentamethylphosphonic (salt of mg) 0.13 0.13 0.13 Alkylethoxysulfate - 3 times ethoxylated 3.0 - - Surfactant nonionic alkyl ethoxy propoxy - 1.5 - Suppressor of the suds 2.0 - - Surfactant non-ionic Olin SLF 18 - - 2.0 Sulfate (rest up to 100%)

Example VI High density compact detergent compositions (0.96 kg / l) A-F for dishwashing according to the invention

Component TO B C D AND F STPP - 51.4 51.4 - - 44.3 Citrate 17.05 - - 49.6 40.2 - Carbonate 17.50 14.0 20.0 8.0 33.6 Baking soda - - - 26.0 - - Silicate 14.81 15.0 8.0 - 25.0 3.6 Metasilicate 2.50 4,5 4,5 - - - PB1 9.74 7.79 7.79 - - - PB4 - - - 9.6 - - Percarbonate - - - - 11.8 4.8 Do not ionic 2.00 1.50 1.50 2.6 1.9 5.9

(Continuation)

Component TO B C D AND F TAED 2.39 - - 3.8 - 1.4 HEDP 1.00 - - - - - DETPMP 0.65 - - - - - Mn TACN - - - - 0.008 - NOBS - 2.40 - - - - PAAC - - 0.008 - - - Catalyst organic 0.0001 0.01 0.6 3 one 2 Paraffin 0.50 0.38 0.38 0.6 - - Protease 0.1 0.06 0.05 0.03 0.07 0.01 Amylase 1.5 1.5 1.5 2.6 2.1 0.8 BTA 0.30 0.22 0.22 0.3 0.3 0.3 Polycarboxylate 6.0 - - - 4.2 0.9 Fragrance 0.2 0.12 0.12 0.2 0.2 0.2 Sulfate / Water 20.57 1.97 2.97 3.6 4,5 3.9 pH (solution to one%) 11.0 11.0 11.3 9.6 10.8 10.9

Example VII Examples A-F of detergent compositions dishwashing granules with an apparent density of 1.02 kg / l according to the invention

Component TO B C D AND F STPP 30.00 33.5 27.9 29.62 33.8 22.0 Carbonate 30.50 30.50 30.5 23.00 34.5 45.0 Silicate 7.40 7.50 12.6 13.3 3.2 6.2 Metasilicate - 4,5 Percarbonate - - - 4.0 PB1 4.4 4,5 4.3 - - NaDCC - - 2.00 - 0.9 Do not ionic 1.0 0.75 1.0 1.90 0.7 0.5 TAED 1.00 - - - NOBS - - - - 2.0 - PAAC - 0.004 - - Catalyst organic 0.05 0.00001 10 7 5 0.8

(Continuation)

Component TO B C D AND F Paraffin 0.25 0.25 - - Protease 0.05 0.06 0.025 0.1 0.02 0.07 Amylase 0.38 0.64 0.46 - 0.6 BTA 0.15 0.15 - 0.2 Fragrance 0.2 0.2 0.05 0.1 0.2 Sulfate / water 23.45 16.87 22.26 30.08 21.7 25.4 pH (solution to one%) 10.80 11.3 11.0 10.70 11.5 10.9

Example VIII

Detergent tablet compositions of A-H examples according to the present invention are they prepare by compressing a granulated detergent composition to dishwashing at a pressure of 13 KN / cm2 in a press 12-head standard rotary:

Component TO B C D AND F G H STPP - 48.8 54.7 38.2 - 52.4 56.1 36.0 Citrate 20.0 - - - 35.9 - - - Carbonate 20.0 5.0 14.0 15.4 8.0 23.0 20.0 28.0 Silicate 15.0 14.8 15.0 12.6 23.4 2.9 4.3 4.2 Protease 0.05 0.09 0.05 0.03 0.06 0.03 0.03 0.1 Amylase 1.5 1.5 1.5 0.85 1.9 0.4 2.1 0.3 PB1 14.3 7.8 11.7 12.2 - - 6.7 8.5 PB4 - - - - 22.8 - 3.4 - Percarbonate - - - - - 10.4 - - Do not ionic 1.5 2.0 2.0 2.2 1.0 4.2 4.0 6.5 PAAC - - 0.016 0.009 - - - - MnTACN - - - - 0.007 - - - TAED 2.7 2.4 - - - 2.1 0.7 1.6 Catalyst organic one 1.4 5 0.7 0.02 one 2 0.4 HEDP 1.0 - - 0.93 - 0.4 0.2 - DETPMP 0.7 - - - - - - - Paraffin 0.4 0.5 0.5 0.55 - - 0.5 - BTA 0.2 0.3 0.3 0.33 0.3 0.3 0.3 - Polycarboxylate 4.0 - - - 4.9 0.6 0.8 -

(Continuation)

Component TO B C D AND F G H PEG - - - - - 2.0 - 2.0 Glycerol - - - - - 0.4 - 0.5 Fragrance - - - 0.05 0.20 0.2 0.2 0.2 Sulfate / water 17.4 14.7 - 15.74 - - - 11.3 Tablet weight 20 g 25 g 20 g 30 g 18g 20 g 25 g 24.0 pH (solution to one%) 10.7 10.60 10.7 10.7 10.9 11.2 11.0 10.8

Example IX Granulated compositions for tissue cleaning

Components Example no. TO B Alkylbenzenesulfonate linear 11.4 10.70 Alkylsulfate tallow 1.80 2.40 Rent C_ {14-15} sulfate 3.00 3.10 Alcohol C_ {14-15}, 7 times ethoxylated 4.00 4.00 Alcohol of tallow, 11 times ethoxylated 1.80 1.80 Dispersant 0.07 0.1 Silicone fluid 0.80 0.80 Citrate trisodium 14.00 15.00 Acid citric 3.00 2.50 Zeolite 32.50 32.10 Copolymer of maleic acid / acid acrylic 5.00 5.00 Acid diethylenetriamine-pentamethylenephosphonic 1.00 0.20 Protease 0.1 0.01 Lipase 0.36 0.40 Amylase 0.30 0.30 Silicate sodium 2.00 2.50 Sulfate sodium 3.50 5.20 Polyvinylpyrrolidone 0.30 0.50 Perborate 0.5 one TAED 1.0 - NOBS - 1.0 Catalyst organic 0.1 one Phenolsulfonate 0.1 - Peroxidase 0.1 0.1 Components minorities up to 100 until the 100

Example X Granulated compositions for tissue cleaning

Components Example no. TO B Rent C 12 sodium benzene sulphonate linear 6.5 8.0 Sulfate sodium 15.0 18.0 Zeolite TO 26.0 22.0 Nitrilotriacetate sodium 5.0 5.0 Polyvinylpyrrolidone 0.5 0.7 TAED 3.0 - NOBS - 2.4 Catalyst organic one 0.5 Acid boric 4.0 - Perborate 0.5 one Phenolsulfonate 0.1 - Protease 0.02 0.05 Loads (silicates; carbonates; perfumes; water, etc.) until the 100 up to 100

Example XI Compact granulated compositions for cleaning woven

Components % in weight Alkylsulfate 8.0 Alkylethoxysulfate 2.0 Mixture of alcohols C25 and C45, 3 and 7 times ethoxylated 6.0 Polyhydroxyamide from acid fatty 2.5 Zeolite 17.0 Silicate laminar / citrate 16.0 Carbonate 7.0 Copolymer of maleic acid / acid acrylic 5.0 Polymer for release of the dirt 0.4 Carboxymethyl cellulose 0.4 N-oxide poly (4-vinylpyridine) 0.1 Copolymer of vinylimidazole and vinyl pyrrolidone 0.1 PEG2000 0.2 Protease 0.03 Lipase 0.2 Cellulase 0.2 TAED 6.0 Percarbonate 22.0 Catalyst organic 0.1 Acid ethylenediamine disuccinic 0.3 Suppressor of the suds 3.5 2,2'-disulfonate disodium of 4,4'-bis (2-morpholino-4-anilin-s-triacin-6-ylamino) stilbene 0.25 4,4'-bis (2-sulfoestyryl) biphenyl disodium 0.05 Water, perfume and minority components until The 100

Example XII Granulated compositions for tissue cleaning

Component % in weight Alkylbenzenesulfonate linear 7.6 Rent C_ {16} -C_ {18} sulfate 1.3 Alcohol C_ {14-15}, 7 times ethoxylated 4.0 Chloride coco-alkyl-dimethyl-hydroxyethylammonium 1.4 Dispersant 0.07 Silicone fluid 0.8 Citrate trisodium 5.0 Zeolite 4A 15.0 Acid copolymer maleic / acrylic acid 4.0 Acid diethylenetriamine-pentamethylenephosphonic 0.4 Perborate 15.0 TAED 5.0 Catalyst organic 2 Clay kind smectite 10.0 Poly (oxy ethylene) (Pm 300,000) 0.3 Protease 0.02 Lipase 0.2 Amylase 0.3 Cellulase 0.2 Silicate sodium 3.0 Carbonate sodium 10.0 Carboxymethyl cellulose 0.2 Brighteners 0.2 Water, perfume and minor components up to 100

Example XIII Granulated compositions for tissue cleaning

Component % in weight Alkylbenzenesulfonate linear 6.92 Alkylsulfate tallow 2.05 Alcohol C_ {14-15}, 7 times ethoxylated 4.4 Rent C 12-15 ethoxy sulfate, 3 times ethoxylated 0.16 Zeolite 20.2 Citrate 5.5 Carbonate 15.4 Silicate 3.0 Copolymer of maleic acid / acid acrylic 4.0 Carboxymethyl cellulase 0.31 Polymer for release of the dirt 0.30 Protease 0.1 Lipase 0.36 Cellulase 0.13 Perborate tetrahydrate 11.64 Perborate monohydrate 8.7 TAED 5.0

(Continuation)

Component % in weight Catalyst organic 0.05 Acid diethylenetriamine-pentamethylphosphonic 0.38 Sulfate from magnesium 0.40 Rinse aid 0.19 Fragrance, silicone suppressors suds 0.85 Components minorities until the 100

Example XIV Granulated compositions for tissue cleaning

Component TO B C Components of granule base  \ hskip0,5cm LAS / AS / AES (65/35) 9.95 - -  \ hskip0,5cm LAS / AS / AES (70/30) - 12.05 7.70  \ hskip0,5cm Aluminosilicate 14.06 15.74 17.10  \ hskip0,5cm Carbonate sodium 11.86 12.74 13.07  \ hskip0,5cm Silicate sodium 0.58 0.58 0.58  \ hskip0,5cm NaPAA solids 2.26 2.26 1.47  \ hskip0,5cm PEG solids 1.01 1.12 0.66  \ hskip0,5cm Brighteners 0.17 0.17 0.11  \ hskip0,5cm DTPA - - 0.70  \ hskip0,5cm Sulfate 5.46 6.64 4.25  \ hskip0,5cm DC-1400 Deaerant 0.02 0.02 0.02  \ hskip0,5cm Humidity 3.73 3.98 4.33  \ hskip0,5cm Components minorities 0.31 0.49 0.31 B.O.T. pulverized  \ hskip0,5cm Surfactant no ionic 0.50 0.50 0.50  \ hskip0,5cm Components agglomerates  \ hskip0,5cm LAS / AS (25/75) 11.70 9.60 10.47  \ hskip0,5cm Aluminosilicate 13.73 11.26 12.28  \ hskip0,5cm Carbonate 8.11 6.66 7.26  \ hskip0,5cm PEG 4000 0.59 0.48 0.52  \ hskip0,5cm Humidity / Components minorities 4.88 4.00 4.36 Additives functional  \ hskip0,5cm Carbonate sodium 7.37 6.98 7.45  \ hskip0,5cm Perborate 1.03 1.03 2.56  \ hskip0,5cm Base coating AC - 1.00 -  \ hskip0,5cm NOBS - - 2.40 Catalyst organic one 0.001 0.01  \ hskip0,5cm Polymer for the release of the dirt 0.41 0.41 0.31  \ hskip0,5cm Cellulase 0.33 0.33 0.24  \ hskip0,5cm Protease 0.1 0.05 0.15  \ hskip0,5cm Flake AE 0.40 0.40 0.29 Liquid pulverized  \ hskip0,5cm Fragrance 0.42 0.42 0.42  \ hskip0,5cm Nonionic Surfactant pulverized 1.00 1.00 0.50  \ hskip0,5cm Minority components until the 100

Example XV Granulated compositions for tissue cleaning

TO B Surfactant  \ hskip0,5cm - Na THE 6.40 -  \ hskip0,5cm - KLAS - 9.90  \ hskip0,5cm - AS / AE3S 6.40 4.39  \ hskip0,5cm - TAS 0.08 0.11  \ hskip0,5cm - C24AE5 3.48 -  \ hskip0,5cm - Genagen - 1.88  \ hskip0,5cm - N-cocoyl N-methyl glucamine (lin) 1.14 2.82  \ hskip0,5cm - C 8-10 dimethyl chloride hydroxyethylammonium 1.00 1.40 Strengthening Additive detergency  \ hskip0,5cm - Zeolite 20.59 13.39  \ hskip0,5cm - SKS-6 10.84 10.78  \ hskip0,5cm - Citric acid 2.00 - Tampon  \ hskip0,5cm - Carbonate 9.60 12.07  \ hskip0,5cm - Baking soda 2.00 2.00  \ hskip0,5cm - Sulfate 2.64 -  \ hskip0,5cm - Silicate 0.61 0.16 Polymer  \ hskip0,5cm - Acrylic acid / maleic acid copolymer (Na) 1.17 1.12  \ hskip0,5cm - CMC 0.45 0.24  \ hskip0,5cm - Polymer 0.34 0.18  \ hskip0,5cm - Hexamethylene diaminotetra-E24 ethoxylated, diuaternized with chloride methyl 1.00 1.00 Enzyme  \ hskip0,5cm - Protease (% enzyme pure) 0.03 0.03  \ hskip0,5cm - Cellulase 0.26 0.26  \ hskip0,5cm - Amylase 0.65 0.73  \ hskip0,5cm - Lipasa 0.27 0.15 Bleaching  \ hskip0,5cm - TAED (100%) 3.85 3.50  \ hskip0,5cm - N- acid phenolsulfonate ester nonanoyl-6-aminocaproic acid - 2.75  \ hskip0,5cm - Percarbonate 16.20 18.30  \ hskip0,5cm - Catalyst organic 0.0005 3  \ hskip0,5cm - HEDP 0.48 0.48  \ hskip0,5cm - EDDS 0.30 0.30 Others  \ hskip0,5cm - Malic particle 2.20 + bicarb  \ hskip0,5cm - Brightener 15/49 0.077 / 0.014 0.07 / 0.014  \ hskip0,5cm - Phthalocyaninesulfonate of zinc 0.0026 0.0026  \ hskip0,5cm - Polydimethylsiloxane with terminal protection units trimethylsilyl 0.25 0.24  \ hskip0,5cm - Soap - 1.00  \ hskip0,5cm - Fragrance 0.45 0.55 Total 100 100

Example XVI

Granulated compositions for cleaning woven TO B Surfactant  \ hskip0,5cm Nalas 6.8 0.4  \ hskip0,5cm KLAS - 10.9  \ hskip0,5cm FAS 0.9 0.1  \ hskip0,5cm ACE 0.6 1.5  \ hskip0,5cm C25AE3S 0.1 -  \ hskip0,5cm AE5 4.2 -  \ hskip0,5cm N-cocoyl-N-methyl glucamine - 1.8  \ hskip0,5cm Genagen - 1.2  \ hskip0,5cm C 8-10 dimethyl hydroxyethyl chloride ammonium - 1.0 Additive reinforcer of the detergency  \ hskip0,5cm SKS-6 3.3 9.0  \ hskip0,5cm Zeolite 17.2 18.9  \ hskip0,5cm Citric acid 1.5 - Tampon  \ hskip0,5cm Carbonate 21.1 15.0  \ hskip0,5cm Baking soda sodium - 2.6  \ hskip0,5cm Sulfate 15.2 5.5  \ hskip0,5cm Acid Malic - 2.9  \ hskip0,5cm Silicate 0.1 - Polymer  \ hskip0,5cm Acrylic acid / maleic acid copolymer (Na) 2.2 0.9  \ hskip0,5cm Hexamethylene diaminotetra-E24 ethoxylated, diuaternized with chloride methyl 0.5 0.7  \ hskip0,5cm Polymer 0.1 0.1  \ hskip0,5cm CMC 0.2 0.1 Enzymes  \ hskip0,5cm Protease (% enzyme pure) 0.02 0.05  \ hskip0,5cm Lipase 0.18 0.14  \ hskip0,5cm Amylase 0.64 0.73  \ hskip0,5cm Cellulase 0.13 0.26 Bleach  \ hskip0,5cm TAED 2.2 2.5  \ hskip0,5cm Acid phenolsulfonate ester N-nonanoyl-6-aminocaproic acid - 1.96  \ hskip0,5cm Percarbonate sodium - 13.1  \ hskip0,5cm PB4 15.6 - Catalyst organic one 0.5  \ hskip0,5cm EDDS 0.17 0.21  \ hskip0,5cm MgSO4 0.35 0.47  \ hskip0,5cm HEDP 0.15 0.34 Rinse aid 0.06 0.04  \ hskip0,5cm Phthalocyaninosulfonate of zinc 0.0015 0.0020  \ hskip0,5cm Polydimethylsiloxane with terminal protection units trimethylsilyl 0.04 0.14  \ hskip0,5cm Soap 0.5 0.7  \ hskip0,5cm Fragrance 0.35 0.45  \ hskip0,5cm Mottled compound 0.5 0.6

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Example XVII

Granulated detergent compositions for laundry XVII A-C in accordance with this invention are of particular utility in the European conditions of machine wash:

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Component TO B C THE 7.0 5.61 4.76 TAS - - 1.57 C45AS 6.0 2.24 3.89 C25E3S 1.0 0.76 1.18 C45E7 - - 2.0 C25E3 4.0 5.5 - QAS 0.8 2.0 2.0 STPP - - - Zeolite TO 25.0 19.5 19.5 Citric acid 2.0 2.0 2.0 NaSKS-6 8.0 10.6 10.6 Carbonate I 8.0 10.0 8.6 MA / AA 1.0 2.6 1.6 CMC 0.5 0.4 0.4 PB4 - 12.7 - Percarbonate - - 19.7 TAED - 3.1 5.0 Catalyst organic 10 0.04 3 Citrate 7.0 - - DTPMP 0.25 0.2 0.2 HEDP 0.3 0.3 0.3 QEA one 0.9 1.2 1.0 Protease 0.02 0.05 0.035 Lipase 0.15 0.25 0.15 Cellulase 0.28 0.28 0.28 Amylase 0.4 0.7 0.3 PVPI / PVNO 0.4 - 0.1 Photoactivated bleach (ppm) fifteen ppm 27 ppm 27 ppm Rinse aid one 0.08 0.19 0.19

(Continuation)

Component TO B C Rinse aid 2 - 0.04 0.04 Fragrance 0.3 0.3 0.3 Effervescent granules (40% malic acid, 40% fifteen fifteen 5 bicarbonate sodium, 20% carbonate sodium) Defoamer type silicone 0.5 2.4 2.4 Minority / inert components until 100%

Example XVIII

The formulations that follow are examples of compositions according to the invention, which may be in the form of granules or pill form.

Component 14 C45 AS / TAS 3.0 THE 8.0 C25AE3S 1.0 NaSKS-6 9.0 C25AE5 / AE3 5.0 Zeolite TO 10.0 SKS-6 (I) (dry addition) 2.0 MA / AA 2.0 Acid citric 1.5 EDDS 0.5 HEDP 0.2 PB1 10.0 NACA OBS 2.0 TAED 2.0 Catalyst organic one Carbonate 8.0 Sulfate 2.0 Amylase 0.3 Lipase 0.2 1 protease 0.02 Minority components (Brightener / SRP1 / CMC / Photoblanqueante / mgSO4 / PVPVI / 0.5 Suppressor of the soaps / PEG) Fragrance 0.5

Example XIX Liquid tissue cleaning compositions

Example no. Component TO B Acid C 12 {14-14} alkenyl succinic 3.0 8.0 Citric acid monohydrate 10.0 15.0 Rent C 12-15 sulfate sodium 8.0 8.0 Sodium sulfate C 12-15 alcohol, 2 times ethoxylated - 3.0 Alcohol C_ {12-15}, 7 times ethoxylated - 8.0 Alcohol C_ {12-15}, 5 times ethoxylated 8.0 - Diethylenetriamine-penta (acid methylene phosphonic) 0.2 - Acid oleic 1.8 - Ethanol 4.0 4.0 Propanediol 2.0 2.0 Protease 0.01 0.02 Suppressor of the suds 0.15 0.15 NaOH  \ hskip2cm up to pH 7.5 Perborate 0.5 one Catalyst organic 0.01 0.5 Phenol sulphonate 0.1 0.2 Peroxidase 0.4 0.1 Water and minority components  \ hskip2cm up to 100%

Example XX Liquid tissue cleaning compositions

Example no Component 17 Nalas (100% A.M) 16 Neodol 21.5 EDDS 1.2 Dispersant 1.3 Perborate 12 Catalyst organic 0.1 Ester acid phenolsulfonate N-nonanoyl-6-aminocaproic acid 6 Protease (% enzyme pure) 0.03 Cellulase 0.03 Solvent (BPP) 18.5 Polymer 0.1 Carbonate 10 FWA fifteen 0.2 TiO_ {2} 0.5 PEG 8000 0.4 Fragrance 1.0-1.2 Suppressor of the soaps 0.06 Water and components minorities up to 100%

Example XXI Effervescent bilayer tablet for denture cleaning fake

 \ hskip1.5cm Example nº Component TO B C D Cap acidic  \ hskip0,5cm Protease 1.0 1.5 0.01 0.05  \ hskip0,5cm Acid tartaric 24.0 24.0 24.00 24.00  \ hskip0,5cm Carbonate sodium 4.0 4.0 4.00 4.00  \ hskip0,5cm Acid sulfamic 10.0 10.0 10.00 10.00  \ hskip0,5cm PEG 20,000 4.0 4.0 4.00 4.00  \ hskip0,5cm Baking soda sodium 24.5 24.5 24.50 24.50  \ hskip0,5cm Persulfate potassium 15.0 15.0 15.00 15.00  \ hskip0,5cm Acid pyrophosphate sodium 7.0 7.0 7.00 7.00  \ hskip0,5cm Silica pyrogenic 2.0 2.0 2.00 2.00  \ hskip0,5cm Tetracetylethylene diamine 7.0 7.0 7.00 7.00  \ hskip0,5cm Taste 1.0 1.0 1.00 1.00 Cap alkaline  \ hskip0,5cm Sodium perborate monohydrate 32.0 32.0 32.00 32.00  \ hskip0,5cm Catalyst organic one 0.05 0.5 2  \ hskip0,5cm Baking soda sodium 19.0 19.0 19.00 19.00  \ hskip0,5cm EDTA 3.0 3.0 3.00 3.00  \ hskip0,5cm Tripolyphosphate sodium 12.0 12.0 12.00 12.00  \ hskip0,5cm PEG 20,000 2.0 2.0 2.00 2.00  \ hskip0,5cm Carbonate sodium 2.0 2.0 2.00 2.00  \ hskip0,5cm Silica pyrogenic 2.0 2.0 2.00 2.00  \ hskip0,5cm Dye / taste 2.0 2.0 2.00 2.00

Example XXII

Granulated detergent compositions for laundry XXII A-E are of particular utility under Japanese machine wash conditions and are prepared from according to the invention:

Component TO B C D AND THE 23.57 23.57 21.67 21.68 21.68 FAS 4.16 4.16 3.83 3.83 3.83 Surfactant no ionic 3.30 3.30 2.94 3.27 3.27 Chloride bis (hydroxyethyl) methyl alkylammonium 0.47 0.47 1.20 1.20 1.20 SKS-6 7.50 7.50 5.17 5.76 5.06 Polyacrylate Copolymer (Pm 11000) 7.03 7.03 14.36 14.36 14.36 (relationship Maleic: Acrylate 4: 6) Zeolite 11.90 11.40 10.69 11.34 11.34 Carbonate 14.90 14.82 11.71 11.18 11.18 Silicate 12.00 12.00 12.37 12.38 12.38 Protease 0.016 0.016 0.046 0.046 0.046

(Continuation)

Component TO B C D AND Lipase - - 0.28 - - Amylase - - 0.62 - - Cellulase - - 0.48 - 0.70 NOBS 3.75 3.75 2.70 2.70 2.70 PB1 3.53 - 2.60 - - Percarbonate sodium - 4.21 - 3.16 3.16 Catalyst organic 0.1 0.01 2 5 0.5 SRP 0.52 0.52 0.70 0.70 0.70 Rinse aid 0.31 0.31 0.28 0.28 0.50 Co-snowflake AE 0.17 0.20 0.17 0.17 0.17 Polydimethylsiloxane - - 0.68 0.68 0.68 Fragrance 0.06 0.06 0.08 - - Fragrance - - - 0.23 0.23 Hydrophobic silica hasty 0.30 0.30 0.30 0.30 0.30 PEG4000 0.19 0.19 0.17 0.17 0.17 Minority / inert components until 100%

Example XXIII

The bleaching detergent compositions that they have the form of granulated laundry detergents Illustrated by the following formulations:

TO B C D AND Catalyst organic 0.05 0.01 0.13 0.04 0.07 Activator conventional (NOBS) 0.00 2.00 1.20 0.70 0.00 Activator conventional (TAED) 3.00 0.00 2.00 0.00 0.00 Activator conventional (NACA-OBS) 3.00 0.00 0.00 0.00 2.20 Percarbonate sodium 5.30 0.00 0.00 4.00 0.00 Perborate sodium monohydrate 0.00 5.30 3.60 0.00 4.30 Alkylbenzenesulfonate linear 12.00 0.00 12.00 0.00 21.00 C45AE0.6S 0.00 15.00 0.00 15.00 0.00 N-oxide dimethyl C2 amine 0.00 2.00 0.00 2.00 0.00 C12 amidopropyl betaine from coconut 1.50 0.00 1.50 0.00 0.00 N-methyl glucamide of palm 1.70 2.00 1.70 2.00 0.00 Chloride C12 dimethylhydroxyethyl ammonium 1.50 0.00 1.50 0.00 0.00 AE23-6.5T 2.50 3.50 2.50 3.50 1.00 C25E3S 4.00 0.00 4.00 0.00 0.00 Tripolyphosphate sodium 25.00 25.00 15.00 15.00 25.00 Zeolite TO 0.00 0.00 0.00 0.00 0.00

(Continuation)

TO B C D AND Copolymer Acrylic Acid / Acid maleic 0.00 0.00 0.00 0.00 1.00 Acid polyacrylic, partially neutralized 3.00 3.00 3.00 3.00 0.00 Agent to release the dirt 0.00 0.00 0.50 0.40 0.00 Carboxymethyl cellulose 0.40 0.40 0.40 0.40 0.40 Carbonate sodium 2.00 2.00 2.00 0.00 8.00 Silicate sodium 3.00 3.00 3.00 3.00 6.00 Baking soda sodium 5.00 5.00 5.00 5.00 5.00 Savinase (4T) 1.00 1.00 1.00 1.00 0.60 Termamyl (60T) 0.40 0.40 0.40 0.40 0.40 Lipolase (100T) 0.12 0.12 0.12 0.12 0.12 Carezyme (5T) 0.15 0.15 0.15 0.15 0.15 Dietilentriaminpenta (acid methylene phosphonic) 1.60 1.60 1.60 1.60 0.40 Rinse aid 0.20 0.20 0.20 0.05 0.20 Photo whitening from kind 0.50 0.00 0.25 0.00 0.00 phthalocyanine zinc sulphonated MgSO4 2.20 2.20 2.20 2.20 0.64 Na_ {SO} {4} Rest Rest Rest Rest Rest

Any of the compositions are used above to wash fabrics at a concentration of 3,500 ppm in water, 25ºC, and with a water: clothes ratio of 15: 1. The typical pH is approximately 9.5 but can be adjusted by changing the proportion between the acid and the sodium salt of the alkylbenzenesulfonate.

Example XXIV

The bleaching detergent compositions that they have the form of granulated laundry detergents Illustrated by the following formulations:

TO B C D AND Catalyst organic 0.06 0.34 0.14 0.14 0.20 Percarbonate sodium 5.30 0.00 0.00 0.00 0.00 Perborate sodium monohydrate 0.00 9.00 17.60 9.00 9.00 Alkylbenzenesulfonate linear 21.00 12.00 0.00 12.00 12.00 C45AE0.6S 0.00 0.00 15.00 0.00 0.00 N-oxide dimethyl C2 amine 0.00 0.00 2.00 0.00 0.00 C12 amidopropyl betaine from coconut 0.00 1.50 0.00 1.50 1.50 N-methyl glucamide of palm 0.00 1.70 2.00 1.70 1.70 Chloride C12 dimethylhydroxyethyl ammonium 1.00 1.50 0.00 1.50 1.50 AE23-6.5T 0.00 2.50 3.50 2.50 2.50 C25E3S 0.00 4.00 0.00 4.00 4.00 Activator conventional (NOBS) 0.00 0.00 0.00 1.00 0.00 Activator conventional (TAED) 1.80 1.00 2.50 3.00 1.00 Tripolyphosphate sodium 25.00 15.00 25.00 15.00 15.00 Zeolite TO 0.00 0.00 0.00 0.00 0.00 Copolymer Acrylic Acid / Acid maleic 0.00 0.00 0.00 0.00 0.00 Acid polyacrylic, partially neutralized 0.00 3.00 3.00 3.00 3.00 Agent to release the dirt 0.30 0.50 0.00 0.50 0.50 Carboxymethyl cellulose 0.00 0.40 0.40 0.40 0.40 Carbonate sodium 0.00 2.00 2.00 2.00 2.00 Silicate sodium 6.00 3.00 3.00 3.00 3.00 Baking soda sodium 2.00 5.00 5.00 5.00 5.00 Savinase (4T) 0.60 1.00 1.00 1.00 1.00

(Continuation)

TO B C D AND Termamyl (60T) 0.40 0.40 0.40 0.40 0.40 Lipolase (100T) 0.12 0.12 0.12 0.12 0.12 Carezyme (5T) 0.15 0.15 0.15 0.15 0.15 Diethylenetriaminpenta (acid methylene phosphonic) 0.40 0.00 1.60 0.00 0.00 Rinse aid 0.20 0.30 0.20 0.30 0.30 Photo whitening zinc phthalocyanine type sulphonated 0.25 0.00 0.00 0.00 0.00 MgSO4 0.64 0.00 2.20 0.00 0.00 Na_ {SO} {4} Rest Rest Rest Rest Rest

Any of the compositions are used above to wash fabrics at a concentration of 3,500 ppm in water, 25ºC, and with a water: clothes ratio of 15: 1. The typical pH is approximately 9.5 but can be adjusted by changing the proportion between the acid and the sodium salt of alkylbenzenesulfonate.

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Example XXV

A bleaching powder detergent comprises the following ingredients:

Component % in weight Catalyst organic 0.07 TAED 2.0 Perborate sodium tetrahydrate 10 Rent C 12 benzenesulfonate linear 8 Phosphate (as sodium tripolyphosphate) 9 Carbonate sodium twenty talcum powder fifteen Rinse aid, fragrance 0.3 Chloride sodium 25 Water and components minorities Rest until 100%

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Example XXVI

A laundry pill is prepared suitable for hand washing stained fabrics by conventional extrusion processes and comprising the following components:

Component % in weight Catalyst organic 0.2 TAED 1.7 NOBS 0.2 Perborate sodium tetrahydrate 12 Rent C 12 benzenesulfonate linear 30 Phosphate (as tripolyphosphate sodium) 10 Carbonate sodium 5 Pyrophosphate sodium 7 Monoethanolamide from coconut 2 Zeolite A (0.1-10 micrometers) 5 Carboxymethyl cellulose 0.2 Polyacrylate (Pm 1400) 0.2 Rinse aid, fragrance 0.2

(Continuation)

Component % in weight Protease 0.3 CaSO_ {4} one MgSO4 one Water 4 Load1 Rest until 100% ^ {1} \ begin {minipage} [t] {145mm} Can be selected from materials suitable such as CaCO3, talc, clay, silicates, and Similar. Acid fillers can be used to reduce the pH. \ end {minipage}

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Example XXVII

A washing detergent composition is prepared of clothing suitable for machine use by conventional methods  and comprising the following composition:

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Component % in weight Catalyst organic 0.82 TAED 7.20 Perborate sodium tetrahydrate 9.2 Carbonate sodium 23.74 Surfactant anionic 14.80 Aluminosilicate 21.30 Silicate 1.85 Acid diethylenetriaminepentaacetic 0.43 Acid polyacrylic 2.72 Rinse aid 0.23 Polyethylene glycol solid 1.05 Sulfate 8.21 Fragrance 0.25 Water 7.72 Improver of the process 0.10 Others 0.43

The composition is used to wash fabrics to a solution concentration of approximately 1,000 ppm at a temperature of 20-40ºC and with a ratio water: approximately 20: 1 fabric.

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Example XXVIII

Component % in weight Catalyst organic 1.0 TAED 10.0 Perborate sodium tetrahydrate 8.0 Carbonate sodium 21.0 Surfactant anionic 12.0 Aluminosilicate 18.0 Acid diethylenetriaminepentaacetic 0.3 Surfactant nonionic 0.5

(Continuation)

Component % in weight Acid polyacrylic 2.0 Rinse aid 0.3 Sulfate 17.0 Fragrance 0.25 Water 6.7 Others 2.95

XXIX example

A bleaching composition suitable for use in geographical areas with phosphates of high formation of soaps with the formula:

Component TO (% in weigh) B (% in weight) Catalyst organic 0.02 0.018 NOBS 1.90 2.00 Perborate sodium tetrahydrate 2.25 3.00 Carbonate sodium 13.00 13.00 Surfactant anionic 19.00 19.00 Surfactant cationic 0.60 0.60 Surfactant no ionic - 0.40 Tripolyphosphate sodium 22.50 22.50 Acid diethylenetriaminepentaacetic 0.90 0.90 Copolymer Acrylic Acid / Acid maleic 0.90 0.90 Carboxymethyl cellulose 0.40 0.40 Protease 0.70 0.70 Amylase 0.36 0.36 Cellulase 0.35 0.35 Rinse aid 0.16 0.18 Sulfate from magnesium 0.70 0.70 Water 3.0 1.0 Sulfate sodium Rest Rest

The composition is used as a substance laundry aid for washing fabrics at a concentration in solution of approximately 850 ppm at a temperature of 5-50ºC and with a water: tissue ratio approximately 20: 1.

The compositions of the present invention may prepare properly through any process chosen by the formulator, non-limiting examples of which are described in US Patents 5,691,297; US 5,574,005; US 5,569,645; US 5,565,422; US 5,516,448; US 5,489,392; and US-5,486,303.

In addition to the previous examples, the bleaching compositions of the present invention may be formulated in any laundry detergent composition adequate, non-limiting examples of which are described in the US Patents 5,679,630; US 5,565,145; US 5,478,489; US 5,470,507; US 5,466,802; US 5,460,752; US 5,458,810; US 5,458,809; Y US 5,288,431.

<110> The Procter & Gamble Company

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Dykstra, Robert

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Dykstra, Robert

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Weed, Penny

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Weed, Penny

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<120> Components of the formulation Stable, compositions and methods of laundry

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<130> 7752M

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<151> 1999-08-27

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<170> PatentIn version 3.0

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         \ vskip1.000000 \ baselineskip
      

         \ vskip0.400000 \ baselineskip
      

<210> 4

         \ vskip0.400000 \ baselineskip
      

<211> 20

         \ vskip0.400000 \ baselineskip
      

<212> DNA

         \ vskip0.400000 \ baselineskip
      

<213> Aspergillus aculeatus

         \ vskip1.000000 \ baselineskip
      

         \ vskip0.400000 \ baselineskip
      

<400> 4

         \ vskip1.000000 \ baselineskip
      

         \ vskip0.400000 \ baselineskip
      

\hskip-.1em\dddseqskip

cttccttacc tcaccatcat

\hfill

20

 \ hskip-.1em \ dddseqskip 

cttccttacc tcaccatcat

 \ hfill 

twenty

         \ vskip1.000000 \ baselineskip
      

         \ vskip0.400000 \ baselineskip
      

<210> 5

         \ vskip0.400000 \ baselineskip
      

<211> 20

         \ vskip0.400000 \ baselineskip
      

<212> DNA

         \ vskip0.400000 \ baselineskip
      

<213> Aspergillus aculeatus

         \ vskip1.000000 \ baselineskip
      

         \ vskip0.400000 \ baselineskip
      

<400> 5

         \ vskip1.000000 \ baselineskip
      

         \ vskip0.400000 \ baselineskip
      

\hskip-.1em\dddseqskip

ttaacatctt ttcaccatga

\hfill

20

 \ hskip-.1em \ dddseqskip 

ttaacatctt ttcaccatga

 \ hfill 

twenty

         \ vskip1.000000 \ baselineskip
      

         \ vskip0.400000 \ baselineskip
      

<210> 6

         \ vskip0.400000 \ baselineskip
      

<211> 20

         \ vskip0.400000 \ baselineskip
      

<212> DNA

         \ vskip0.400000 \ baselineskip
      

<213> Aspergillus aculeatus

         \ vskip1.000000 \ baselineskip
      

         \ vskip0.400000 \ baselineskip
      

<400> 6

         \ vskip1.000000 \ baselineskip
      

         \ vskip0.400000 \ baselineskip
      

\hskip-.1em\dddseqskip

agctttccct tctctccctt

\hfill

20

 \ hskip-.1em \ dddseqskip 

agctttccct tctctccctt

 \ hfill 

twenty

         \ vskip1.000000 \ baselineskip
      

         \ vskip0.400000 \ baselineskip
      

<210> 7

         \ vskip0.400000 \ baselineskip
      

<211> 28

         \ vskip0.400000 \ baselineskip
      

<212> DNA

         \ vskip0.400000 \ baselineskip
      

<213> Aspergillus aculeatus

         \ vskip1.000000 \ baselineskip
      

         \ vskip0.400000 \ baselineskip
      

<400> 7

         \ vskip1.000000 \ baselineskip
      

         \ vskip0.400000 \ baselineskip
      

\hskip-.1em\dddseqskip

gccaccctgg cttccgctgc cagcctcc

\hfill

28

 \ hskip-.1em \ dddseqskip 

gccaccctgg cttccgctgc cagcctcc

 \ hfill 

28

         \ vskip1.000000 \ baselineskip
      

         \ vskip0.400000 \ baselineskip
      

<210> 8

         \ vskip0.400000 \ baselineskip
      

<211> 20

         \ vskip0.400000 \ baselineskip
      

<212> DNA

         \ vskip0.400000 \ baselineskip
      

<213> Aspergillus aculeatus

         \ vskip1.000000 \ baselineskip
      

         \ vskip0.400000 \ baselineskip
      

<400> 8

         \ vskip1.000000 \ baselineskip
      

         \ vskip0.400000 \ baselineskip
      

\hskip-.1em\dddseqskip

gacagtagca atccagcatt

\hfill

20

 \ hskip-.1em \ dddseqskip 

gacagtagca atccagcatt

 \ hfill 

twenty

         \ vskip1.000000 \ baselineskip
      

         \ vskip0.400000 \ baselineskip
      

<210> 9

         \ vskip0.400000 \ baselineskip
      

<211> 20

         \ vskip0.400000 \ baselineskip
      

<212> DNA

         \ vskip0.400000 \ baselineskip
      

<213> Aspergillus aculeatus

         \ vskip1.000000 \ baselineskip
      

         \ vskip0.400000 \ baselineskip
      

<400> 9

         \ vskip1.000000 \ baselineskip
      

         \ vskip0.400000 \ baselineskip
      

\hskip-.1em\dddseqskip

agcatcagcc gctttgtaca

\hfill

20

 \ hskip-.1em \ dddseqskip 

agcatcagcc gctttgtaca

 \ hfill 

twenty

         \ vskip1.000000 \ baselineskip
      

         \ vskip0.400000 \ baselineskip
      

<210> 10

         \ vskip0.400000 \ baselineskip
      

<211> 20

         \ vskip0.400000 \ baselineskip
      

<212> DNA

         \ vskip0.400000 \ baselineskip
      

<213> Aspergillus aculeatus

         \ vskip1.000000 \ baselineskip
      

         \ vskip0.400000 \ baselineskip
      

<400> 10

         \ vskip1.000000 \ baselineskip
      

         \ vskip0.400000 \ baselineskip
      

\hskip-.1em\dddseqskip

ccatgaagtt caccgtattg

\hfill

20

 \ hskip-.1em \ dddseqskip 

ccatgaagtt caccgtattg

 \ hfill 

twenty

         \ vskip1.000000 \ baselineskip
      

         \ vskip0.400000 \ baselineskip
      

<210> 11

         \ vskip0.400000 \ baselineskip
      

<211> 20

         \ vskip0.400000 \ baselineskip
      

<212> DNA

         \ vskip0.400000 \ baselineskip
      

<213> Aspergillus aculeatus

         \ vskip1.000000 \ baselineskip
      

         \ vskip0.400000 \ baselineskip
      

<400> 11

         \ vskip1.000000 \ baselineskip
      

         \ vskip0.400000 \ baselineskip
      

\hskip-.1em\dddseqskip

gcactgcttc tctcccaggt

\hfill

20

 \ hskip-.1em \ dddseqskip 

gcactgcttc tctcccaggt

 \ hfill 

twenty

         \ vskip1.000000 \ baselineskip
      

         \ vskip0.400000 \ baselineskip
      

<210> 12

         \ vskip0.400000 \ baselineskip
      

<211> 20

         \ vskip0.400000 \ baselineskip
      

<212> DNA

         \ vskip0.400000 \ baselineskip
      

<213> Aspergillus aculeatus

         \ vskip1.000000 \ baselineskip
      

         \ vskip0.400000 \ baselineskip
      

<400> 12

         \ vskip1.000000 \ baselineskip
      

         \ vskip0.400000 \ baselineskip
      

\hskip-.1em\dddseqskip

gtgggcggcc cctcaggcaa

\hfill

20

 \ hskip-.1em \ dddseqskip 

gtgggcggcc cctcaggcaa

 \ hfill 

twenty

         \ vskip1.000000 \ baselineskip
      

         \ vskip0.400000 \ baselineskip
      

<210> 13

         \ vskip0.400000 \ baselineskip
      

<211> 20

         \ vskip0.400000 \ baselineskip
      

<212> DNA

         \ vskip0.400000 \ baselineskip
      

<213> Aspergillus aculeatus

         \ vskip1.000000 \ baselineskip
      

         \ vskip0.400000 \ baselineskip
      

<400> 13

         \ vskip1.000000 \ baselineskip
      

         \ vskip0.400000 \ baselineskip
      

\hskip-.1em\dddseqskip

acgctcctcc aattttctct

\hfill

20

 \ hskip-.1em \ dddseqskip 

acgctcctcc aattttctct

 \ hfill 

twenty

         \ vskip1.000000 \ baselineskip
      

         \ vskip0.400000 \ baselineskip
      

<210> 14

         \ vskip0.400000 \ baselineskip
      

<211> 19

         \ vskip0.400000 \ baselineskip
      

<212> DNA

         \ vskip0.400000 \ baselineskip
      

<213> Aspergillus aculeatus

         \ vskip1.000000 \ baselineskip
      

         \ vskip0.400000 \ baselineskip
      

<400> 14

         \ vskip1.000000 \ baselineskip
      

         \ vskip0.400000 \ baselineskip
      

\hskip-.1em\dddseqskip

ggctggtagt aatgagtct

\hfill

19

 \ hskip-.1em \ dddseqskip 

ggctggtagt aatgagtct

 \ hfill 

19

         \ vskip1.000000 \ baselineskip
      

         \ vskip0.400000 \ baselineskip
      

<210> 15

         \ vskip0.400000 \ baselineskip
      

<211> 20

         \ vskip0.400000 \ baselineskip
      

<212> DNA

         \ vskip0.400000 \ baselineskip
      

<213> Aspergillus aculeatus

         \ vskip1.000000 \ baselineskip
      

         \ vskip0.400000 \ baselineskip
      

<400> 15

         \ vskip1.000000 \ baselineskip
      

         \ vskip0.400000 \ baselineskip
      

\hskip-.1em\dddseqskip

ggcgcagagt ttggccaggc

\hfill

20

 \ hskip-.1em \ dddseqskip 

ggcgcagagt ttggccaggc

 \ hfill 

twenty

         \ vskip1.000000 \ baselineskip
      

         \ vskip0.400000 \ baselineskip
      

<210> 16

         \ vskip0.400000 \ baselineskip
      

<211> 21

         \ vskip0.400000 \ baselineskip
      

<212> DNA

         \ vskip0.400000 \ baselineskip
      

<213> Aspergillus aculeatus

         \ vskip1.000000 \ baselineskip
      

         \ vskip0.400000 \ baselineskip
      

<400> 16

         \ vskip1.000000 \ baselineskip
      

         \ vskip0.400000 \ baselineskip
      

\hskip-.1em\dddseqskip

caacatcccc ggtgttctgg g

\hfill

21

 \ hskip-.1em \ dddseqskip 

caacatcccc ggtgttctgg g

 \ hfill 

twenty-one

         \ vskip1.000000 \ baselineskip
      

         \ vskip0.400000 \ baselineskip
      

<210> 17

         \ vskip0.400000 \ baselineskip
      

<211> 347

         \ vskip0.400000 \ baselineskip
      

<212> DNA

         \ vskip0.400000 \ baselineskip
      

<213> Aspergillus aculeatus

         \ vskip1.000000 \ baselineskip
      

         \ vskip0.400000 \ baselineskip
      

<400> 17

14

         \ vskip1.000000 \ baselineskip
      

         \ vskip0.400000 \ baselineskip
      

<210> 18

         \ vskip0.400000 \ baselineskip
      

<211> 294

         \ vskip0.400000 \ baselineskip
      

<212> DNA

         \ vskip0.400000 \ baselineskip
      

<213> Aspergillus aculeatus

         \ vskip1.000000 \ baselineskip
      

         \ vskip0.400000 \ baselineskip
      

<400> 18

fifteen

Claims (2)

1. A bleaching composition comprising a organic catalyst compound together with or without a source of peroxygen, wherein said organic catalyst compound has a shelf life of the organic catalyst greater than or equal to 30 minutes and is a cationic organic catalyst compound that has the following formula: 16 in where 17 and wherein R 50 -R 54 are independently selected from a substituted or unsubstituted radical selected from the group consisting of H, alkyl, cycloalkyl, alkylaryl, aryl, aralkyl, heterocyclic ring radicals, linear or branched silyl, nitro, halo, cyano, alkoxy, keto and carboalkoxy, provided that any R 50 -R 54 can be attached to any other R 50 -R 54 to form part of a common ring; and when R 54 is H, R 50 -R 51 does not combine with any R 53 -R 53 to form an aromatic ring, X- is a balancing counterion of suitable charges, and v is an integer from 1 to 3, characterized in that at least one of R 50 -R 51 is not H. 2. A bleaching composition according to the claim 1, wherein neither R 50 nor R 51 are H.