MXPA02008067A

MXPA02008067A - Laundry additive sachet.

Info

Publication number: MXPA02008067A
Application number: MXPA02008067A
Authority: MX
Inventors: Duca Valerio Del
Original assignee: Procter & Gamble
Priority date: 2000-02-17
Filing date: 2001-02-13
Publication date: 2003-02-27
Also published as: CA2396931A1; JP2005507432A; CA2397241C; JP2013067802A; DE60035902T2; DE60035902D1; WO2001061099A1; EP1255807A1; ES2290059T3; AU2001218076A1; CA2397241A1; CN1401030A; BR0108441A; AR035167A1; WO2002008371A2; CN1434857A; ATE369417T1; EP1255807B1; WO2001060966A1; CN1225537C

Abstract

The present invention relates to laundry additive sachets. The sachets comprise at least two compartments and may comprise further compartments. At least one of the compartments comprises a liquid laundry additive composition.

Description

SACO PE ADF ttVO P ñÁt é iA TECHNICAL FIELD The present invention relates to the field of laundry additives designed to be used in conjunction with a conventional laundry detergent. These laundry additives are designed ^^. "normally to increase the performance of the conventional detergent." The laundry additives herein are provided in the form of a water-soluble bag 10 comprising at least two compartments.

BACKGROUND OF THE INVENTION The laundry additive products are well known in the 15 technique. Such products have been commonly used to increase the performance of conventional detergent, mainly for washing, more commonly providing an additional bleaching performance. Conventional laundry additives are in the form of powders, liquids or gels, but more recently, additives have been introduced into the market. 20 in the form of tablets. It is found that tablets are credible to the consumer because more accurate dosing is possible and overdosing or underdosing with waste is reduced. Moreover, consumers are attracted to such products in a single dose because they They are less prone to leakage or leakage. However, applicants have found that although such tablets are preferred by consumers there is still a desire for a product where the consumer does not have to be in direct contact with the ingredients of the composition. Accordingly, it is an object of the present invention to provide a unit dose laundry additive composition, wherein the user does not come into direct contact with the ingredients of the composition. The objective is met by a laundry additive bag comprising a liquid laundry additive composition. A particular problem of using a liquid composition as opposed to a particulate composition for filling the sack is that the ingredients, especially aggressive ingredients such as bleaching agents, can dissolve or damage the materials forming the sack, resulting in premature dissolution of the sack. and releasing the liquid additive composition for laundry. Additionally, some liquid ingredients may simply leak through the wall of the bag, draining the composition of the bag such that at the time of use, the amount of laundry additive composition is not the correct dose. It has also been the object of the present invention to provide an additive laundry product that provides more than one benefit. This objective is achieved by incorporating different ingredients to provide the different benefits. However it has been discovered that these ingredients They are not always compatible. In fact in some instances the ingredients react with each other so that at least one of the ingredients is completely consumed before use by the consumer. In such instances the performance of the laundry additive, of course, is adversely affected. Hence, it has been the object of the present invention to provide a laundry additive in the form of a bag comprising at least two compartments and comprising at least one liquid composition.

BRIEF DESCRIPTION OF THE INVENTION In accordance with the present invention there is provided a laundry additive bag comprising one or more liquid compositions, wherein the bag comprises two or more compartments made of film material or sheet substantially water soluble. According to a second aspect of the present invention there is provided a process for treating fabrics with a laundry additive bag according to the present invention in conjunction with a conventional laundry detergent in the presence of water. According to a further aspect of the present invention, the use of a bag of agreement GO is provided? the present invention as a laundry additive. In addition, the use of a bag according to the present invention is provided for cleaning and / or softening fabrics. Finally, the use of a bag in accordance with the present invention to hibernate and / or provide an easy ironing benefit.

DETAILED DESCRIPTION OF THE INVENTION Laundry additive bag The present invention relates to a laundry additive bag comprising one or more liquid compositions, which are described in more detail below. The bag comprises at least two compartments and is made of a film material or sheet substantially soluble in water. Sacks comprising liquid or particulate compositions have been explained in the prior art. However, the sacs were typically insoluble in such a way that they could be removed after the end of the wash, or were unsatisfactorily soluble in water. The most commonly described water soluble sacs of the prior art are made by using polyvinyl alcohol (PVA). However, bags made using PVA are sensitive to bleaching agents, so that if a composition, especially a liquid composition comprising a bleaching agent, is to be filled in the bag, the bag would degrade and break before being used. by the consumer due to the effect of the bleaching agent on the PVA. The applicants have faced This problem using particulate whitening agents, in a particulate but preferably liquid matrix. The applicants have also faced the known problem of PVA bags which gel upon contact with water. This phenomenon of gelification occurs where the outer surface of the PVA bag dissolves in water, but instead of dissipating in the surrounding water, it forms a gel surrounding the bag, preventing further dissolution in the bag. The result is that the bag does not dissolve completely, leaving sack residue on the fabrics. Applicants have discovered that using an elaborate bag using 10 a hydrophobically modified cellulose polymer for example and more preferably hydroxypropylmethylcellulose (HPMC), problems associated with PVA can be avoided. The HPMC is not only more stable to the bleach but also does not produce the phenomenon of gelling as observed with PVA and for these reasons it is preferred to prepare the bag using 15 HPMC. The bags can be prepared according to methods known in the art. More specifically, the sacks are prepared by first cutting a piece of adequate size film / támína. The sheet is ^^ fold to form the necessary number and size of compartments and 20 sealing the edges using any suitable technology, for example sealed by heat.

Active composition for laundry The bag as described above comprises at least two compartments. At least one of the compartments is filled, at least to some degree, with at least one liquid laundry additive composition. The other compartment may be filled with the same or a different liquid composition, or alternatively a particulate composition. More preferably the compartments are filled, at least to some degree, with a different composition. By the term "different composition" it means that the first and / or second composition comprises at least one 'ingredient that is not present in the other composition. In the embodiment in which the sack comprises a third or subsequent compartment, the compartment (s) may be filled to a greater degree with a third or subsequent composition which is different from any of the other compositions, for example the first or second composition , in the case where the third composition exists. In a preferred embodiment, the first composition is a liquid or particulate, preferably particulate, composition comprising ingredients selected from the group listed under Additive Ingredients for laundry. The second composition comprises a bleaching agent, different from that of the first composition if present, and is in liquid form. Bleaching agents are described in more detail below, however the bleaching agent that is preferred for use in the second composition of this embodiment is a particulate peracid.

In a still more preferred embodiment, the peracid is selected from the pre-formed monoperoxycarboxylic acid scale which is described in more detail below. In an even more preferred embodiment, the preformed peracid is phthaloyl amido peroxyhexanoic acid, known as PAP. The preformed peracid is preferably used in the form of particles, and then suspended in a liquid matrix. The liquid matrix where it is present is substantially non-aqueous which means that it does not comprise a water level that would result in the dissolution of the material forming the sack. The Applicants have found that the preferred ingredients that are used to suspend PAP (suspending agents) are solvents that do not dissolve or damage the material forming the bag over time. More preferably the suspending agent is a long chain, low polarity solvent. By long chain it means solvents comprising a carbon chain greater than 6 carbon atoms and by low polarity means a solvent having a dielectric constant of less than 40. Preferred solvents include C12-14 paraffin and more preferably isoparaffin of C12-14. The benefit of the present embodiment is the significant improvement in removal of bleachable dirt provided by the laundry additive. In an alternate and equally preferred embodiment the second composition is the same as described above, however the first composition is a fabric softening composition, comprising an ingredient that softens fabrics and also returns to the treated fabrics more easy to iron The first composition of this embodiment may be a liquid, but preferably it is in the form of particles. The softening ingredient may be present in an amount of 20% to 80% by weight of the first composition. The remaining ingredients can be selected from any of those listed under Additive Ingredients for Laundry. It is also contemplated that the preceding embodiment may be altered in such a way that the ingredient that provides performance in the first composition in place of a softening ingredient is, for example, one or more enzymes, especially carezime, an organic polymeric compound, dirt, dye transfer inhibitor, a brightener and mixtures thereof. In a further alternative embodiment it is also preferable to make a bag of laundry additive following the same structure of composition as described in the first previous embodiment, in which an additional element other than a softening ingredient, for example as defined in paragraph above, it can be added to the first, second or first and second compositions. The liquid composition of the present invention, wherein it is used to suspend a particulate component, may also comprise other structuring ingredients in order to stabilize the matrix. A structuring agent that is preferred is a combination of sodium alkylene sulfonate (LAS) and sodium sulfate which has been dehydrated to form a crystalline structure.

Fabrics treated with the compositions * of this ,. invention comprising a softening ingredient not only improve the softness of the fabrics, but also make the fabrics easier to iron.

This benefit of easy ironing is perceived as the fabrics have not only fewer wrinkles, but also the wrinkles are easier to remove for example when ironing. 0 Laundry Additive Ingredients The compositions that are used can include a variety of different ingredients including builders, surfactants, enzymes, bleaching agents, alkalinity sources, dyes, perfume, lime soap dispersants, organic polymeric compounds including agents dye transfer inhibition polymers, crystal growth inhibitors, heavy metal ion sequestrants, metal ion salts, enzyme stabilizers, corrosion inhibitors, foam suppressors, solvents, fabric softening agents, optical brighteners, and hydrotropes.

Means of detergency composition The compositions of the present invention preferably contain a builder compound, typically present at a level of 1% to 80% by weight, preferably 10% to 70% by weight. so, more preferably from 20% to 60% by weight of the composition of active detergent components.

Water-soluble detergent composition compound Suitable water-soluble builder compounds include water-soluble monomeric polycarboxylates, or their acid forms, homo- or copolymeric polycarboxylic acids or salts thereof in which the polycarboxylic acid comprises at least two separate carboxylic radicals one of the other by no more than two carbon atoms, carbonates, bicarbonates, borates, phosphates and mixtures of any of the foregoing. The carboxylate or polycarboxylate builder may be of the monomeric or oligomeric type, although monomeric polycarboxylates are generally preferred for reasons of cost and performance. Suitable carboxylates containing a carboxy group include the water soluble salts of lactic acid, glycolic acid and ether derivatives thereof. Polycarboxylates containing two carboxy groups include the water-soluble salts of succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid and fumaric acid, as well as ether carboxylates and sulfinyl carboxylates . Polycarboxylates containing three carboxy groups include, in particular, citrates, aconitrates and water-soluble citraconates, as well as the succinate derivatives such as the carboxy ethyloxysuccinates described in British Patent No. 1, 379,241, the lactoxysuccinates described in British Patent No. 1, 389,732 and aminosuccinates described in Dutch Application 7205873, and oxypolycarboxylate materials such as 5-oxa-1, 1, 3-propanedicarboxylates described in British Patent No. 1, 387,447. Polycarboxylates containing four carboxy groups include the oxydisuccinates described in British Patent No. 1, 261, 829, 1, 1, 2,2-etanttracarboxylates, 1,1, 3,3-propanetracarboxylates and the 1, 1, 2,3- 10 propanetracarboxylates. Polycarboxylates containing sulfo substituents include the sulfosuccinate derivatives described in the British patents Nos. 1, 398,421 and 1, 398,422 and in the patent of E.U.A. No. 3,936,448 and the ^ r ^ »sulfonated pyrolysed citrates described in British Patent No. 1, 439,000. The alicyclic and heterocyclic polyocarboxylates include 15 cyclopentane-cis.cis.cis-tetracarboxylates, cyclopentadiene pentacarboxylates, 2,3,4,5, -tetrahydrofuran-cis, cis, cis-tetracarboxylates, 2,5-tetrahydrofuran-cis-dicarboxylates, 2,2,5,5 -tetrahydrofuran-tetracarboxylates, 1, 2j3,4,5,6, -hexane-hexacarboxylates and carboxymethyl derivatives of polyhydric alcohols such as sorbitol, mannitol and xylitol. Aromatic polycarboxylates include acid 20 melitic, pyromellitic acid and the phthalic acid derivatives described in British Patent 1, 425, 433.

Of the above, preferred polycarboxylates are hydrocarboxylates containing up to three carboxy groups per molecule, most particularly citrates. The origin acids of the monomeric or oligomeric polycarboxylate chelating agents or mixtures thereof with their salts, for example mixtures of citric acid or citrate / citric acid are also contemplated as useful builders components. # Borate builders, as well as builders that contain borate-forming materials 10 that can produce borate under detergent storage conditions or under washing conditions can also be used but are not preferred under wash conditions. 50 ° C, especially from less than 40 ° C. Examples of carbonate builders are the15 alkaline earth metal and alkali metal carbonates, including sodium carbonate and sesquicarbonate and mixtures thereof with ultra fine calcium carbonate as described in German patent application No. 2,321, 001, published on November 15, 1973. highly detergency Preferred for use in the present invention are water-soluble phosphate builders. Specific examples of water-soluble phosphate builders are metalalkaline tripolyphosphates, sodium, potassium and ammonium pyrophosphate, sodium and potassium pyrophosphate and ammonium, sodium and potassium orthophosphate, polymethane / sodium phosphate in which the degree of polymerization is in the range of 6 to 21, and salts of phytic acid. Specific examples of water-soluble phosphate builders are metalalkaline tripolyphosphates, sodium, potassium and ammonium pyrophosphate, potassium and sodium ammonium pyrophosphate, potassium and sodium orthophosphate, and polymeta / sodium phosphate, in which the degree of polymerization it is on the scale of 6 to 21, and the salts of phytic acid.

Meanstock of partially soluble or insoluble detergency The compositions of the present invention, especially those in the form of particles, may contain a partially soluble or insoluble builder compound. Examples of partially water-soluble detergency builders include crystalline layered silicates as described, for example, in EP-A-0164514, DE-A-3417649 and DE-A-3742043. Preferred are the crystalline layered sodium silicates of the general formula: NaMSixO2 + 1 »and H20 wherein M is sodium or hydrogen, x is a number from 1.9 to 4 e and is a number from 0 to 20. Crystallised stratified sodium silicates of this type preferably have a two-dimensional "sheet" structure, as the so-called structure d-stratified, as described in EP 0 164514 and EP 0 293640. Methods for the preparation of crystalline layered silicates of this type are described in DE-A-3417649 and DE-A-3742043. For the purposes of the present invention, x in the above general formula has a value of 2, 3 or 4 and preferably is 2. The most preferred crystalline layered sodium silicate compound has the formula d-Na2Si20s, known as NaSKS- 6 (trade name), available from Hoechst AG. The crystalline layered sodium silicate material is preferably present in granular detergent compositions as a 10 particle in intimate admixture with a solid, water soluble, ionizable material, as described in PCT patent application No. W092 / 18594. The solid, water soluble, ionizable material is selected from organic acids, salts of organic or inorganic acid and mixtures thereof, with citric acid being preferred. Examples of widely water-soluble detergency builders include sodium aluminosilicates. Suitable aluminosilicates include the aluminosilicate zeolites having the unit cell formula Naz [(AIO2) z. { SiO2) and] »xH2O in which z and y are at least 6; the molar ratio of z to y is from 1.0 to 0.5 and x is at least 5, preferably from 7.5 to 276, more preferably 10 to 264. The aluminosilicate material is in hydrated form and is preferably crystalline, containing from 10% to 28%, more preferably from 18% to 22% of water in bound form.

"" "* Zeolites and aluminosilicate may be naturally occurring materials, but are preferably synthetically derived.Crystal synthetic aluminosilicate ion exchange materials are available under the designations Zeolite A, Ze Nta 5 - . 5-B, Zeolite P, Zeolite X, Zeolite HS and mixtures thereof. A preferred method for synthesizing aluminosilicate zeolites is that described by Schoeman et al (published in Zeolite (1994) 14 (2), 110-116) in which the author describes a method for preparing colloidal aluminosilicate zeolites. The particles of aluminosilicate zeolites Colloidal particles should preferably be such that no more than 5% of the particles are of a size larger than 1 μm in diameter and no more than 5% of the particles are of size less than 0.05 μm in diameter. ^^^ 9 Preferably the particles of aluminosilicate zeolites have an average particle diameter size between 0.01 μm and 1 μm, more 15 preferably between 0.05 μm and 0.9 μm, more preferably between 0.1 μm and 0.6 μm. Zeolite A has the formula: Na12 [(Al? 2) i2 (Si? 2) i2] -xH20 20 in which x is from 20 to 30, especially 27. Zeolite X has the formula: Na86 [(Al? 2) 86 (SiO2) l06] "276H2 ° - to zeolite MAP, as described in EP-B- 384,070 is a preferred builder preferred herein.

The preferred aluminosilicate zeolites are the colloidal aluminosilicate zeolites. When used as a component of a detergent composition, colloidal aluminosilicate zeolites, especially colloid zeolite A, provide improved detergency builder performance in terms of providing improved spot removal. The improved detergency builder performance is also seen in terms of reduced fabric embedding and improved whiteness maintenance; problems that are believed to be associated with poorly constructed detergent compositions. 10 A surprising discovery is that the mixed detergent compositions of aluminosilicate zeolite comprising zeolite A colloid and zeolite Y colloid provide equal scavenger performance of onion Ü ^ I calcium against an equal weight of zeolite A commercially available. Another surprise discovery is that mixed detergent compositions 15 of aluminosilicate zeolite, described above, provide improved yield of magnesium ion sequestrant against an equal weight of commercially available zeolite A.

^ P Surfactant 20 Suitable surfactants are selected from anionic, nonionic, cationic, ampholytic, and zwitterionic surfactants, and mixtures thereof. The surfactant is typically present at a level of 0.2% to 30% by weight, more preferably 0.5% to 10% by weight, more preferably from 1% to 5% by weight of the composition of active detergent components. A typical list of anionic, nonionic, ampholytic and zwitterionic classes, as well as species of these surfactants, is given in the U.S. patent. No. 3,929,678, issued to Laughlin and Heuring on December 30, 1975. A listing of suitable cationic surfactants is given in the U.S.A. No. 4,259,217, issued to Murphy on March 31 * March 1981. A list of surfactants typically included in laundry detergent compositions is given, for example, in EP-A-0414 10,549 and PCT applications Nos. WO 93/08876 and WO 93/08874.

Nonionic surfactant? ^^ * Essentially any nonionic surfactants useful for detersive purposes can be included in the compositions. 15 Non-limiting, preferred classes of useful non-ionic surfactants are listed below.

Nonionic surfactant of ethoxylated alcohol ^^ Alcohyl condensation products of alcohols Aliphatics with 1 to 25 moles of ethylene oxide are suitable for use herein. The alkyl chain of the aliphatic alcohol may be either straight or branched, primary or secondary, and generally contains from 6 to 22 carbon atoms. Particularly preferred are the condensation products of alcohols having an alkyl group containing from 8 to 20 carbon atoms with from 2 to 10 moles of ethylene oxide per mole of alcohol.

Surface-active alkoxylated alkoxylate surfactant A suitable blocked end alkyl alkoxylate surfactant is the poly (oxyalkylated) alcohols represented by the formula: R? O [CH2CH (CH3) 0]? [CH2CH2?] And [CH2CH (OH) R2] (1) Wherein Ri is a linear or branched aliphatic hydrocarbon radical having from 4 to 18 carbon atoms; R2 is a linear or branched aliphatic hydrocarbon radical having from 2 to 26 carbon atoms; x is an integer that 3 ^ r 'has an average value of 0.5 to 1.5, more preferably 1; and y is an integer having a value of at least 15, more preferably at least 20. Preferably, the surfactant of formula I, at least 10 carbon atoms in the terminal epoxy unit [CH2CH (OH) R2]. Suitable surfactants of formula I, according to the present invention, are Olin POLY-TERGENT® SLF-18B nonionic surfactants F ^ Corporation, as described, for example, in WO 94/22800, published on 20 October 13, 1994, by Olin Corporation.

Ploxyalized Eagle Alcohols) of Blasted Ether Preferred surfactants for use herein include the poly (oxy-alkyl) alcohols of blocked ether having the formula: R1O [CH2CH (R3) 0] x [CH2] kCH (OH) [CH2] jOR2 wherein R1 and R2 are aliphatic or aromatic hydrocarbon radicals, linear or branched, saturated or unsaturated, having from 1 to 30 carbon atoms; R3 is H or a linear aliphatic hydrocarbon radical having 1 to 4 carbon atoms; x is an integer having an average value of 1 to 30, in which when x is 2 or larger R3 may be the same or different ykyj are integers having an average value of 1 to 12, and more preferably 1 to 5 R1 and R2 are preferably aliphatic or aromatic hydrocarbon radicals, linear or branched, saturated or unsaturated, having from 6 to 22 carbon atoms, with from 8 to 18 carbon atoms being most preferred. H or a linear aliphatic hydrocarbon radical having 1 to 2 carbon atoms is more preferred for R3. Preferably x is an integer having an average value of 1 to 20, more preferably 6 to 15. As described above, when, in the preferred embodiments, and x is greater than 2, R3 may be the same or different. That is, R3 can vary between any of the heterohexy units as described above. For example, if x is 3, R3 can be selected to form ethyleneneoxy (EO) or propyleneneoxy (PO) and can vary in order of (EO) (PO) (EO), (EO) (EO) (PO); (EO) (EO) (EO); (PO) (EO) (PO); (PO) (PO) (EO) and (PO) (PO) (PO). Of course, the integer three is selected for example only and the variation can be much longer with a value of highest integer for x and includes, for example, multiple units (EO) and a 5 much smaller number of units (PO). Particularly preferred surfactants are as described above include those that have a low turbidity point of less than 20 ° C. These low cloud point surfactants can be used in conjunction with a high turbidity dot surfactant as described in detail below for superior fat cleaning benefits.

The most preferred blocked ether poly (oxyalkylated alcohol) surfactants are those in which k is 1 and j is 1 such that the surfactants have the formula: R10 [CH2CH (R3) 0] xCH2CH (OH) CH2OR2 wherein R1, R2 and R3 are as defined above and x is an integer with an average value of 1 to 30, preferably 1 to 20, and even more - * preferably from 6 to 18. Surfactants are more preferred in the 20 which R1 and R2 are on the scale of 9 to 14, R3 is H forming ethyleneneoxy and x It is on the scale of 6 to 15.

The ether-blocked poly (oxyalkylated alcohol) surfactants comprise three general components, ie a linear alcohol or branched, an alkaline oxide and a blocked end-of ether alquílfco. The blocked end alkyl ether and the alcohol serve as a hydrophobic, oil soluble portion of the molecule while the alkylene oxide group forms the water soluble portion, hydrophilic of the molecule. These surfactants exhibit significant improvements in film formation characteristics and stain removal and removal of greasy stains, when used in conjunction with high cloud point surfactants, in relation to conventional surfactants. Generally speaking, the blocked ether poly (oxyalkylene) surfactants of the present invention can be produced by reacting an aliphatic alcohol with an epoxide to form an ether which is then reacted with a base to form a second epoxide. The second epoxide is then reacted with an alkoxylated alcohol to form the novel compounds of the present invention. Examples of methods for preparing the blocked ether poly (oxyalkylated) alcohol surfactants are described below: Non-ionic surfactant of ethoxylated / propoxylated fatty alcohol Ethoxylated fatty alcohols of Cß-C-iß and mixed ethoxylated / propoxylated C6-C18 fatty alcohols are suitable surfactants for use herein, particularly where water-soluble Preferably the ethoxylated fatty alcohols are the ethoxylated fatty alcohols of C? OC-, 8 with an ethoxylation degree of from 3 to 50, more preferably those are the ethoxylated fatty alcohols of C? 2-C? 8 clone a degree of ethoxylation of 3 to 40. Preferably the mixed ethoxylated / propoxylated fatty alcohols have an alkyl chain length of 10 to 18 carbon atoms, a degree of ethoxylation of 3 to 30 and a degree of propoxylation of 1 to 10.

EO / PO nonionic condensates with propylene glycol The condensation products of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol are suitable for use herein. Serving ^^^ Hydrophobic of these compounds preferably has a molecular weight of 1500 to 1800 and exhibits insolubility in water. Examples of compounds of this The type includes certain commercially available Pluronic® surfactants, marketed by BASF.

EO nonionic condensation products with propylene / ethylene diamine adducts The condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylenediamine are suitable for use herein. The hydrophobic portion of these products consists of the reaction product of ethylenediamine and J r [rbpileno bn excess, and generally has a molecular weight of 2500 to 3000. Examples of this type of nonionic surfactant include certain of the commercially available Tetronic® compounds, marketed by BASF.

Anionic surfactant Essentially any anionic surfactants useful for detersive purposes are suitable. These may include salts (including, for example, sodium, potassium, ammonium and substituted ammonium salts such as mono-, di- and triethanolamine salts) of the anionic sulfate, sulfonate, carboxylate and sarcosinate surfactants. Anionic sulfate surfactants are preferred. ^ Other anionic surfactants include isethionphals such as acyl isethionates, N-acyl taurates, fatty acid amides of methyl 15 tauride, alkyl succinates and sulfosuccinates, monoesters of sulfosuccinate (especially saturated and unsaturated C12-C18 monoesters) sulfosuccinate diesters (especially saturated and unsaturated C6-C14 diesters), N-acyl sarcosinates. Resin acids and cold acids F hydrogenates are also suitable, such as rosin, hydrogenated rosin 20 and hydrogenated resin acids and resin acids present in or derived from tallow oil.

Sulphonic anionic surfactant The sulfate anionic surfactants suitable for use herein include linear and branched, primary and secondary alkyl sulfates, alkyl ethoxy sulfates, fatty oleyl glycerol sulfates, 5 ethylene oxide ethers of alkylphenol, the acyl glucaminsuffonates of C5-C- | 7-N- (C-1-C4 alkyl) and -N- (C1-C2 hydroxyalkyl), and alkylpolysaccharide sulfates such as the alkyl polyglycoside sulphates (described in F is present non-sulphonated non-ionic compounds). The alkylsulfate surfactants are preferably selected from linear and branched C-io-C-is alkylsulfates, more preferably the branched chain C11-C15 alkyl sulfates and the W * straight chain C12-C14 alkyl sulfates. The alkyl ethoxy sulfate surfactants are preferably selected from the group consisting of the C- or C 8 alkyl sulfates which 15 have been ethoxylated with 0.5 to 20 moles of ethylene oxide per molecule. More preferably, the alkyl ethoxy sulfate surfactant is a C 11 -C 18 alkyl sulfate. preferably C11-C15 which has been ethoxylated with 0.5 to 7, preferably 1 to 5, moles of ethylene oxide per molecule.

# A particularly preferred aspect of the invention employs 20 mixtures of the preferred alkyl sulfate and alkyl ethoxysulfate surfactants. Such mixtures have been described in PCT application No. WO 93/18124.

Sulfonated anionic tensio-bivalent agent Sulfonate anionic surfactants suitable for use herein include C5-C20 linear athenylbenzene sulphonate salts. alkyl ethers sulfonates, Cg-C22 alkan sulfonates 5 primary or secondary, C6-C24 olefinsulfonates, sulfonated polycarboxylic acids, alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfonates and any mixtures thereof.

Carboxylate Anionic Surfactant 10 Suitable carboxylate anionic surfactants include alkylethoxycarboxylates, alkylpolyethoxy polycarboxylate surfactants and soaps ("alkylcarboxyls"), especially carboxylate anionic surfactants. ^^ r% certain secondary soaps such as those described herein. Suitable alkylethoxycarboxylates include those with the The formula RO (CH2CH20) xCH2C00-M + in which R is a C $ to C C alkyl group. it is on the scale from 0 to 10, and the ethoxylate distribution is such that, based on weight, the amount of material in which x is 0 is less than 20% and M is a cation. Suitable alkylpolyethoxy polycarboxylate surfactants f include those having the formula RO- (CHR- | -CHR2-0) -R3 20 * "in which R is an alkyl group of CQ to CJ S. x is from 1 to 25, R- | and R2 are selected from the group consisting of hydrogen, methyl acid radical, succinic acid radical, hydroxysuccinic acid and mixtures of same, and R3 is selected from the group consisting of hydrogen, substituted or unsubstituted hydrocarbon having from 1 to 8 carbon atoms, and mixtures thereof. Suitable soap surfactants include the secondary soap surfactants that contain a carboxyl unit connected to a secondary carbon. The preferred secondary soap surfactants for use herein are the members • water-soluble substances selected from the group consisting of the water-soluble salts of 2-methyl-1-undecanoic acid, 2-et? L-1-decanoic acid, 2-propyl-1-10 nonanoic acid, 2-butyl-1 acid -octanoic acid and 2-pentyl-1-heptanoic acid. Certain soaps can also be included as suds suppressors. ^ ^^ i Metalalkaline Sarcosinate Surfactant Other suitable anionic surfactants are the 15 metalalkaline sarcosinates of the formula R-CON (R1) CH2COOM, in which R is a linear or branching C5-C17 alkyl or alkenyl group R ^ is a C1-C4 alkyl group and M is an alkali metal ion. Preferred examples are myristyl or oleoyl methylsarcosinates in the form of their sodium salts. Amphoteric Surfactant The amphoteric surfactants suitable for use herein include amine oxide surfactants and alkylamphocarboxylic acids. '^ xS, Suitable amine oxides include those compounds having the formula R3 (OR4) xN (R5) 2f in which R ^ is selected from an alkyl, hydroxyalkyl, acylamidopropyl and alkylphenyl group or mixtures thereof, which contains 8 to 26 carbon atoms; R4 is an alkylene or hydroxyalkylene group containing from 2 to 3 carbon atoms, or mixtures thereof; x is from 0 to 5, preferably from 0 to 3; and each R§ is an alkyl or hydroxyalkyl group containing from 1 to 3 carbon atoms, or a polyethylene oxide group containing from 1 to 3 ethylene oxide groups. Alkyl dimethylamine oxide of C? O_18 and acylamidoalkyldimethylamine oxide of C? O- < 8- A suitable example of an alkylamphodicarboxylic acid is Miranol (MR) C2M Conc., Manufactured by Miranol, Inc., Dayton, NJ.

Zwitterionic Surfactant Zwitterionic surfactants may also be incorporated in the detergent compositions herein. These surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. The surfactants of sultaine and betaine are illustrative zwitterionic surfactants that can be used herein.

Suitable betaines are those compounds that have the formula R (R ') 2N + R2COO- in which R is a hydrocarbyl group of CQ-C-) Q, each R1 is typically C1-C3 alkyl, and R2 is a hydrocarbyl group of C-J-C5. Preferred betaines are the betaines of C12-C18 dimethyl ammonium hexanoate and C5-C18 acylamidopropane (or ethane) dimethyl (or diethyl) betaines. Also, complex betaine surfactants are suitable for use herein.

Cationic surfactants The cationic ester surfactants used in this invention are preferably a water dispersible compound having surfactant properties comprising at least one ester linkage (ie, -COO-) and at least one cationically charged group. Other suitable cationic ester surfactants, including the agents 15 choline ester surfactants have been described, for example, in the US patents. Nos. 422,8042, 4239660 and 4260529. Suitable cationic surfactants include the quaternary ammonium surfactants selected from agents • C6-C16 mono alkenyl ammonium surfactants, preferably N-alkyl C6-C6 in which the remaining N positions are substituted by methyl, hydroxyethyl or hydroxypropyl groups.

The softening agent The softening ingredients of the present invention can be selected from any known ingredients that provide a fabric softening benefit. The clay minerals that are used to provide the softening properties of the compositions herein can be described as expandable, three-layered clays, ie, aluminosilicates and • magnesium silicates, which have an ion exchange capacity of at least 50 meq / 100 g of clay. The term "expandable" as used to describe clays refers to the ability of the stratified clay structure to swell, or expand, upon contact with water. The three-layer expandable clays that are used in the present are those materials classified geologically as smectites. There are two different classes of smectite-type clays; in the first one, aluminum oxide is present in the silicate crystal loop; in the second class of smectites, magnesium oxide is present in the silicate crystal loop. The general formulas of these smectites are Al2 (Si2O5) 2 (OH) 2 and Mg3 (Si205) (OH) 2 for the type of aluminum oxide clay f and magnesium, respectively. It must be recognized that the scale of the water of hydration in the above formulas may vary with the processing to which the clay has been subjected. This is irrelevant to the use of the smectite dices in the present invention in that the expanding characteristics of the hydrated clays are dictated by the silicate loop structure, adi of silicate loop. Adiofonally, the substitution of atom by iron and magnesium can occur within the crystal loop of the srrectites, while metal cations such as Na +, Ca ++, as well as H +, can be co-present in the hydration water to provide electrical neutrality. 5 Except as noted here below, such cation substitutions are inconsequential to the use of clays herein because the desirable physical properties of the clays are not substantially altered by them. The three layer expandable aluminosilicates useful in the The present invention is further characterized by a dioctahedron glass loop, while the three layer expandable magnesium silicates have an & trioctahedron glass loop. As noted hereinabove, the clays that are used in the compositions of the present invention contain cationic counterions 15 such as protons, sodium ions, potassium ions, calcium ions, magnesium ions, and the like. It is usual to distinguish between clays based on a cation absorbed predominantly or exclusively. For example, a sodium clay is one in which the cation absorbed is primarily sodium. Such absorbed cations can become involved in reactions of 20 exchange with cations present in aqueous solutions. A typical exchange reaction involving a smectite-like clay is expressed by the following equation: Smectite clay (Na) + NH4OH smectite clay (NH4) + NaOH Because in the aforementioned equilibrium reaction, an equivalent weight of ammonium ion replaces a sodium equivalent weight, it is customary to measure cation exchange capacity (sometimes called "base exchange capacity") in terms of milliequivalents per 100 g of clay (meq / 100 g). The cation exchange capacity of clays can be measured in various ways, including by electrodialysis, by exchange with ammonium atoms followed by grinding or by a methylene blue process, as fully explained in Grimshaw, "The Chemistry and Physics of Clays ", pages. 264-265, Interscience (1971). The cation exchange capacity of a clay mineral is related to such factors as the expandable properties of the clay, the loading of the clay, the cell, in turn, is determined at least in part by the loop structure, and Similar. The ion exchange capacity of clays varies widely on the scale of about 2 meq / 100 g for kaolinites to about 150 meq / 100 g, and higher, for certain clays of the montmorillonite variety. Iite clays have an ion exchange capacity somewhere in the lower portion of the scale, that is, around 26 meq / 100 g for an average illite clay. The illite and kaolinite clays, with their relatively low exchange capacities, are preferably not used as the clay in the present compositions. In fact, such clay and kaolinite clays are a major component of clay soils and, as noted above, they are removed from the fabric surfaces by means of the compositions herein. However, the smectites, such as nontonite, which have an ion exchange capacity of about 70 meq / 100 g, and montmorillonite, which has a larger exchange capacity of 70 meq 100 g, have been found which are useful in the compositions herein in that they are deposited on the fabrics to provide the desired softening benefits. Agree with this, F the clay minerals useful herein can be characterized as three-layer expandable smectite-type clays that dye a capacity of 10 ion exchange of at least about 50 meq / 100 g. Although one does not wish to be limited by theory, it appears that advantageous benefits of softness (and preferably debugging of dye, etc.) of the compositions herein can be obtained and are. attributable to the physical characteristics and properties of ion exchange 15 of the clays that are used in them. That is, experiments have shown that non-expandable clays such as kaolinites and litas, which are both classes of clays that have an ion exchange capacity below 50 meq / 100 g, do not provide • the beneficial aspects of the clays that are used in the compositions of 20 the present. The smectite clays used in the compositions herein are all commercially available. Such clays include, for example, montmorillonite, volconscoite, nontronite, hectorite, saponite, "1 t sauconite, and vermiculite. The clays herein are available from several commercial brands, for example, Thixoget # 1® and Gelwhite GP® from Georgia Kaolin Co., Elizabeth, New Jersey; Volclay BC® and Volclay # 325, from American Colloid Co., Skokie, Illinois; Black Hitls bentonite BH450®, from 5 International Minerals and Chemicals; and Veegum Pro and Veegum F, from R.T. Vanderbilt It should be recognized that such smectite-type minerals obtained under the trademarks mentioned above may comprise # mixtures of the various discrete mineral entities. Such mixtures of the smectite minerals are suitable for use herein. Although any of the smectite-type clays having an exchange capacity of at least about 50 meq / 100 g are useful in the present, certain clays are preferred. For example, Gelwhite GP® is an extremely white form of smectite clay and is therefore preferred when formulating detergent compositions. 15 white granules Volclay BC®, which is a smectite-type clay mineral that contains at least 3% iron (expressed as Fe2? 3) in the crystal loop, and which has a very high ion exchange capacity, is one of the clays more effective and effective for use in compositions for ^ laundry and is preferred from a product performance point of view. The clay minerals suitable for use herein can be selected by virtue of the fact that the smectites exhibit a real X-ray diffraction pattern of 14A. This characteristic pattern, taken in combination with measurements of exchange capacity carried out in the In a manner described above, it provides a basis for selecting particular smectite-type micronutrients for use in the granular detergent compositions described herein. The clay is preferably mainly in the form of 5 granules, with at least 50%, preferably at least 75%, and more preferably at least 90% being in the form of granules having a size of at least OJ mm up to 1.8 mm, preferably up to 1 J8 mm, "preferably from 0J5 mm to 0.85 mm Preferably the amount of clay in the granules is at least 50%, more preferably at least 70%, and 10 more preferably at least 90% by weight of the granules. Smectite clays are described in the US patents Nos. 3,862,058, 3,948,790, 3,954,632 and 4,062,647. European patents Nos. EP-A-299,575 and EP-A-313,146 in the name of The Procter and Gamble Company describe organic polymeric clay flocculation agents 15 suitable. Other suitable softening ingredients are long chain polymers and copolymers which are derived from monomers such as ethylene oxide, acrylamide, acrylic acid, ethyl dimethylamino methacrylate, vinyl alcohol, vinyl pyrrolidone and ethylene imide. Polymers of ethylene oxide, acrylamide and acrylic acid are preferred. These polymers preferably have an average molecular weight on the scale of 100,000 to 10 million, more preferably 150,000 to 5 million. The average molecular weight of a polymer can be easily measured using chromatography of gelf permeation against polyethylene oxide standards of narrow molecular weight distributions. The most preferred polymers are polyethylene oxides. Other suitable softening ingredients include cationic fabric softening agents also can be incorporated into polymer composition according to the present invention which are suitable for use in laundry washing methods. Suitable cationic fabric softening agents include tertiary amines or water-insoluble dilarga-chain amide materials as described in GB-A-1, 514, 276 and EP-B-0,011, 340. • Enzymes ^^^, Where these enzymes are present are selected from the group consisting of cellulases, hemicellulases, peroxidases, proteases, 15-glucoamylases, amylases, lipases, xylanases, phospholipases, esterases, cutinases, pectinases, keratanases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tanases, pentosanas, malanases, β-glucanases, arabinosidases, hyaluronidase, chondroitinase, laccase or mixtures thereof. Preferred enzymes include protease, lipase, cutinase and / or cellulase, in conjunction with one or more vegetal cement wall degrading enzymes.

Cellulases useful in the present invention include both bacterial and fungal cellulases. Preferably, they will have an optimum pH between 5 and 12 and an activity above 50 CEVU (cellulose viscosity unit). Suitable cellulases are described in the U.S.A. No. 5,435,307, Bargesgoard et al, J61078384 and WO96 / 02653 which describes a fungal cellulase produced respectively from Humicola nsolens, Trichoderma, Thievalla and Sporotrichum. EP 739 982 describes isolated cells of novel species of Bacillus. Suitable cellulases are also described in GB-A-2,075,028; GB-A-2,095,275; DE-10 OS-2,247,832 and WO 95/26398. * Examples of said cellulases are the cellulases produced by ^ a strain of Humicola insolens (Humicola grísea var. thermoidea), F ^^ • particularly the DSM 1800 strain of Humicola. Other suitable cellulases are the cellulases originated from Humicola insolens that have a weight 15 molecular of approximately 50 KDa, an isoelectric point of 5.5, and containing 415 amino acids, and an endoglucanase of ~ 43kD derived from Humicola insolens, DSM 1800, exhibiting cellulase activity; an endoglucanase component that is preferred has the sequence of • amino acid described in PCT patent application No. WO 91/17243.

Also suitable cellulases are the EGIII cellulases of Tríchoderma longibrachiatum described in WO 94/21801, Genencor, published on September 29, 1994. Particularly suitable cellulases are cellulases which have color care benefits. Examples of said cellulases are the cellulases described in European patent application No. 91202879.2, filed on November 6, 1991 (Novo). Carezyme and Celluzyme (Novo Nordisk A / S) are especially useful. See also WO 91/17244 and WO 91/21801. Other cellulases suitable for fabric care and / or cleaning properties are described in WO 96/34092, W096 / 17994 and WO 95/24471. Said other cellulases are normally incorporated in the detergent composition at levels of 0.0001% to 2% of active enzyme by weight of the detergent composition. Peroxidase enzymes are used in combination with oxygen sources, for example, percarbonate, perborate, persulfate, hydrogen peroxide, etc. They are used for "bleaching in solution", that is, to avoid the transfer of dyes or pigments removed from substrates during washing operations, to other substrates in the washing solution. Peroxidase enzymes are known in the art and include, for example, horseradish peroxidase, ligninase, and haloperoxidase such as chloro- and bromo-peroxidase. Peroxidase-containing detergent compositions are described, for example, in the PCT International Application WO89 / 099813, WO 89/09813 and European Patent Application No. 91202882.6, filed on November 6, 1991 and EP No. 96870013.8, filed on February 20, 1996. The laccase enzyme is also suitable. Preferred enhancers are fentiazine and phenoxasine, 10-phenothiazinopropionic acid (PPT), 10-ethylphenothiazine-4-carboxylic acid (EPC), 10-phenoxazinopropionic acid (POP) and 10'-phenylphenoxazine (described in WO 94/12621) and substituted syringates (substituted C3-C5 alkylshtyates) and phenols. Percarbonate or sodium perborate are preferred sources of hydrogen peroxide. Said cellulases and / or peroxidases are normally incorporated in the detergent composition at levels of 0.0001% to 2% active enzyme by weight of the detergent composition. • Other preferred enzymes that can be included in the detergent compositions of the present invention include lipases. The 10 lipase enzymes suitable for detergent use include those produced by microorganisms of the Pseudomonas group, such as • Pseudomonas stutzeri ATCC 19,154, as described in the patent.

•: British 1, 372,034. Suitable lipases include those that show a positive immunological cross-reaction with the lipase antibody, 15 produced by the microorganism Pseudomonas fluorescent lAM 1057. This lipase is available from Amano Pharmaceutlcal Co. Ltd., Nagoya, Japan, under the trade name Lipase P "Amano", hereinafter referred to as "Amano-P". Other suitable commercial lipases include Amano-OEiS, ex-Chromobacter viscosum ph lipases, for example Chromobacter viscosum var. 20 lipoliticum NRRLB 3673, from Toyo Jozo Co., Tagata, Japan; Chromobacter viscosum lipases from U.S. Biochemical Corp, E.U.A. and Disoynth Co., Holland and lipases ex Pseudomonas gladioli. Lipases especially suitable are lipases such as M1 Lipase ^ and Lipomax ^ (Gist- . . fe- -. : - - Brocades) and Lipotase ^ and L olase Ultra ^ (Novo), which have been found to be very effective when used in combination with the compositions of the present invention. Also suitable are the lipolytic enzymes described in EP 258 068, WO 92/05249 and WO 95/22615 by Novo Nordisk, and in WO 94/03578, WO 95/35381 and WO 96/00292 by Unilever. Also suitable are cutinases [EC 3.1.1.50] which are ^ f ^ can be considered as a special type of lipase, ie lipases that do not require interfering activation. The addition of cutinases to compositions Detergents have been described in, for example, WO-A-88/09367 (Genencor); WO 90/09446 (Plant Genetic System), and WO 94/14963 and WO 94/14964 (Unilever).

The lipases and / or cutinases are normally incorporated in the detergent composition at levels of 0.0001% to 2% active enzyme by weight of the detergent composition. Suitable proteases are the subtilisins that are obtained from particular strains of B.subtilis and B.licheniformis (subtilisin BPN and BPN '). Other suitable proteases are obtained from a Bacillus strain, having a maximum activity in the entire pH range of 8 to 12, developed and sold as ESPERASE ^ by Novo Industries A S of Denmark, in 20"Novo" ahead. The preparation of this enzyme and analogous enzymes is described in GB 1, 243,784, to Novo. Other suitable proteases include ALCALASE®, DURAZYM® and SAVINASE® from Novo and MAXATASÉ®, MAXACAL®, PROPERASE® and MAXAPEM® (Maxacal manipulated with proteins) of Gist-Brocades. Proteotitic enzymes also encompass modified bacterial serine proteases, such as those described in European Patent Application No. 87303761.8, filed April 28, 1987 (particularly pages 17, 24 and 98) and which is referred to herein as "5". Protease B ", and in the European patent application EP 199 404, Venegas, published on October 29, 1986, which refers to a modified bacterial serine protease that is referred to herein as" Protease A ". It preferred ^ n ^ plus the one in the present so-called "Protease C" which is a variant of a Bacillus alkaline serine protease in which lysine replaces arginine in position 27, tyrosine replaces valine in position 104, serine replaces asparagine at position 123 and alanine replaces threonine at position 274. Protease C is described in EP 90915958.4, which corresponds ^ f ^ - »WO 91/06637, published on May 16, 1991. Genetically modified variants are also included herein, particularly from 15 protease C. A preferred protease, referred to as "Protease D", is a variant of carbonyl hydrolase having an amino acid sequence that is not found in nature, which is derived from a carbonyl hydrolase ? precursor replacing a different amino acid with a plurality of 20 amino acid residues at a position in said carbonyl hydrolase equivalent to the +76 position, preferably also in combination with one or more amino acid residue positions equivalent to those selected from the group consisting of +99, +101, +103, + 104, +107, +123, i +27, +105, +109, +126, +128, +135, +156, +166, +195, +197, +204, +206, +210, +216, +217, +218, +222 , +260, +265, and / or +274 in accordance with the numeration of Bacillus amyloliquefaciens sustilysin as it is disclosed in WO 95/10591 and in the patent application of C. Ghosh, et al, "Bleaching 5 Compositions Comprising Protease Enzymes", which has the serial number of E.U.A. 08 / 322,677, filed October 13, 1994. Also suitable for the present invention are the proteases described in patent applications EP 251 446 and WO 91/06637, the BLAP® protease described in WO91 / 02792 and their variants described in WO 10 95/23221. See also a high pH protease from Bacillus sp. NCIMB A 40338 described in WO 93/18140 A to Novo. Enzyme detergents comprising protease, one or more other enzymes and a reversible protease inhibitor are described in WO 92/03529 A to Novo. When desired, it is A protease having decreased adsorption and increased hydrolysis is available as described in WO 95/07791 to Procter & Gamble. A recombinant trypsin-like protease for detergents suitable herein is described in WO 94/25583 to Novo. Other suitable proteases are described in EP 516 200 by Unilever. Other preferred enzymes include the protease enzymes that. are a variant of carbonyl hydrolase having an amino acid sequence that is not found in nature, which is derived by replacing a plurality of amino acid residues of a carbonyl precursor hydrolase with different amino acids, in which said residuals * of amino acids replaced in the precursor enzyme correspond to the +210 position in combination with one or more of the following residues: +33, +62, +67, +76, + 100, +101, +103, +104, +107, +128, +129, +130, +132, +135, +156, +158, +164, +166, +167, +170, +209, +215, +217, +218 and +222, where the numbered positions correspond to subtilisin that occurs naturally from Bacillus amyloliQuefaciens or to equivalent amino acid residues in other carbonyl hydrolases or subtilisins (such as Bacillus lentus subtilisin). Preferred enzymes of this type include those that have position changes +210, +76, +103, +104, +156, and. +166 The proteolytic enzymes are incorporated into the detergent compositions of the present invention at a level of from 0.0001% to 2%, preferably from 0.001% to 0.2%, more preferably from 0.005% to 0J% pure enzyme by weight of the composition. Amylases (a and / or ß) can be included for the removal of carbohydrate-based stains. WO94 / 02597, Novo Nordisk A / S, published on February 3, 1994, describes cleaning compositions incorporating mutant amylases. See also WO / 95/10603, Novo Nordisk A / S, published April 20, 1995. Other amylases known to be used in cleaning compositions include both and β-amylases. A-amylases are known in the art and include those described in the U.S.A. No. 5,003,257; EP 252,666; WO / 91/00353; FR 2,676,456; EP 285,123; EP 525,610; EP 368,341; and in the description of British Patent No. 1, 296,839 (Novo). Other suitable amylases are the amylases of improved stability described in W094 / 18314, published August 18, 1994 and WO 96/05295, Genencor, published February 22, 1996, and the amylase variants having further modification in the progenitor. Immediate, available from Novo Nordisk AS, described in WO95 / 10603, published April 1995. Also suitable are the amylases described in EP 277 216, WO 95/26397 and WO 96/23873 (all by Novo Nordisk).

Examples of commercial a-amylases products are Purafact Ox Am®, from Genencor and Termamyl®, Ban®, Fungamyl® and Duramyl®, all available from Novo Nordisk A / S Denmark. The document WO95 / 26397 describes other suitable amylases: α-amylases characterized by having a specific activity at least 25% greater than the specific activity of Termamyl® at a temperature range of 25 ° C to 55 ° C and a pH value on the scale of 8 to 10, measured by the Phadebas activity test of a-amylase. The variants of the above enzymes are suitable, described in WO96 / 23873 (Novo Nordisk). Other amylolytic enzymes GO? improved properties with respect to the level of activity and the combination of Thermostability and highest activity level are described in W095 / 35382. Preferred amylase enzymes include those described 'in WO95 / 26397 and in the co-pending application PCT / DK96 / 00056 by Novo Nordisk.

The amylolytic enzymes are incorporated in the detergent compositions of the present invention at a level of 0.0001% to 2%, preferably from 0.00018% to 0.06%, more preferably from 0.00024% to 0.048% pure enzyme by weight of the composition. In a particularly preferred embodiment, the detergent tablets of the present invention comprise amylase enzymes, particularly those described in W095 / 26397 and the co-pending application PCT / DK96 / 00056 by Novo Nordisk in combination with a complementary amylase. 10 By "complementary" means the addition of one or more suitable amylases for detergent purposes. Examples of complementary (a and / or β) amylases are described below. WO94 / 02597 and WO95 / 10603, Novo Nordisk A / S describe cleaning compositions incorporating mutant amylases. Other amylases known to be used in 15 cleaning compositions include α and β-amylases. The α-amylases are known in the art and include those described in the E.LMA patent. No. 5,003,257; EP 252,666; WO / 91/00353; RF 2,676,456; EP 285,123; EP 525,610; EP 368,341; and in the description of British Patent No. 1, 296,839 # (Novo) Other suitable amulases are amylases with improved stability 20 described in WO94 / 18314, published on August 18, 1994 and WO 96/05295, Genencor, and the amylase variants having further modification in the immediate parent, available from Novo Nordisk A / S described in WO95 / 10603. Also suitable are the amylases described in EP 277 216, Nofdisk). Examples of commercial α-amylase products are Purafact Ox Am®, from Genencor and Termamyl®, Ban®, Funga yl® and Duramyl, all available from Novo Nordisk A / S Denmark. WO95 / 26397 describes other suitable amylases: α-amylases characterized in that they have a specific activity at least 25% higher than the specific activity of Termamyl® at a temperature range of 25 ° C to 55 ° C and a value of pH on the scale of 8 to 10, measured by the test F ® Phadebas of α-amylase activity. Other amylolitic enzymes with improved properties with respect to activity level and combination 10 of thermostability and higher activity level are described in WO95 / 35382. Preferred complementary amylases for the present invention are the amylases sold under the trademark Purafec Ox AM® m described in WO 94/18314, WO95 / 05295 sold by Genencor; Termamyl® Ban®, Fungamyl® and Duramyl®, all available from Novo Nordisk A / S and 15 Maxamyl® by Gist-Brocades. Said complementary amylase is generally incorporated in the detergent compositions of the present invention at a level of from 0.0001% to 2%, preferably from 0.00018% to 0.06%, more preferably f 'from 0.00024% to 0.048% pure enzyme by weight of the composition .

Preferably a weight ratio of pure amylase enzyme specific to the complementary amylase is comprised between 9: 1 to 1: 9, more preferably between 4: 1 to 1: 4, and more preferably between 2: 1 and 1: 2.

The above-mentioned enzymes may have any suitable origin, such as vegetable, animal, bacterial, fungal and yeast. The origin can also be mesophilic or extremophile (psychrophilic, psibrotrophic, thermophilic, barophilic, alkalophilic, acidic, halophilic, etc.). The 5 purified or unpurified forms of these enzymes can be used. Also included by definition are the mutants of wild enzymes. Mutants can be obtained, for example, by manipulation of protein and / or genetics, • chemical and / or physical modifications of wild enzymes. The common practice is also the expression of the enzyme through a host organism in which the genetic material responsible for the production of the enzyme has been cloned. Said enzymes are normally incorporated in the composition F. detergent at levels of 0.0001% to 2% active enzyme by weight of the detergent composition. Enzymes may be added as separate individual ingredients (pellets, granules, stabilized liquids, etc. containing an enzyme) or as mixtures of two or more enzymes (eg, cogranulates). Other suitable detergent ingredients that can be added f > are the enzyme oxidation purifiers that are described in the application 20 of copending European patent 92970018.6, filed on January 31, 1992. Examples of said enzyme oxidation scavengers are ethoxylated tetraethylenepolyamines.

A range of enzyme materials and means for their incorporation into synthetic detergent compositions is also disclosed in WO 9307263 and WO 9307260 to Genencor International, WO 8908694 A to Novo, and E.U.A. 3,553,139, January 5, 1971 to McCarty et al. 5 Enzymes are also described in E.U.A. 4,101, 457, Place et al, July 18, 1978 and in E.U.A. 4,507,219, Hughes, March 26, 1985. Useful enzyme materials for liquid detergent formulations and their • Incorporation into said formulations are described in E.U.A. 4,261, 868, Hora et al, April 14, 1981. Enzymes to be used in detergents 10 can be stabilized by various techniques. Enzyme stabilization techniques are described and illustrated in E.U.A. 3,600,319, August 17, 1991, Gedge et al, EP 199,405 and EP 200,586, October 29, 1986, Venegas.

* ^ ^ * Enzyme stabilization systems are also described, for example, in E.U.A. 3,519,570. A Bacillus sp. AC13 useful and that gives proteases, xylanases and Cellulases are described in WO 9401532 A to Novo.

Bleaching agent Suitable bleaching agents include chlorine m: bleaching agents that release chlorine and oxygen, preferably a bleaching agent 20 which releases oxygen contains a source of hydrogen peroxide and an organic peroxyacid bleach precursor cond. The production of the organic peroxyacid occurs by an in situ reaction of the precursor with a source of hydrogen peroxide. The sources of hydrogen peroxide which are preferred include inorganic perhydrated whiteners. In a preferred aspect a preformed organic peroxyacid is incorporated directly into the coition in a liquid matrix as a suspended particle as described above. Also disclosed are coitions containing mixtures of a source of hydrogen peroxide and an organic peroxyacid precursor in combination with a preformed organic peroxyacid.

Inorganic Perhydrate Blanctants The particulate coitions preferably include a source of hydrogen peroxide, such as a bleach that releases oxygen. Suitable sources of hydrogen peroxide include the inorganic perhydrate salts. The inorganic perhydrate salts are normally incorporated in the sodium salt form at a level of 1% to 40% by weight, more preferably 2% to 30% by weight and more preferably 5% to 25% by weight of the coitions . Examples of inorganic perhydrate salts include perborate, percarbonate, perphosphate, persulfate and persilicate salts. The inorganic perhydrate salts are usually the alkali metal salts. The inorganic perhydrate salt can be included as the crystalline solid without additional protection. However, for certain perhydrate salts, the preferred embodiments of said granular coitions use a form coating of the material which provides better stability under * storage for the perhydrate salt in the granulated product. The sodium perborate may be in the form of the monohydrate of the nominal formula NaB 2 H 2 o 2 or the tetrahydrate Na B 2 H 2 2.3 2.3 H 2 - 5 The alkali metal percarbonates, particularly sodium percarbonate, are the preferred perhydrates for inclusion in coitions according to the invention. Sodium percarbonate is a # addition cond having a formula corresponding to 2Na2C? 3-3H2? 2 and commercially available as a crystalline solid. 10 Sodium percarbonate, being an addition cond of hydrogen peroxide, tends in the solution to release hydrogen peroxide quite rapidly which may increase the tendency for its n ^^^ * very localized bleach concentrations. The percarbonate is more preferably incorporated into said coitions with coating it 15 which provides stability in the product. A suitable coating material that provides stability in the product comprises a mixed salt of a water-soluble alkali metal sulfate and carbonate. Said coatings together with coating processes have been previously described in GB-1, 466,799, granted 20 to Interox on March 9, 1977. The weight ratio of the mixed salt to percarbonate coating material is in the range of 1: 200 to 1: 4, more preferably 1: 99 to 1: 9, and more preferably from 1:49 to 1:19. Preferably, the mixed salt is sodium sulfate and sodium carbonate which has the general formula Na2S? 4.n.Na2C? 3 in fa cuaf n is from 0.1 to 3, preferably n is from 0.3 to 1.0 and more preferably n is from 0.2 to 0.5. Another suitable coating material that provides stabilization in product, comprises sodium silicate of ratio of Si 2: Na 2? of 1.8 > 1 to 3 0: 1, preferably 1.8: 1 to 2.4: 1 and / or sodium metasilicate, preferably applied at a level of 2% to 10% (usually 3% to 5%) of S? 02 by weight of the inorganic perhydrate salt Magnesium silicate can also be included in the coating. Coatings that contain silicate and borate salts or boric or other inorganic acids are also suitable.

Peroxyacid bleach precursor Peroxyacid bleach precursors are compounds that react with hydrogen peroxide in a perhydrolic reaction to produce a peroxyacid. Peroxyacid bleach precursors can generally be represented as: O II X-C-L wherein L is a residual group, and X is essentially any functionality, such that in perhydrolysis, the structure of the produced peroxyacid is: II X-C-OOH Peroxyacid bleach precursor compounds are preferably incorporated at a level of from 0.5% to 20% by weight, more preferably from 1% to 10% by weight, most preferably from 1.5% to 5% by weight of the compositions. Suitable peroxyaoid bleach precursor compounds typically contain one or more N- or O-acyl groups, which may be selected from a wide variety of classes. Suitable classes F include anhydrides, esters, imides, lactams and acylated derivatives of imidazoles and oximes. Examples of useful materials within these classes are described in GB-A-1586789. Suitable esters are described in GB-A-836988, 864798, 1 147871, 2143231 and EP-A-0170386.

Residual groups The residual group, hereinafter group L, must be sufficiently reactive so that the perhydrolysis reaction occurs within the optimum time frame (e.g., a wash cycle). However, if L is very reactive, this activator will be difficult to stabilize for use in a bleaching composition. The preferred L groups are selected from the group consisting of: Ot O O - N - C - R1 -? N - - C- CH- R4 fe R5 Y I Y R3 Y - 0 - CH = C - CH = < CH, -O-CH = C- CH = CH2 and mixtures thereof, in which R ^ is an alkyl, aryl or alkaryl group containing 1 to 14 carbon atoms, R3 is an alkyl chain that contains 1 to 8 carbon atoms, R4 is H or R ^, R5 is a chain alkenyl containing 1 to 8 carbon atoms and Y is H or a group solubilizer. Any of Rl, R ^ and R4 can be essentially replaced by any functional group including, for example, alkyl, hydroxy groups, alkoxy, halogen, amine, nitrosyl, amide and ammonium or alkylammonium.

The preferred olubilizing groups are -SOs ^ M *, -C? 2"M +, - S? 4-M +, -N + (R3) 4X- and 0 < -N (R3) - and most preferably -S? 3"M + and -CO2 * M +, wherein R3 is an alkyl chain containing 1 to 4 carbon atoms, M is a cation that provides solubility to the bleach activator and X is an anion that provides solubility to the bleach activator. Preferably, M is an alkali metal, ammonium or substituted ammonium cation, F with sodium and potassium being preferred, and X is a halide, hydroxide, methylisulfate or acetate anion. 10 Perbenzoic acid precursor Perbenzoic acid precursor compounds provide • perbenzoic acid in the perhydrolysis. Suitable O-acrylated perbenzoic acid precursor compounds include the substituted and unsubstituted benzoyl oxybenzenesulfonates, including for example benzoyl oxybenzene sulfonate: The products of the benzoylation of sorbitol, glucose and all saccharides with benzoylating agents are also suitable, including for example: i_L *, i .- Ac = COCH3; Bz = Benzoyl 5 The perbenzoic acid precursor compounds of the imide type include N-benzoyl succinimide, tetrabenzoylethylenediamine and the N-benzoyl substituted ureas. Suitable midazole perbenzoic acid precursors F include N-benzoyl imidazole and N-benzoyl benzimidazole and other perbenzoic acid precursors containing a useful N-acyl group include N-benzoyl pyrrolidone, dibenzoyl taurine and benzoyl pyroglutamic acid. Other perbenzoic acid precursors include benzoyldiacyl peroxides, benzoyltetraacyl peroxides, and the compound having the F formula: Phthalic anhydride is another perbenzoic acid precursor compound suitable herein: Suitable N-acylated lactam perbenzoic acid precursors have the formula: wherein n is from O to 8, preferably from O to 2, and R6 is a benzoyl group.

Precursors derived from perbenzoic acid The precursors derived from perbenzoic acid provide perbenzoic acids substituted in the perhydrolysis. Suitable substituted perbenzoic acid-derived precursors include any of the perbenzoic precursors described herein in which the benzoyl group is substituted by any non-positively charged (i.e., non-cationic) functional groups including, for example, alkyl groups, hydroxy, alkoxy, halogen, amine, nitrosyl and amide. A preferred class of substituted perbenzoic acid precursor compounds are the substituted amide compounds of the following general formulas: R1- C-N-R2-C-L or R1-N- C-R2-C-L II I II L II II O R5 O R50 O wherein R1 is an aryl or alkaryl group with 1 to 14 carbon atoms, R2 is an alkarylene group containing 1 to 14 carbon atoms, and R ^ is H or an alkyl, aryl or alkaryl group containing 1 to 10 carbon atoms and L can be essentially any residual group. R1 preferably contains from 6 to 12 carbon atoms. R2 preferably contains from 4 to 8 carbon atoms. R1 may be aryl, substituted aryl or alkylaryl containing branching, substitution, or both and may originate from synthetic sources or natural sources including, for example, tallow fat. Analogous structural variations for R2 are permissible. The substitution may include alkyl, aryl, halogen, nitrogen, sulfur and other typical substituent groups or organic compounds. R5 is preferably H or methyl. R1 and R5 must not contain more than 18 carbon atoms in total. The 10 amide-substituted bleach activating compounds of this type are described in EP-A-0170386.

Cationic Peroxyacid Precursors Cationic peroxyacid precursor compounds produce cationic peroxyacids in perhydrolysis. Typically, the cationic peroxyacid precursors are formed by replacing the peroxyacid part of a suitable peroxyacid precursor compound with a positively charged functional group, such as an ammonium or alkylammonium group, preferably an ethyl group or 20 methylammonium. The cationic peroxyacid precursors are typically present in the compositions as a salt with a suitable anion, such as, for example, a halide ion or a methylisulfate ion.

The peroxyacid precursor compound which will be so cationically substituted may be a perbenzoic acid precursor compound or a substituted derivative thereof, as described hereinabove. Alternatively, the peroxyacid precursor compound may be a precursor alkylcarboxylic acid compound or an amide substituted alkylperoxyacid precursor as described hereinafter. Cationic peroxyacid precursors are described in the U.S. Patents. Nos. 4,751, 015; 4,988,451; 4,397,757; 5,269,962; 10 5,127,852; 5,093,022; 5,106,528; U.K. 1, 382.594; EP 475,512, 458,396 and 284,292; and in JP 87-318,332. Suitable cationic peroxyacid precursors include • any of the substituted alkyl or benzoyloxybenzene sulphonates of ammonium or substituted alkylammonium, the N-acylated caprolactams and the benzoylperoxides of monobenzoyltetraacetyl glucose. A preferred cationically substituted benzoyloxybenzenesulfonate is 4- (trimethylammonium) methyl derivative of benzoyloxybenzene sulfonate: A preferred cationically substituted alkyloxybenzene sulphonate has the formula: Preferred cationic peroxyacid precursors of the N-acylated caprolactam class include the methylenebenzoyl-saprolactams of ^ W F trialkylammonium, particularly the trimethylammonium methylenebenzoyl caprolactams: ^^ Other preferred cationic peroxyacid precursors of the N-acylated caprolactam class include the methylenealkyl caprolactams of 15 trialkylammonium: Another preferred cationic peroxyacid precursor is 2- (N, N) N -trimethyl ammonium) ethylsodium 4-sulfophenyl carbonate chloride.

Precursors of germanic acid carboxylic acid blanoueb The precursors of bleaching of atcarboxycarboxylic acid form percarboxylic acids in the perhydrolysis. Preferred precursors of this type provide peracetic acid in the perhydrolysis. 5 The alkylpercarboxylic acid precursor compounds Preferred of the metric type include the N, NN, N, N-tetraacetylated alkylene diamines in which the alkylene group contains from 1 to 6 carbon atoms, particularly those compounds in which the alkylene group contains 1, 2 and 6 carbon atoms . Tetraacetylethylenediamine (TAED) is particularly preferred. Other preferred alkylpercarboxylic acid precursors include sodium 3,5,5-trimethylhexanoyloxybenzenesulfonate (iso-NOBS), sodium nonailoxybenzenesulfonate (NOBS), sodium acetoxybenzenesulfonate (ABS) and pentaacetylglucose. 15 Alkyl precursors Ixylacid substituted with amide The amide substituted alkylperoxy acid precursor compounds are also suitable, including those of the following formulas W mW general: 20 R1- C-N-R2-C-L or R1-N- C-R2-C-L ll l II L II II O R5 O R50 O wherein R1 is an alkyl group of 1 to 14 carbon atoms, R2 is an alkylene group containing 1 to 14 carbon atoms, and R5 is H or an alkyl group containing 1 to 10 carbon atoms and L can be essentially any residual group. R1 preferably contains from 6 to 12 carbon atoms. R2 preferably contains from 4 to 8 carbon atoms. R1 may be straight or branched chain alkyl containing branching, substitution, or both and may originate from synthetic sources or natural sources including, for example, tallow fat. Analogous structural variations for R2 are permissible. The substitution may include alkyl, aryl, halogen, nitrogen, sulfur and other typical substituent groups or organic compounds. R5 is preferably H or methyl. R1 and R5 must not contain more than 18 carbon atoms in total. Amide-substituted bleach activating compounds of this type are described in EP-A-0170386.

Benzoxazine organic peroxyacid precursors Also suitable are the benzoxazine type precursor compounds such as those described for example in EP-A-332,294 and EP-A-482,807, particularly those having the formula: including benzoxazines substituraás of the type: wherein Ri is H, alkyl, alkaryl, aplo, arylalkyl, and wherein R 2, R 3, R 4 and R 5 may be the same or different substituents selected from H, 9 'halogen, alkyl, alkenyl, aryl, hydroxyl, alkoxy, amino, alkylamino, COOR6 (in which R6 is H or an alkyl group) and carbonyl functions. An especially preferred precursor of the benzoxazine type is: 15 Preformed organic peroxyacid The organic peroxyacid bleach system may contain, in addition to, or as an alternative to, an organic peroxyacid bleach precursor compound, a preformed organic peroxyacid, ^^^ typically at a level of 0.5% to 25% by weight, more preferably 1% at 20% by weight of the composition. A preferred class of organic peroxyacid compounds are the amine substituted compounds of the following general formulas: R1- C-N-R2- C-OOH # 1 'N-C-R2-C-OOH II I II I II II O R5 OR R5 O O wherein R1 is an alkyl, aryl or alkaryl group with from 1 to 14 atoms carbon, R2 is an alkylene, arylene and alkarylene group containing 1 to 14 carbon atoms, and R ^ is H or an alkyl, aryl or alkaryl group containing from 1 to 10 carbon atoms. R1 preferably contains from 6 to 12 carbon atoms. R2 preferably contains from 4 to 8 carbon atoms. R1 may be straight or branched chain alkyl containing branching, substitution, or both and may originate from synthetic sources or natural sources including, for example, tallow fat. Variations are permissible structural analogues for R2. The substitution may include alkyl, aryl, halogen, nitrogen, sulfur and other typical substituent groups or organic compounds. R5 is preferably H or methyl. R1 and R5 must not contain more than 18 carbon atoms in total. Amide-substituted organic peroxy acid compounds of this type are described in EP-A-0170386. Other organic peroxyacids include diacyl and tetraacylperoxides, especially diperoxydodecanoic acid, diperoxytetradecanedioic acid and diperoxyhexadecanedioic acid. The peroxide Dibenzoyl is a preferred organic peroxyacid herein. They are also suitable herein are mono- and diperazelaic acid, mono- and diperbrasilíco. i The monoperoí farbóxílicos acids. preformed (hereinafter referred to as pethidrite) suitable for use herein are mono-peracids, which means that the peracid contains a peroxygen group. Preferably the peracid is in solid form. In a preferred embodiment of the present invention, the peracid has the general formula: X-R-C (0) OOH ^^ wherein R is a linear or branched alkyl chain having at least one 10 carbon atom and X is hydrogen or a substituent group selected from the group consisting of alkyl, especially alkyl chains of 1 to 24 carbon atoms, aryl, halogen, ester, ether, amine, amide, amino phthalic f. substituted, imide, hydroxide, sulfide, sulfate, sulfonate, carboxylic, hetercyclic, nitrate, aldehyde, phosphonate, phosphonic or mixtures thereof. More particularly, the R group preferably comprises up to 24 carbon atoms. Alternatively, the R group may be a branched alkyl chain comprising one or more side chains comprising substituent groups selected from the group consisting of aryl, halogen, ester, ether, amine, amide, substituted phthalic amino, imide, 20 hydroxide, sulfide, sulfate, sulfonate, carboxylic, hetercyclic, nitrate, aldehyde, ketone or mixtures thereof.

In a peracid I preferred the group X, according to the previous general formula, it is a phthalimide group. Accordingly, particularly preferred peracids are those that have the formula generates: wherein R is C1-20 and wherein A, B, C and D are independently hydrogen groups or substituents selected from the group consisting of alkyl, hydroxyl, nitro, halogen, amine, ammonium, cyanide, carboxylic, sulfate, sulfonate, aldehydes and mixtures thereof. In a preferred aspect of the present R is an alkyl group having from 3 to 12 carbon atoms, more preferably from 5 to 9 carbon atoms. Preferred substituent groups A, B, C and D are linear or branched alkyl groups having from 1 to 5 carbon atoms, but more preferably hydrogen. The preferred peracids are selected from the group consisting of phthaloylamido peroxyhexanoic acid, phthaloylamido peroxyheptanoic acid, phthaloylamido peroxyoctanoic acid, phthalosylamido peroxynanoic acid, phthaloylamido peroxydecanoic acid and mixtures thereof. In a particularly preferred aspect of the present invention, the peracid has the formula such that R is C5H10, ie, phthaloylamido peroxyhexanoic acid, or PAP. This peracid is preferably used as a wet or solid cake, which is virtually insoluble in water and is available from Ausimont under the trade name Euroco. The peracid is preferably used at a level of from 0.1% to 30%, more preferably from 0.5% to 18% and more preferably from 1% to 12% by weight of the composition.

Bleach Catalyst Containing Metal The compositions described herein that contain bleach as an active detergent component may contain 10 additionally as a preferred component a bleaching catalyst 'that contains metal. Preferably the bleaching catalyst that confers F, metal is a bleaching catalyst containing transition metal, more * preferably a bleach catalyst containing manganese or cobalt. The compositions of the present invention may comprise an effective amount of a bleach catalyst. The term "an effective amount" is defined as "an amount of the transition metal bleach catalyst present in the compositions of the present invention, or during use in accordance with the methods of The present invention, which is sufficient, under any conditions that are used comparatively or of use, to result in at least partial oxidation of the materials that are intended to be oxidized by the composition or method ".

Preferably the orfloflions of the present invention comprise from 1 ppb 0.0000001%), more preferably from 100 ppb (0.00001%), even more preferably from 500 ppb (0.00005%), even more preferably from 1 ppm (0.0001%) to 99.9%, more preferably at 50%, still more preferably at 5%, still more preferably at 500 ppm (0.05%) by weight of the composition, of a metal bleach catalyst as described hereinafter. A suitable type of bleach catalyst is a catalyst comprising a heavy metal cation of defined bleach catalytic activity, such as copper cations, iron, an auxiliary metal cation having little or no catalytic bleaching activity, such as cations of zinc or aluminum, and a scavenger having defined stability constants for the auxiliary metal and catalytic cations, particularly ethylenediaminetetraacetic acid, ethylenediaminetetra- (methylene phosphonic acid) and the water soluble salts thereof. Said catalysts are described in the patent of E.U.A. No. 4,430,243. Preferred types of bleach catalysts include the manganese-based complexes described in the U.S.A. No. 5,246,621 and in the patent of E.U.A. No. 5,244,594. Preferred examples of these catalysts include Mn'V2 (u-0) 3 (1, 4,7-trimetiM, 4,7-triazacyclononane) 2- (PF6) 2, Mnl || 2 (u-0)? (u-OA O, 4,7-trimethyl-1, 4,7-triazacyclononane) 2- (Cl? 4) 2, MnlV4 (u-0) E? (1, 4,7-triazacyclononane) 4- (Cl? 4) 2, Mn '|| Mn'V4 (u-0)? (u-0Ac) 2 < 1, 4,7-tri? I, 4,7-triazacictononane) 2- (Cl? 4) 3 and mixtures thereof. Others are described in the publication of European Patent Application No. 549,272. Other ligands suitable for use herein include 1, 5,9-trimethyl-1, 5,9-triazacyclododecane, 2-methyl-1, 4,7- 5 triazacyclononane, 2-methyl-1, 4,7-tpazacyclononane, 1,2,4,7-tetramethyl-1, 4,7-triazacyclononane and mixtures thereof. The bleach catalysts used in the present compositions may also be selected as is suitable for the present invention. For examples of suitable bleach catalysts 10 see U.S. Patent No. 4,246,612 and U.S. Patent No. No. 5,227,084. See also the patent of E.U.A. No. 5,194,416, which teaches mononuclear manganese (IV) complexes such as Mn (1,4,7-trimethyl-1,4,7-triazacyclononane) (OCH 3) 3 (PF 6). Still another type of bleaching catalyst as described in 15 patent of E.U.A. No. 5,114,606, is a water-soluble complex of manganese (III) and / or (IV) with a ligand that is a non-carboxylate polyhydroxy compound having at least three consecutive C-OH groups. Preferred Hgandos include sorbitol, iditol, dulsitol, mannitol, xylitol, * BF arabitol, adonitol, meso-erythritol, meso-isonitol, lactose, and cough mixtures 20 same. U.S. Patent No. 5,114,611 teaches a bleach catalyst comprising a complex of transition metals, including Mn, Co, Fe, or Cu, with a l} §nda nll ílferb) * cíctfct > . These Kgandos are of the formula: R2 R3 R1- N = C 1- B-C i = N-R4 wherein R1, R2, R3 and R4 can each be selected from H, substituted alkyl and aryl groups such that each R1-N = C-R2 and R3-C = N-R4 form a five or six membered ring . Said ring can be replaced additionally. B is a bridging group selected from O, S, CR5R6, NR7 and C = 0, wherein R5, R6 and R7 may each be H, alkyl or aryl groups, including substituted or unsubstituted groups. Preferred ligands include pyridine, pyridazine, pyrimidine, pyrazine, imidazole, pyrazole, and triazole rings. Optionally, said rings can be substituted with substituents such as alkyl, aryl, alkoxy, halogenide, and nitro. Particularly preferred is the 2,2'-bispyridylamine ligand. Preferred bleach catalysts include complexes of Co, Cu, Mn, Fe, -bispyridylmethane and -bispyridylamine. Highly preferred catalysts include Co (2,2'-bispyridiamide) CI2, Di (isothiocyanate) bispyridylamine-cobalt (II), trisdispyridylamine-cobalt perchlorate (II), Co (2,2'-b-pyridylamine ) 202CI04, Bis- (2,2'-bispyridylamine) copper perchlorate (ll), iron tris (di-2-pyridylamine) perchlorate (II), and mixtures thereof.

Preferred examples include bnuclear Mn in complex with tetra-N-deaminated and bi-N-dentate ligands, including N4Mn "^ (u- 0) 2Mn'vN4) + y [B¡py2Mn '"(u-0) 2Mnlvbipy2] - (CI04) 3. Although the structures of the manganese complexes 5 bleach catalysts of the present invention have not been elucidated, it can be speculate that they comprise chelators or other hydrated coordination complexes that result from the interaction of the carboxyl and nitrogen atoms of the ligand with the manganese cation.Similarly, the oxidation state of the manganese cation during the The catalytic process is not known with certainty, and it can be the valence state (+ II), (+ III), (+ IV), or (+ V). Due to the six possible points of adhesion of the ligand to the manganese cation, it can be speculated reasonably that multi-nuclear species and / or "cage" structures may exist in the aqueous bleaching medium. Whatever the form 15 in which the active Mn ligand species can currently exist function in an apparently catalytic manner to provide improved bleaching performance on difficult soils such as tea, tomato sauce, coffee, wine, juice and the like. • Other bleach catalysts are described, for example, in the European Patent Application No. 408,131 (Cobalt Complex Catalysts), European Patent Applications Publication Nos. 384,503 and 306,089 (Metalloporphyrin Catalysts), E.U.A. 4,728,455 (manganese / multidentate ligand catalyst), E.U.A. 4,711, 748 and patent application European Publication No. of manganese absorbed on aluminosilicate), E.U.A. 4,601, 845 (aluminosilicate support with manganese and zinc or magnesium sai), E.U.A. 4,626,373 (manganese / ligand catalyst), E.U.A. 4,119,557 (ferric complex catalyst), German patent specification 2,054,019 (cobalt chelator catalyst), Canadian 866,191 (salts containing transition metals), E.U.A. 4,430,243 (chelators with manganese cations and cations of Non-catalytic F metal) and E.U.A. 4,728,455 (manganese gluconate catalysts). Other preferred examples include cobalt (III) catalysts having the formula: F Co [(NH3) nM'mB'bT'tQqPp] Yy in which the cobalt is in the oxidation state +3, n is an integer from 0 to 5 (preferably 4 or 5, more preferably 5); M 'represents a monodentate ligand; m is an integer from 0 to 5 (preferably 1 or 2, more preferably 1); B 'represents a bidentate ligand; b is an integer from 0 to 2; T'represents a tridentate ligand; t is 0 or 1; Q is a tetradenthate ligand; q is 0 or 1; P is a pentadentate ligand; p is O or l; and n + m + 2b + 3t + 4q + 20 5p = 6; Y is one or more selected counterions suitably present in a number y, where y is an integer from 1 to 3 (preferably 2 to 3, more preferably 2 when Y is a charged anion -1), to obtain a balanced charge salt , the preferred Y is selected from the group consisting of clomor, nitrate, nitrite, sulfate, tetrahydrate, carbonate, and combinations thereof; and in which in addition to the one of the coordination sites adhered to the cobalt is labile under the use of an automatic machine for dishwashing and the remaining coordination sites stabilize the cobalt under conditions of automatic dishwashing machine. Thus, the reduction potential of cobalt (III) to cobalt (II) under alkaline conditions is less than 0.4 volts (preferably less than 0.2 volts) versus a normal hydrogen electrode. Preferred cobalt catalysts of this type have the 10 formula: [Co (NH3) n (M ') m] Yy wherein n is an integer from 3 to 5 (preferably 4 or 5, more preferably '5); M "is a labile coordinating portion, preferably selected from the 15 group consisting of chlorine, bromine, hydroxide, water and (when m is larger than 1) combinations thereof; m is an integer from 1 to 3 (preferably 1 or 2, more preferably 1); m + n = 6; and Y is a selected counterion suitably present in a number y, which is an integer from 1 to 3 (preferably 2 to 3, more preferably 2 when Y is an anion ^^ ^ 20 loaded -1) to obtain a balanced load salt. The preferred cobalt catalyst of this type useful herein are cobalt pentaamine chloride salts having the formula [Co (NH3) 5CI] Yy, and especially [Co (NH3) 5CI] CI2.

Most preferred are the methods of the present invention which utilize cobalt bleach catalysts (III) having the formula: [Co (NH3) n (M) m (B) b] Ty 5 in which the cobalt is in the +3 oxidation state; n is 4 or 5 (preferably 5); M is one or more ligands coordinated to cobalt by a site; m is 0, 1 or 2 (preferably 1); B is a ligand coordinated to • cobalt through two sites; b is 0 or 1 (preferably 0), and when b = 0, then m + n = 6, and when b = 1, then m = 0 and n = 4; and T is one or more 10 selected selected counterions present in a number and, where y is an integer to obtain a balanced charge salt (preferably y is 1 to 3, more preferably 2 when T is a charged anion -1); and wherein said catalyst additionally has a constant base hydrolysis rate of less than 0.23 M "1 s" 1 (25 ° C). The preferred T is selected from the group consisting of clomor, iodide, b-, formate, nitrate, nitrite, sulfate, sulfite, citrate, acetate, carbonate, bromide, PF6", BF", B (Ph) ", phosphate, phosphite , silicate, tosylate, methanesulfonate, and combinations thereof Optionally, T may be protonated if there is more than one anionic group in T, for example, HP042", HCO3", H2PO4", ^^ f 20 etc. Additionally, T can be selected from the group consisting of non-traditional inorganic anions such as anionic surfactants (for example linear alkylbenzene sulphonates (LAS), alkyl sulfates (AS), ^ 3 alkylethoxysulfonates (AES), etc.) #################################################### The M portions include, but are not limited to, for example, F ", S04" 2, NCS ", SCN". S203"2, NH3, P043", and carboxylates (which Preferably they are monocarboxylates, but more than one carboxylate may be present in the portion as long as the cobalt linkage is only one carboxylate per portion, in which case the other carboxylate in the M portion can be protonated or in the form of its salt). Optionally, M can be protonated if there is more than one anionic group in M (eg, 10 HP042", HC03", H2P04", HOC (0) CH2C (0) 0-, etc.). The preferred M-portions are acidic. substituted and unsubstituted C1-C30 carboxylic acids having ^ ~ * formulas: "RC (?) o- in which R is preferably selected from the group consisting of hydrogen 15, and substituted and unsubstituted C 1 -C 30 alkyl (preferably C Ciß), C 6 -C 30 aryl (preferably C 1) -Ciß) substituted and unsubstituted and C3-C30 (preferably C5-C18) substituted and unsubstituted heteroaryl, in which the substituents are selected from the group consisting of -NR'3 > -NR '+, - C (0) OR', -OR ', -C (0) NR'2, in which R' is selected from the consistent group 20 of hydrogen and portions of Ci-Cß. Said substituted R thus includes the portions - (CH2) nOH and - (CH2) nNR'4 +, in which n is an integer from 1 to 6, preferably from 2 to 10, and more preferably from 2 to 5.

The most preferred M are carboxylic acids having the above formula wherein R is selected from the group consisting of hydrogen, mephyl, ethyl, propyl, straight or branched C4-C12 alkyl, and benzyl. The most preferred R is methyl. Preferred M-moieties of carboxylic acid include formic, benzoic, cationic, nonanoic, decanic, dodecanoic, malonic, maleic, succinic, adipic, phthalic, 2-ethylenexanic, naphthenic, oleic, palmitic, triflate, tartrate, stearic, butyric, citric, acrylic, aspartic, F fumárico, laurico, linoleic, lactic, malic, and especially acetic. The B portions include carbonate, di- and higher carboxylates 10 (for example oxalate, malonate, malic, succinate, maleate), picolinic acid, and alpha and beta amino acids (for example glycine, alanine, beta-alanine, phenylalanine). '^ mw The cobalt bleach catalysts useful herein are known, being described for example together with their hydrolysis rates 15 of base in M. L. Tobe, "Base Hydrolysis of Transition-Metal Complexes", Adv. Inoro. Bioinorg. Mech .. (1983), 2, pages 1-94. For example, Table 1 on page 17 provides base hydrolysis rates (designated as koi) for cobalt pentaamine catalysts that form ^ K f complex with oxalate (kO = 2.5 x 10"4 m" 1 s "1 (25 ° C)), NCS- (kOH = 5.0 x 10" 4 m "1 20 s "1 (25 ° C)), format (kOH = 5.8 x 10" 4 m "1 s" 1 (25 ° C)) and acetate (kOH = 9.6 x 10"4 m" 1 s "1 (25 C)). The most preferred cobalt catalysts useful herein are the salts of cobalt pentaamtnoacetate having the formula [Co (NH3) _5? Ac] Ty, wherein OAc represents an acetate portion, and especially domro de dé cobalto, [C? (NH3) 5? AcJCl2 as well as [Co (NH3) 5OAc] (OAc) 2); [Co (NH3) 5? Ac] (PF?) 2; [Co (NH3) 5OAc] (S04); [Co (NH3) 5OAc] (BF4) 2; and [Co (NH3) 5? cKN03) 2 (in the present "CAP"). These cobalt catalysts are readily prepared by known procedures, as taught for example in the Tobe article above and the references cited therein, in the U.S. Patent. No. 4,810,410, to Diakun et al, issued March 7, 1989, J. Chem. Ed. (1989), 66 (12), 1043-45; The Synthesis and Characterization of Inorganic 10 Compounds, W.L. Jolly (Prentice-Hall, 1970), pp. 461-3; Inorg. Chem .. 18, 2023-2025 (1979); Inorg. Synthesis, 173-176 (1960); and Journal of Phvsieal. Chemistrv, 56, 22-25 (1952); as well as the synthesis examples provided hereinafter. Cobalt catalysts suitable for incorporation into the detergent compositions of the present invention can be produced in accordance with the synthetic moieties described in the patents of E.U.A. Nos. 5,559,261, 5,581, 005, and 5,597,936, the disclosure of which is incorporated herein by reference. ^^^ Other suitable bleach catalysts include transition metal bleach catalysts comprising: i) a transition metal selected from the group consisting of Mn (ll), Mn (lll), Mn (IV), Mn (V), Fe (ll), Fe (lll), Fe (IV), Co (l), Co (ll), Co (lll), Ni (l), Ni (ll), Ni (lll), Cu (l), Cu (ll), Cu (lll), Cr (ll), Cr (lll), Cr (IV), Cr (V), Cr (VI), V (IH), V (IV), V (V), Mo (IV), Mo (V), Mof) JW ff) and W (V), W (VI), Pd («), Ru (ll), Ru (* H) and Ru < IV), preferably Mn (ll), Mn (lll), Mn (IV), Fe (ll), Feftl), Fe (IV), Cr (ll), Cr (lll), Cr (IV), Cr (V ) Cr (VI), and mixtures thereof; ii) a macropolyclical cross-linked ligand coordinated by four or five donor atoms to the same transition metal comprising: a) an organic macrocyclic ring containing four or more F donor atoms (preferably at least 3, most preferably at least 4, of these donor atoms are N) separated from each other by 10 covalent bonds of 2 or 3 non-donor atoms, two to five (preferably three to four, most preferably four) of these donor atoms being coordinated to the same transition metal atom in the ^ W r. complex; (ii) b) a crossed bridge chain, which covalently connects at least 2 non-adjacent donor atoms of the organic macrocyclic ring, said non-adjacent covalently connected donor atoms are donor bridgehead atoms that are coordinated with the same metal of transition in the complex, and wherein said crossed bridge chain comprises from 2 to 10 atoms (preferably the chain of 20, crossed bridge is selected from 2, 3 or 4 non-donor atoms, and 4-6 non-donor atoms with a additional donor atom); and iii) optionally, one or more non-macropolicic ligands preferably selected from the group consisting of H 2 O, ROH, NR 3, RCN, OH ", OOH-, RS", RO ", RCOO", OCN; SCN ', N3", CN", F ", Cl", Br ", I", 02", N03", N02", S0 2", S032", P0 3", organic phosphates, organic phosphonates, organic sulfates, organic sulfonates, and aromatic N-donors such as pyridines, pyrazines, pyrazoles, imidazoles, benzimidazoles, pyrimidines, triazoles and thiazoles with R being H, optionally substituted alkyl, optionally substituted aryl. The preferred cross-linked macropolycyclic ligands are select from the group consisting of: a) a macropolycyclic cross bridge ligand of formula (I) having denticity of 4 or 5: • d); B) a macropolycyclic bridged ligand of formula (II) having denticity of 5 or 6: c) the cross-linked macropolycyclic ligand of formula (III) having denticity of 6 or 7: ("i); where each unit E represents the portion that holds the formula (CRn) a-X- (CRn) a ', s? BSí jsas "X" "1 § £" 3 * "-fen bde X is selected from the group consisting of oxyglyph, sulfur1, -f? * -, phosphorus, or X represents a covalent bond where E has the formula: (CRn) a- (CRn) a 'for each unit E the sum of a + a 'is independently selected from 5 1 to 5, each unit G is a portion (CRn) b, each unit R is independently selected from H, alkyl, alkenyl, alkynyl, aryl, alkylaryl, alkylaryl, and heteroaryl, or two or more R units are covalently linked to form an aromatic, heteroaromatic, cycloalkyl, or heterocycloalkyl ring, each unit D is a donor atom independently selected from the group consisting of nitrogen, oxygen, sulfur, and phosphorus , and at least two atoms comprising D units are bridgehead donor atoms coordinated with the transition metal, the B units are a carbon atom, a D unit, or a cycloalkyl or heterocyclic ring, each n being a whole independently selected from 1 and 2, 15 completing the valence of the carbon atoms to which the R units are covalently bound; each n 'is an integer independently selected from 0 and 1, completing the valence of donor atoms D to which the R portions are covalently bound; every n "is a whole Wm independently selected from 0, 1, and 2 by completing the valence of the 20 B atoms to which the R portions are covalently bound; each aya 'is an integer independently selected from 0 to 5, where the sum of all a + a' values in the ligand of formula (I) is within the range of about 8 to about 12, the sum of all the values a + a 'in the ligand of formula (II) is found within the scale c approximately 10 to approximate, and the sum of all values a + a 'in the ligand of formula (III) is within the range of about 12 to about 18; each b is an integer 5 independently selected from 0 to 9, or in any of the above formulas, one or more of the portions (CRn) b covalently linked from any atom D to B are absent as long as at least two (CRn ) b covalently link two of the donor atoms D to atom B in the formula, and the sum of all the indices b lies within the range of about 2 to about 5. An additional description of the bleach catalysts of the present invention The invention can be found in WO 98/39406 F A1, published on September 11, 1998, WO 98/39098 A1, published September 11, 1998, and WO 98/39335 A1, published on September 11, 1998, all of which are included herein. reference. The nomenclature herein to describe transition metal bleach catalysts is the same style of nomenclature that is used in the references mentioned above. However, the F chemical names of one or more ligands that are described herein may vary from the chemical name assigned under the rules of the International Union of Pure and Applied Chemistry (IUPAC). For example, a preferred ligand for the purposes of the present invention, 5,12-dimethyl-1, 5,8,12-tetraaza-bicyclo [6.6.2] hexadecane, has the name IUPAC 4,11-dimefil- s I * 1, 4,8,11-tetraaza-bicyclo [6? 6t2] h ^ xadecane. Additional preferred ligand Jn is 5,12-dimethyl-1,5,8,12-tetraaza-bicyclo [6.6] phydecacane. Bleach catalysts useful in the compositions of the invention may generally include known compounds wherein they conform to the definition of the invention, as well as, more preferably, any of a large number of new compounds expressly designed for the purpose of the invention. use in present laundry. The bleach catalysts # suitable for use in the compositions herein further include, for example: Dichloro-5,12-dithmet-1, 5,8,12-tetraazabicyclo [6.6.2] hexadeca Manganese (ll); Dichloro-4,10-dimethyl-1,4,7,10-tetraazabicyclo [5.5.2] tetradecan Manganese (II); Hexafluorophosphate of Diaquo-5,12'-dimethyl-1, 5,8,12-15 tetraazabicyclo [6.6.2] hexadecane Manganese (ll); Hexafluorophosphate of Aquo-hydraxy-5,12 * d-methyl-1, 5,8,12- "tetraazabicyclo [6.6.2] hexadecane Manganese (III); Diax-4,10-dimethyl-1,4,7,10-flv tetraazabicyclo [5.5.2] tetradecane Manganese (II) hexafluorophosphate; 20 Diaquo-5,12-dimethyl-1, 5,8,12-tetraazabicyclo [6.6.2] hexadecane Manganese tetrafluoroborate (II); Tetrafluoroborate of diaquo-4,10 * dimethyl-1, 4,7,10-tetraazabicyclo [5.5.2] tetradecane Manganese (II); Hexafluorophosphate of t »chloro-5,12-dimethyl-1, 5,8,12-tetraazabicyclo [6.6.2] hexadecane Mangan 5Ó (IN); Dichloro-5,12-di-n-butyl-1, 5,8,12-tetraaza-bicyclo [6.6.2] hexadecane Manganese (ll); 5 Dichloro-5, 12-d? Benc? L-1, 5,8,12-tetraazabic? Clo [6.6.2] hexadecane Manganese (ll); Dichloro-5-n-butyl-12-methyl-1, 5,8,12-tetraaza • bicyclo [6.6.2] hexadecane Manganese (ll); Dichloro-5-n-octyl-12-methyl-1, 5,8,12-tetraaza-10 bicyclo [6.6.2] hexadecane Manganese (ll); Dichloro-5-n-butyl-12-methyl-1, 5,8,12-tetraazabicyclo [6.6.2] hexadecane Manganese (II); Dichloro-5,12-dimethyl-1, 5,8,12-tetraazabicyclo [6.6.2] hexadecane Iron (II); Dichloro-4,10-dimethyl-1, 4,7,10-tetraazabicyclo [5.5.2] tetradecane Iron (II); Dichloro-5,12-dimethyl-1, 5,8,12-tetraazabicyclo [6.6.2] hexadecane Copper (II); j Dichloro-4,10-dimethyl-1, 4,7,10-tetraazabicyclo [5.5.2.] tetradecane 20 Copper (II); Dichloro-5,12-dimethyl-1, 5,8,12-tetraazab-Cyclo. { 6.6.2] hexadecane Cobalt (II); Dichloro-4, 1 Cobalt (II); Dichloro 5,12-dimefyl-4-phenyl-1, 5,8, 12-tetraazabicyclo [6.6.2] hexadecane Manganese (ll); Dichloro-4,10-dimethyl-3-phenyl-1,4,7,10-tetraazabicyclo [5.5.2] tetradecane Manganese (II); Dichloro-5, 12-dimethyl-4,9-diphenyl-1, 5,8,12-tetraazabicyclo [6.6.2] hexadecane Manganese (ll); Dichloro-4,10-dimethyl-3,8-diphenyl-1,4,7,10-tetraazabicyclo [5.5.2] tetradecane Manganese (II); Dichloro-5,12-dimethyl-2,11-defense-1, 5,8,12-tetraazabicyclo [6.6.2] hexadecane Manganese (II); Dichloro-4, 10-dimethyl-4,9-diphenyl-1,4,7,10-tetraazabicyclo [5.5.2] tetradecane Manganese (II); Dichloro-2,4,5,9,11,16-hexamethyl-1, 5,8,12-tetraazabicyclo [6.6.2] hexadecane Manganese (ll); Dichloro-2,3,5,9, 10,12-hexamethyl-1, 5,8, 12-tetraazabicyclo [6.6.2] hexadecane Manganese (ll); Dichloro-2,2,4,5,9,9,11,18-octamethyl-1, 5,8,12-tetraazabicyclo [6.6.2] hexadecane Manganese (II); Dichloro-2,2,4,5,9,11,11,18-octamethyl-1, 5,8,12-tetraazabicyclo [6.6.2] hexadecane Manganese (II); Dicyro-3,3,5,10,1O, 12-hexmettNf, d, 8, f2-tetraazabicyclo [6.6.2] hexadecane Mangan afll); Dichloro-3,5, 10, 12-tetramethyl-1, 5,8,12-tetraazabicyclo [6.6.2] hexadecane Manganese (ll); D? Chloro-3-butyl-5, 10,12Jrimet? L-1, 5,8,12-tetraazabicyclo [6.6.2] hexadecane Manganese (ll); Dichloro-1, 5,8,12-tetraazabicyclo [6.6.2] hexadecane Manganese (ll); Dichloro-1, 4,7,10-tetraazabicyclo [5.5 2] tetradecane Manganese (H); Dichloro-1, 5,8,12-tetraazabicyclo [6.6.2] hexadecane iron (II); Dichloro-1, 4,7,10-tetraazabicyclo [5.5.2] tetradecane iron (II); Aquo-chloro-2- (2-hydroxyphenyl) -5,12-dimethyl-1, 5,8,12-tetraazabicyclo [6.6.2] hexadecane Manganese (II); Aquo-chloro-10- (2-hydroxybenzyl) -4,10-dimethyl-1, 4,7,10-tetraazabicyclo [5.5.2] tetradecane Manganese (II); Chloro-2- (2-hydroxybenzyl) -5-methyl 1,5,8,8-tetraazabicyclo [6.6.2] hexadecane Manganese (ll); Chloro-10- (2-hydroxybenzyl) -4-methyl-1, 4,7,10-letraazabicyclo [5.5.2] tetradecane Manganese (II); Chloro-5-methyl-12- (2-picolyl) -1,5,8,12-etraazabicyclo [6.6.2] hexadecane Manganese (ll); Chloro-4-methyl-10- (2-piccolyl) -1,4,7,10-tetraazabicyclo [5.5.2] tetradecane Manganese (II); Dichloro-5- (2 * sulfate) dodecylH2 * 1I5r8, 2-tetraazabicyclo [6.6.2] hexadecane Aquo-Chloro- (fe sulfate) dodecyl-12-methyl-1, 5,8,12-tetraazabicyclo [6-.6.2] hexadecane Manganese (ll); Aquo-Chloro-5- (3-sulfonopropyl) -12-methyl-1, 5,8, 12-tetraazabicyclo [6.6.2] hexadecane Manganese (II); Chloride of Dichloro-5- (Trimethylammoniumpropyl) dodecyl-12-methyl-1, 5,8,12-tetraazabicyclo [6.6.2] hexadecane Manganéso (Ill); Dichloro-5,12-dimethyl-1, 4,7,10,13-pentaazabicyclo [8.5.2] heptadecane Manganese (ll); D -doro-14,20-d-methyl-1, 10,14,20-tetraazatriiclo [8.6.6] docosa-3 (8), 4,6-triene Manganese (ll); Dichloro-4,11-dimethyl-1, 4,7,11-tetraazabicyclo [6.5.2] pentadecane Manganese (II); Dichloro-5,12-dimethyl-1, 5,8,12-tetraazabicyclo [7.6.2] heptadecane Manganese (ll); Dichloro-5,13-dimethyl-1, 5,9,13-tetraazabicyclo [7.7.2] heptadecane Manganese (II); Dichloro-3,10-bis (butylcarboxy) -5,12-dimethyl-1, 5,8,12-tetraazabicyclo [6.6.2] hexadecane Manganese (II); Diaquo-3,10-dicarboxy-5,12-dimethyl-1, 5,8,12-tetraazabicyclo. { 6.6.2] Manganese hexadecane (ll); Hexafl tetracycle [7.7.7J3 J manganese (ll); Trifluoromethanesulfono-20-methyl-1, 9,20,24,25-pentaaza-5-tetracyclo [7.7.7 13 7J 11 15.] pentacosa-3,5,7 (24), H J3,15 (25) -hexaeno Manganese (ll) Tfluoromethanesulfonate, Trifluoromethanesulfone-20-methyl-1,9,20) 24,25-pentaaza-tetracycle [7.7.7J3'7J 11'15.] Pentacosa-3,5,7 (24), 11, 13 , 15 (25) -hexane Iron (ll) Trifluoromethanesulfonate; 10 Chloro-5 hexafluorophosphate, 12,17-trimethyl-1, 5,8,12,17-pentaazabicyclo [6.6.5] nonadecane Manganese (II); Chloro-4,10,15-trimethyl-1, 4,7,10,15-A 'pentaazabicyclo [5.5.5] heptadecane Manganese (II) hexafluorophosphate; Chloro-5,12,17-trimethyl-1, 5,8,12, 7- 15 pentaazabicyclo [6.6.5] nonadecane Manganese (II); Chlorine Cl.lO.ld.-trimethyl-1H.IO.Id-pentaazabicyclo [5.5.5] heptadecane Manganese (II); Dichloro 5,12,15,16-tetramethyl-1, 5,6,12-tetraazabicyclo [6.6.2] hexadecane Manganese (II); and ^ w 20 Chloro 5-methyl-12- (2'-oxobenzyl) -1,5,8,12-tetraazabicyclo [6.6.2] hexadecane Manganese (II). Additional suitable complexes useful as transition metal bleach catalysts additionally include not only monometallic, mononuclear types such as those illustrated above, but also bimewfiÉfe, fr'mrietálícos or cluster types. The monometallic, mononuclear compounds are preferred. as defined herein, a monometallic transition metal bleach catalyst contains only one transition metal atom per mole of complex. A mononuclear, monometallic complex is one in which any donor atoms of the essential macrocyclic ligand are bonded to the same transition metal atom, i.e., the essential ligand "does not bridge" through two or more transition metal atoms. Additional examples of manganese transition metal complexes are the complexes of manganese (III) and manganese (IV) having the general formula: in which X is independently a coordinating or training species 25 of bridge non-limiting examples of which are H20, 022 ', -OH, H02", SH', H ^^ S2",> SO, Cl", SCN ", N3", N3", RS03", RCOO ", NH2 \ and NR3, where R is H, alkyl, aryl, each of which is optionally substituted, and R 1 COO, wherein R 1 is an alkyl, aryl unit, each of which may be optionally substituted; i l.

L is a ligand and is an organic molecule that contains a number of nitrogen atoms that e ©. My | -ri by means of all or some of said nitrogen atoms to the manganese centers; Z denotes the charge of the complex and is an integer that can have a positive or negative value: Y is a monovalent or multivalent counter ion, which provides charge neutrality, which depends on the z charge of the complex; and q is z / Y.

# Preferred of these manganese compounds are those in which said coordinating or bridge-forming group X is either CH3COO ", O2", and mixtures thereof, preferably when said manganese atom is in the oxidation state (IV) and X is O2. "The ligands that are preferred are those containing at least three carbon atoms. nitrogen and which are coordinated by means of three nitrogen atoms to one of the manganese centers and are preferably of macrocyclic nature. Preferred ligands have the formula: - [NR3- (CRlfFPjqWß-, in which t is an integer having the value 2 or 3; s is an integer having the value 3 or 4; q is an integer having the value 0 or 1, R1 and R2 are each independently selected from hydrogen, alkyl, aryl, each of which may be optionally substituted, R3 is independently selected 25 of hydrogen, alkyl, aryl, each of which may be optionally substituted.

Preferred non-standard examples of FTs are 1, 4,7-trimefyl-1,4,7-tria2-acyllononane and 1, 2,4,7-tetramethylene, 4,7-triazacyclononane (Me -TACN).

The selection of the counterion Y to establish neutrality of 5 load is not critical to the activity of the complex. Non-limiting examples of said counterions are chloride, sulfate, nitrate, methylisulfate, ions of surfactants, such as long chain alkyl sulphates, alkylsulfonates; F alkylbenzenesulfonates, tosylate, trifluoromethylsulfonate, perctorate, BPh4 \ PF6 ', and mixtures thereof.

Examples of manganese compounds of this type include:) [(Me3-TACN) Mnlv (m-O) 3Mnlv (Me3-TACN)] 2+ (PF6") 2; ii) [(Me4-TACN) Mnlv (m-0) 3Mnlv (Me4-TACN)] 2+ (PF6") 2; ¡) [(Me3-TACN) iyinll, (m-0) (m-OAc) 2MnIII (Me3-TACN)] 2+ (PF6") 2; V) [(Me4.TACN) Mnlll (m-0) (m-OAc) 2Mnl "(Me4-TACN)] 2+ (PF6") 2; 15 The additional manganese complex catalysts are the mononuclear complexes that have the formula: [Lmnlv (OR) 3] And in which the manganese, Mn, is in the oxidation state +4; R is a ^ f ^ radical of C C2o selected from the group consisting of alkyl, cycloalkyl, Aryl, benzyl, and combinations of radicals thereof; at least two radicals R can also be connected to each other as to form a unit of formation of bridge between two oxygens that coordinate with manganese; L is a ligand selected from a C3-C60 radical having the I * minus 3 nifréQeno atoms coordinated with the manganese; and Y is to go »oxidatively stable counter-ion of the load of the complex. Non-limiting examples of preferred complexes are those in which L is 1,4,7-trimethyl-1,4,7-triazacyclononane and 2-methyl-1,4,7-trimetho-1,4,7-tzazacyclononane, and R is Ci alkyl. Additional examples of manganese complex catalysts that are capable of bleaching in the absence of a source of ^ BP hydrogen peroxide or other peroxygen bleaching agent include those having the formula: 10 [LMnXp] zYq * in which manganese can be in any of the states of oxidation II, III or IV; each X independently represents a species 15 coordinator with the exception of RO ", such as CI", Br ", I", F ", NCS", N3 \ l3", NH3, RCOO ", RS03", [NR3 (CR1 (R2) t] s- i RSo4-, wherein R is alkyl or aryl wherein each may be optionally substituted, 20 OH ", 022", H02" , H20, SH, CN ", OCN", S42 ', and mixtures thereof, p is an integer from 1 to 3, z denotes the charge of the complex and is an integer that can be positive, zero, or negative; is a contyraion the selection of which depends on the z charge of the complex, q = z / Y, and L is a ligand that has the formula: 25 where t is 2; s is 3; R2 and R3 is selected from a hydrogen-free, C1-C6 alkyl, aryl,? -AT% alkyl or from which it may be optionally substituted. A particularly useful metal bleach catalyst is "Bicyclamate" (5J2-dimethyl-1, 5,8,12-tetraaza-bicyclo [6.6.2] hexadecane) is prepared according to J. Amer. Chem. Soc, (1990), 112, 8604. Bleach catalysts can be co-processed with auxiliary materials such as to reduce the color impact if desired for aesthetics of the product, or they can be included in particles containing enzyme as illustrated below, or the compositions can be elaborated so that 15 contain "points" of catalyst.

Organic polymeric compound Organic polymeric compounds can be added ^? »As preferred components of the compositions according to the invention. By "organic polymeric compound" is meant essentially any organic polymeric compound that is commonly found in detergent compositions having dispersing, anti-redeposition, dirt release or other detergent properties. 9 The organic polymeric compound - typically incorporates in detergent compositions of the inve / lw at a level of 0.1% to 30%, preferably from 0.5% to 15%, more preferably from 1% to 10% by weight of the compositions. Examples of organic polymeric compounds include homo- or copolymeric, water-soluble polycarboxylic acids, modified polycarboxylates or their salts in which polycarboxylic acid is used. • comprises at least two carboxyl radicals separated from one another by no more than two carbon atoms. The polymers of this last type are 10 described in GB-A-1, 596,756. Examples of such salts are polyacrylates of molecular weight 2,000-10,000 and their copolymers with any other monomer units including modified acrylic, fumaric, maleic, ataconic, aconitic, mesaconic, citraconic, and methylenemalonic acid or its salts, maleic anhydride, acrylamide, alkylene. , vinyl methyl ether, styrene and 15 any mixtures thereof. Copolymers of acrylic acid and maleic anhydride having a molecular weight of 5,000 to 100,000, more preferably 20,000 to 100,000 are preferred. Polymers that contain acrylic acid available F commercially preferred having a molecular weight below 15,000 20 include those sold under the trademark Sokalan PA30, PA20, PA15, PA10 and Sokalan CP10 by BASF GmbH, and those sold under the trademark Acusol 45N, 480N, 460N by Rhom and Hass.

Preferred acrylic acid-containing copolymers include those which contain as a ipionomer units: a) from 90% to 10%, preferably from 80% to 20% by weight of acrylic acid or its salts and b) from 10% to 90%, preferably from 20% to 80% by weight of a substituted acrylic monomer or its salts having the general formula - [CR2-CR? (CO-0-R3)} - in which at least one of the substituents R1 f R2 or R3, preferably R1 or R ^ is an alkyl or hydroxyaikyl group of 1 to 4 carbons, R1 or R2 can be a hydrogen and R3 can be a hydrogen or metal salt alkaline. More preferred is a substituted acrylic monomer in which R1 is methyl, R2 is hydrogen (ie a methacrylic acid monomer). The most preferred copolymer of this type has a molecular weight of 3500 and contains 60% to 80% by weight of acrylic acid and 40% to 20% by weight of methacrylic acid. The polyamine and modified polyamine compounds are useful herein including those aspartic acid derivatives such as those described in EP-A-305282, EP-A-305283 and EP-A-351269. Other optional polymers may be polyvinyl alcohols and modified and unmodified acetates, modified cellulosics and cellulosics, polyoxyethylenes, polyoxypropylenes, and copolymers thereof, modified and unmodified, esters of ethylene or propylene glycol terephthalate or mixtures thereof with polyoxyalkylene units. Suitable examples are described in the patents of E.U.A. Nos. 5,591,703, 5,597,789 and 4,490,271. 7? ^% Dirt Lifting Agents Suitable poiimeric soil release agents include those soil release agents having: (a) one or more nonionic hydrophilic components consisting essentially of (i) 5 polyoxyethylene segments with a degree of polymerization of at least 2, or (ii) oxypropylene or polyoxypropylene segments with a degree of polymerization of 2 to 10, wherein said hydrophilic segment does not encompass If there is no oxypropylene unit unless it is adhered to adjacent portions at each end by ether linkages, or (ii) a mixture of oxyalkylene units comprising oxyethylene of 1 to 30 oxypropylene units, said hydrophilic segments preferably comprise at least 25% of oxyethylene units and more preferably, especially F for said components having from 20 to 30 oxypropylene units, at least 50% oxyethylene units; or (b) one or more hydrophobic components 15 comprising (i) oxyalkylene terephthalate segments of C3, in which, if said hydrophobic components also comprise oxyethylene terephthalate, the ratio of oxyethylene terephthalate: oxyalkylene terephthalate units of C3 is 2: 1 or lower, (ii) C4-C6 alkylene segments or C-C6 oxyalkylene, or mixtures thereof, (iii) poly (vinyl ester) segments, preferably 20 polyvinylacetate, which has a degree of polymerization of at least 2, or (iv) - C4 alkyl ether substituents or C4 hydroxyalkyl ether, or mixtures thereof, in which said substituents are present in the form of C C4 alkyl ether cellulose derivatives or eth »'. $. dro) ÜAl ^ M? M S * - C4, or mixtures thereof, or a (a) and (b). Typically, the polyoxyethylene segments of (a) (i) will have a degree of polymerization of 200, although higher levels may be used, preferably from 3 to 150, more preferably from 6 to 100. The hydrophobic oxyalkylene segments of C4- Suitable C6s include, but are not limited to, polymeric end release agents. # blocked, such as M? 3S (CH2) nOCH2CH20-, where M is sodium and n is an integer of 4-6, as described in the patent of E.U.A. No. 4,721, 580, 10 issued on January 26, 1988 to Gosselink. The polymeric soil release agents useful herein also include cellulose derivatives such as cellulosic polymers * ^^ J hydroxy ether, copolymer blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene terephthalate oxide, and the like. Said agents are commercially available and include cellulose hydroxyethers such as METHOCEL (Dow). The cellulosic soil release agents for use herein also include those that are selected from the group consisting of C 1 -C 4 alkyl and hydroxy alkyl cellulose f of C 4; see the patent of E.U.A. No. 4,000,093, issued December 28 to 20 Nicol, et al. Dirt release agents characterized by hydrophobic poly (vinyl ester) segments include grafted copolymers of poly (vinyl ester), for example CrCß vinyl esters, preferably poll (vmílacetato) grafted on base fibers] áe ó o of polyalkalkylene, as polietüeíio oxide base constructions. See the European patent application, published on April 22, 1987 by Kud, et al. Another suitable dirt release agent is a 5 copolymer having random blocks of ethyleneneterephthalate and polyethyleneneterephthalate oxide (PEO). The molecular weight of this release agent - Polymeric dirt is on the scale of 25,000 to 55,000. See the patent for E.U.A. No. 3,959,230 to Hays, issued May 25, 1976, and the patent of E.U.A. No. 3,893,929 to Basadur, issued July 8, 1975. Another suitable polymeric soil release agent is a polyester with repeating units of ethylene terephthalate units containing 10-15% by weight of ethylene terephthalate units together with 90-80. % in 9 weight of polyoxyethylene terephthalate units, derived from a polyoxyethylene glycol of average molecular weight of 300-5,000. Another suitable polymeric soil release agent is a sulphonated product of a substantially linear ester oligomer comprising an oligomeric ester base structure of terephthaloyl and oxyalkylenoxy repeating units and terminal derivatives adhered ijflp covalently to the base strength. Those agents of liberation of 20 dirt are fully described in the US patent. No. 4,968,451, issued November 6, 1990 to J.J. Scheibel and E.P. Gosselink. Other suitable polymeric soil release agents include the terephthalate polyesters of the U.S.A. No. 4,711, 730, issued on 8 December 1987 to Gossellnk, et al., the blocked end ammonium olrgomeoping esters of the U.S. patent. Hof "4 ^ 21 f580, from January 26, 1988 to Gosselin, and the block oligomeric block copolymers of US Pat. No. 4,702,857, issued October 27, 1987 to 5 Gosselink. Polymers also include the soil release agents of U.S. Patent No. 4,877,896, issued October 31, 1989 to Maldonado et al, which F describes anionic terephthalate esters, especially sulfoaroyl, blocked end esters. Another soil release agent is an oligomer with repeating units of terephthaloyl units, sulfoisotereftafoyl units, oxyethyloxy units and oxy-1,2-propylene. The repeating units form the base structure of the oligomer and preferably are terminated with blocked ends of the modified isethionate. A release agent Particularly preferred soiling of this type comprises a sutphosisophthaloyl unit, 5 terephthaloyl units, oxyethylenenoxy and oxy-1, 2-propyleneoxy units in a ratio of 1.7 to 1.8 and two units of sodium sodium 2- (2-hydroxyethoxy) -ethanesulfonate. locked. 20 Heavy Metal Ion Sequester The compositions of the invention may contain as an optional component a heavy metal ion sequestrant. By heavy metal ion hijacker means in this components * which act to sequester (chelate) heavy metal ions. These "components may also have calcium and magnesium ionizing capabilities, but preferably show selectivity for binding heavy metal ions such as iron, manganese and copper. Heavy metal on-line hijackers are generally present at a level of 0.005% to 20%, preferably from 0.1% to 10%, most preferably 0.25% to 7.5% and more preferably 0.5% to 5% by weight of the compositions The heavy metal ablators, which are acidic in nature, having for example functionalities of phosphonic acid and carboxylic acid, can be present either in their acid form or as a complex / salt with a suitable counter cation as a Alkali metal or alkali metal, ammonium ion, or substituted ammonium, or any mixtures thereof. Preferably the salts / complexes are water-soluble. The molar ratio of said counter cation to the heavy metal ion sequester is preferably at least 1: 1. Heavy metal ion sequestrants suitable for use herein include organic phosphonates, such as the aminoatquilenpoll (alkylene phosphonates), alkali metal ethan-1-hydroxy diphosphonates, and nitrilotrimethylene phosphonates. Preferred among the above species are diethylenetriaminpenta (methylene phosphonate), eti? Diaiamintri (methyl phosphonate), hexamethylenediamintetra (methylene phosphonate) and hydroxyethylene 1,1 diphosphonate. v * ¿v is Another sin metal ion sequestrant suitable for use herein includes nitriloiriae ^ cp acid. and polylaminocarboxylic acids such as ethylenediaminetetraacetic acid, ethylenetriamine pentacetic acid, ethylenediamine disuccinic acid, ethylenediamine diglutaric acid, 2-hydroxypropylenediamine disuccinic acid or any salt thereof. Especially preferred is ethylenediamine-N, N'-disuccinic acid (EDDS) or the alkali metal, ferrous alkali metal, ammonium or substituted ammonium salts thereof, or mixtures thereof. The preferred EDDS compounds are the free acid forms and the sodium or magnesium salt or complex thereof. Organodiphosphonic acid, which does not contain nitrogen as part of its chemical structure. This definition therefore excludes the aminophosphonate organ, which however can be included in the compositions of the invention as heavy metal ion sequestering components. The organodiphosphonic acid is preferably a C1-C4 organodiphosphonic acid, more preferably a C2 organodiphosphonic acid, such as ethylene diphosphonic acid, or more preferably ethane hydroxy-1, 1-diphosphonic acid (HEDP) and may be present in partially or completely ionized form, particularly as a salt or complex. < - - Tidesoluble sulfate sulfate The compositions confer ophetically a water-soluble sulfate salt. When present, the water-soluble sulfate salt is at a level of from 0.1% to 40%, more preferably from 1% to 30%, more preferably from 5% to 25%, by weight of the compositions. The water-soluble sulfate salt can be essentially any sulfate salt with any countercation. Preferred salts are selected of alkali metal or alkaline earth metal sulfates, particularly sodium sulfate. 10 Alkali metal silicate * An alkali metal silicate is a preferred component of the * compositions of the present invention. A preferred alkali metal silicate is sodium silicate having a Si? 2: Na2? from 1.8 to 3.0, 15 preferably 2.4 to 2.4, more preferably 2.0. The sodium silicate is preferably present at a level of less than 20%, preferably from 1% to 15%, more preferably from 3% to 12% by weight of SiO2. The alkali metal silicate can be in the form of anhydrous salt or a hydrated salt. The alkali metal silicate can also be present as 20 a component of an alkalinity system. The alkalinity system also preferably contains sodium metasilicate, present at a level of at least 0.4% SiO2 by weight. Sodium metasilicate has a nominal Si? 2: Na20 ratio of 1.0. The relationship by weight of sodium silicate to sodium metasilicate, measured as SiO, is preferably from 50: 1 to 5: 4, more preferably from 15: 1 to 2: 1, more preferably from 10: 1 to 5: 2. 5 Colorant The term "colorant", as used herein, means any substance that absorbs specific wavelengths of light from the visible light spectrum. Said colorants when added to a detergent composition have the effect of changing the visible color and so Both the appearance of the detergent composition. The dyes can be, for example, inks or pigments. Preferably the dyes are stable in the * composition in which they have to be incorporated. In this way in a high pH composition the dye is preferably alkaline stable and in a low pH composition the dye is preferably stable acid.

The first and / or second and / or subsequent composition may contain a colorant, a mixture of colorants, particles with colorant or mixture of particles with colorant so that the various phases have different visual appearances. Preferably one of any of the first or second phases comprises a colorant. Where the first and Secondly and / or the subsequent phase comprises a dye, it is preferred that the dyes have a different visual appearance.

This system is Erftima Preferred enzyme containing compositions herein may comprise from 0.001% to 10%, preferably from 0.005% to 8%, more preferably from 0.01% to 6%, by weight of a 5-enzyme system. The enzyme stabilizer system can be any system stabilizer that is compatible with the detersive enzyme. Said stabilizing systems may comprise calcium ion, boric acid, propylene glycol, • short chain carboxylic acid, boronic acid, chlorine bleach scrubbers and mixtures thereof. Said stabilizer systems may also comprise reversible enzyme inhibitors, such as reversible protease inhibitors.

#: Foam suppression system The detergent tablets of the present invention, when 15 formulations for use in compositions for machine washing, preferably comprise a foam suppression system present at a level from 0.01% to 15%, preferably from 0.05% to 10%, most preferably from 0.1% to 5% by weight of the composition. The suds suppression systems suitable for use In the present invention can essentially comprise any known antifoam compound, including, for example, antifoam compounds of silicone and 2-alkyl alkanol antifoaming compounds. The systems of suppression of pronated foams and antifoaming compounds are described in solid PCT No. WO93 / 08876 and EP-A-705324.

Polymeric dye transfer inhibiting agents The compositions herein may also comprise from 0.01% to 10%, preferably from 0.05% to 0.5% by weight of polymeric dye transfer inhibiting agents. The polymeric dye transfer inhibiting agents are preferably selected from polymers of N-oxide 10 polyamine, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinylpyrrolidone polymers or combinations thereof.

Optical brightener The compositions suitable for use in methods of 15 laundry laundry as described herein, optionally also contain from 0.005% to 5% by weight of certain types of hydrophilic optical brighteners. The hydrophilic optical brighteners useful herein include those having the structural formula: ? * - "wherein Rj is selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl; R2 is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, morphino, chloro and amino, and M is a salt-forming cation such as sodium or potassium When in the above formula R- | is anilino, R2 is N-2-b? s-hydroxyethyl and M is a cation like sodium, the brightener is acid. , 4'-b? S [(4-an? Lino-6- (N-2-bis-hydroxy-ethyl) -s-triazin-2-yl) amino] -2,2'-esfilbendisulfonic acid and disodium salt. of particular brightener is sold commercially under the trade name Tinopal-UNPA-GX by Ciba-Geigy Corporation.The Tinopal-UNPA-GX is the preferred hydrophilic optical brightener useful in the detergent compositions herein.When in the above formula, R- is anilino, R2 is N-2-hydroxyethyl-N-2-methylamino and M is a cation such as sodium, the brightener is the disodium salt of 4,4'-bis [(4-anilino-6- (N -2-hydroxy-1-N-methylamino) -s- triazine-2-yl) amino] -2,2'-sp ilbenedisulfonic. This particular brightener species is marketed under the trade name Tinopal 5BM-GX by Ciba-Geigy Corporation. When in the previous formula, R- | is anilme, R2 is morphillin and M is a cation such as sodium, the brightener is the sodium salt of 4,4-bis [(4-anilino-6-morphino-s-triazine-2-yl) amino] 2 acid. , 2, -stilbendisulfonic. This particular kind of brightener is sold commercially under the trade name Tinopal AMS-GX by Ciba-Geigy Corporation.

* Other preferred optical brighteners are those known as Brightener 49 available from Ciba-Geigy.

Other Optional Ingredients Other optional ingredients suitable for inclusion in the compositions of the invention include perfumes and filler salts, with sodium sulfate being a preferred filler salt. pH of the compositions The compositions of the present invention are preferably not formulated to have unduly high pH, «Cr * preference has a pH measured as a 1% solution in distilled water of from 7.0 to 12.5, more preferably from 7.5 to 11.8, more preferably from 8.0 to 11.5. 15 EXAMPLES The present example is illustrative of the additive bags for laundry as described herein and does not mean that it is limiting. twenty Compartment 1 Powder (15 g) Percarbonate 15% TAED 5% Clay softener 67% Polyethylene oxide average molecular weight FWp 500 Of 0 2% Citric acid 5% Bicarbonate 5% Lower 1% Total 100% Compartment 2 Liquid (15 g) Isoparaffin 55% CLASS * 5% PAP 25% NOBS 15% Total 100% '' CLASS = structure linear alkyl benzene sulphonate (LAS).

Claims

1 - . 1 - A bag of laundry additive characterized in that it comprises one or more liquid compositions, wherein the bag comprises two or more compartments made of film material or sheet substantially soluble in water, 2.- The bag of laundry additive in accordance with Claim 1, further characterized in that the bag comprises three or more compartments. 3. The bag of laundry additive according to any of the preceding claims, further characterized in that the water-soluble film or sheet material is hydroxypropylmethylcellulose. 4. The bag of laundry additive according to any of the preceding claims, further characterized in that it comprises at least two different liquid compositions, the first and second compositions differ in the presence of at least one ingredient. 5. The bag of laundry additive according to claim 2, further characterized in that it comprises at least three compositions, the first, second and third compositions differ by the presence of at least one ingredient. 6. - The bag of laundry additive according to claim 2 or 5, further characterized in that the first, second and third compositions differ from each other in such a way that at least one ingredient is present in a composition that is not present in E any of the two remaining compositions. 7 .- The bag of laundry additive according to any of the preceding claims, further characterized in that the first composition comprises an ingredient selected from a softening ingredient, enzyme, organic polymeric compound, dirt release agent, transfer inhibitor of dye, brightener and mixtures thereof. 8.- The laundry additive bag in accordance with any of the preceding claims, further characterized in that the second composition comprises a bleaching ingredient which is a Preformed monoperoxycarboxylic acid, preferably phthaloylamidoperoxyhexanoic acid. 9. A process for treating fabrics with a bag of laundry additive as claimed in any of the claims precedents in conjunction with a conventional laundry detergent in the presence of water. 10. The use of a bag as claimed in any of claims 1 to 8 as a laundry additive. 11. - The use of a bag as claimed in any of claims 1 to 8 for cleaning and / or softening fabrics. 1

2 - The use of a sack as claimed in any of claims 1 to 8 to clean and / or provide an easy ironing benefit F F